WO2016111576A1 - Method for manufacturing device comprising inorganic/organic hybrid perovskite compound film and device comprising inorganic/organic hybrid perovskite compound film - Google Patents

Abstract

A method for manufacturing a device comprising an inorganic/organic hybrid perovskite compound film, according to the present invention, comprises the steps of: a) laminating a first structure and a second structure to allow the first surface layer and the second surface layer to be in contact with each other, the first structure comprising a first surface layer containing at least one material of i) to v) below, the second structure comprising a second surface layer containing, independently from the first surface layer, at least one material of i) to v) below; and b) applying heat and physical force to the laminate in which the first structure and the second structure are laminated: i) an inorganic/organic hybrid perovskite compound, ii) an organic halide, iii) a metal halide, iv) an inorganic/organic perovskite compound precursor, and v) a metal halide precursor.

Description

 Specification

 NAME OF THE INVENTION: A method for producing a device comprising an organic / organic hybrid perovskite compound film and an element comprising an organic / organic hybrid perovskite compound film

 Technical Field

 [1] The present invention provides a method for producing a non-organic hybrid perovskite compound film and

 The present invention relates to a method for manufacturing a device including an organic / organic hybrid perovskite compound film, and to produce a high quality inorganic / organic hybrid perovskite compound film in a simple and low temperature process, which is suitable for mass production. The present invention relates to a large-area non-organic hybrid perovskite compound film and a method for manufacturing a device including the same.

 Background

 [2] Organic / organic hybrid perovskite compounds, also referred to as organometal halide perovskite compounds, consist of organic cations (A), metal cations (M), and halogen anions (X). ，

Chemically representative of AMX ₃ with a perovskite structure. Specifically, the inorganic / organic hybrid perovskite compound represented by the chemical formula of AMX ₃ is an MX ₆ octahedron microcorner-sharing ( In the corner-shearing three-dimensional network, A organic cations are located in the middle.

 Perovskite compounds are very commercially available because they have very low material prices, low temperature processes and low cost solution processes, and active research is being conducted in various fields such as light emitting devices, memory devices, sensors, and photovoltaic devices.

 [3] As described above, the inorganic / organic hybrid perovskite compound is

 Self-assembling and crystallizing features offer the advantage of low temperature solution processing, but difficult to control fast crystallization and self-assembly, making it difficult to produce thin films with true dense and flat surfaces.

 [4] The present applicant has noticed a remarkable high level in Korean Patent Application Publication No. 2014-0035284.

 A new structure of a solar cell having a power generation efficiency has been proposed, and a method of producing an organic / organic hybrid perovskite compound film having a flat surface by using a solution coating method has also been proposed.

 [5] However, in order to commercialize inorganic / organic hybrid perovskite compound-based devices, high-quality dense membranes can be manufactured, but they can be processed in large areas, have high reproducibility, minimize the use of volatile organic solvents, and are simpler and more controlled. It is a reality that simple and simple manufacturing process technology development should be undertaken.

 [6] The present applicant has a high density and high quality of coarse grains.

It is possible to manufacture perovskite compound film, suitable for practical commercialization, The company has developed the technology to manufacture high quality inorganic / organic hybrid perovskite compound films in a low cost, fast and simple process, which led to the present invention. Detailed description of the invention

 Technical task

 [7] The purpose of the present invention is to produce high quality organic / organic hybrid perovskite compound film, low cost, fast and simple process organic / organic hybrid

 The present invention provides a method for producing an organic / organic hybrid perovskite compound film which can produce a perovskite compound film, has excellent reproducibility and process stability, and can be processed in a large area.

 [8] Another object of the present invention is the organic / organic hybrid perovskite compound film.

 It is to provide a method for manufacturing a device provided.

 [9] Another object of the present invention is to provide a binding method for binding two structures via an organic / organic hybrid perovskite compound film.

 [10] Another object of the present invention is to provide a method for manufacturing a solar cell in which an inorganic / organic hydride perovskite compound is provided with a light absorber.

 [11] Another object of the present invention is to provide a solar cell manufacturing laminate which manufactures a solar cell in which an inorganic / organic hybrid perovskite compound is provided with a light absorber.

 [12] Another object of the present invention is to provide a solar cell in which an inorganic / organic hydride perovskite compound is provided as a light absorber.

 Task solution

 [13] A method for fabricating a device having an inorganic / organic hybrid perovskite compound film according to the present invention includes: a) i) V) a first structure comprising a first surface worm containing at least one substance; Independent of the U surface layer; iv) laminating a second structure comprising a second surface layer containing at least a substance, the first surface layer and the second surface layer to abut, and b) the lower 11 structure and the second structure. Applying heat and physical forces to the loaded laminate.

 [14] i) organic / organic hybrid perovskite compounds

 [15] ii) organic halides

 [16] iii) metal halides

 [17] iv) organic hybrid perovskite compounds precursors

[18] V) metal halide precursors

[19] In one embodiment according to the manufacturing method of the present invention, the first surface layer and the _second surface layer have a single inorganic / organic hybrid by the application of the thermal and physical forces of step b).

 It can be converted into a perovskite compound film.

[20] In one embodiment according to the manufacturing method of the present invention, the first surface layer contained

The pair of materials contained in the material-second surface layer can be one of the following: [21] 1) organic / organic hybrid perovskite compounds-organic / organic hybrid perovskite compounds

[22] 2) organic / organic hybrid perovskite compounds -organic / organic hybrid

 Perovskite Compound Precursor

[23] 3) organic / organic hybrid perovskite compound precursors -organic / organic hybrid perovskite compound precursors

[24] 4) metal halide precursors -organic halides

[25] 5) metal halides, organic halides

 [26] In one embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer are independently of each other, i to v) at least one of the coating films in which particles of at least one substance is applied, i to v). It can be made of a porous membrane of one substance, i ~ v) of at least one dense membrane of a substance or a combination thereof.

 [27] In one embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer independently of each other i-v) at least a single layer, i-v) at least two substances. It may be a single layer containing, or i-v) at least two layers each of which is a laminated layer laminated.

 In an embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer may be patterned in a shape corresponding to each other.

In an embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer may be formed independently by printing, coating or deposition.

[3] In one embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer are independently of each other, i ~ v) a solution in which at least one substance is dissolved or at least one of the above i ~ v). It can be formed using dispersed slurry or ink.

[31] In one embodiment according to the manufacturing method of the present invention, the first surface layer and the second surface layer

 At least one surface layer contains i) an inorganic / organic hybrid perovskite compound, i) a surface layer containing an inorganic / organic hybrid perovskite compound, and ii) a layer of inorganic / organic hybrid perovskite compound precursor. Alternatively, it can be prepared by thermal treatment of a laminate comprising iii) a metal halide precursor and iv) an organic halide.

[32] In one embodiment according to the method of the present invention, i) no organic / organic hybrid

 The perovskite compound may satisfy the following formula (1), (2) or (3).

 [33] (Formula 1)

[34] AMX ₃

 [35] In Formula 1, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions are silver and amidinium ions, Μ is a divalent metal ion and X is a halogen ion.

 [36] (Formula 2)

[37] A (M _{1 -a} N _a ) X ₃ In Formula 2, A is a monovalent cation, A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium-based ion, M is a divalent metal ion, and N Is a doped metal ion in which at least one of a monovalent metal ion and a trivalent metal ion is selected from silver, a is a real number with 0 <a ≦ 0.1, and X is a halogen ion.

 [39] (Formula 3)

[40] A (N ' _1-h N¾X ₃

 [41] In Formula 3, A is a monovalent cation, A is an organic ammonium silver,

Amidinium group silver or organic ammonium ion and amidinium-based ion, N ¹ is a monovalent metal silver, Ν ² is a trivalent metal ion, b is

 It is a real number with 0.4 <= b <= 0.6, and X is a halogen ion.

[42] In one embodiment according to the manufacturing method of the present invention, Formula 1, Formula 2 or Formula

At 3, A is A χ ₎ A, A ^a is an amidinium ion, A ^b is an organic ammonium ion,

X can be a real number from 0.3 to 0.05.

[43] In one embodiment according to the manufacturing method of the present invention, Formula 1, Formula 2 or Formula

In 3, X may contain two different halogen ions.

[44] In one embodiment according to the manufacturing method of the present invention, Formula 1, Formula 2 or Formula

At 3, X is X ^a _(1-y) X ^b _y , which is Χ iodide, X ^b is silver, and y is 0.05 to

May be a mistake of 0.3.

In one embodiment according to the manufacturing method of the present invention, iv) the organic halide may satisfy the following formula (4).

[46] (Formula ⁴ )

[47] AX

 [48] In Formula 4, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, and X is a halogen ion.

 [49] In one embodiment according to the manufacturing method of the present invention, V) a metal halide is

 Formula 5, Formula 6 or Formula 7 may be satisfied.

 [50] (Formula 5)

[51] MX ₂

 In Chemical Formula 5, M is a divalent metal ion and Χ is a halogen ion.

[53] (Formula 6)

_{[54] (M ,. a N} a) X 2

 In Formula 6, M is a divalent metal ion, N is a doped metal ion selected from at least one of a monovalent metal ion and a trivalent metal ion, a is a real number having 0 <a≤0.1, and X is halogen It is an ion.

[56] (Formula ⁷ )

[57] (N ⁱ _1-b N ² _b ) X ₂ In formula 7, N ¹ is a monovalent metal ion, N ² is a trivalent metal ion, b is

It is a real number with 0.4 <= b <= 0.6, and X is a halogen ion.

In one embodiment according to the manufacturing method of the present invention, the physical force may include a compressive force.

 In one embodiment according to the method of the present invention, the application of the heat and physical force of step b) may be hot pressing.

In one embodiment according to the manufacturing method of the present invention, hot pressing may be performed at a temperature of 50 to 250 ^° C. and a pressure of 1 to lOOMPa.

In an embodiment according to the manufacturing method of the present invention, the hot pressing may be performed in a vacuum and atmospheric pressure atmosphere.

[63] In one embodiment according to the method of the present invention, the first structure comprises a U-substrate and

 The first electrode may further include a first electrode positioned on the first substrate.

[64] In one embodiment according to the method of the present invention, the second structure comprises a second substrate and

 It may further include a second electrode positioned on the second substrate.

[65] In one embodiment according to the manufacturing method of the present invention, the first structure is on the first electrode

 It may further include an electron carrier located.

In one embodiment according to the manufacturing method of the present invention, the electron transporter may be organic or inorganic.

 In an embodiment according to the manufacturing method of the present invention, the electron transporter may have a dense membrane or a porous membrane structure.

[68] In one embodiment according to the method of the present invention, the second structure is formed on the second electrode.

 It may further include a hole carrier located.

In one embodiment according to the manufacturing method of the present invention, the hole transporter may be organic or inorganic.

 In an embodiment according to the manufacturing method of the present invention, the hole transporter may have a dense membrane or a porous membrane structure.

In one embodiment according to the manufacturing method of the present invention, the first substrate and the second substrate may be a flexible substrate.

 In an embodiment according to the manufacturing method of the present invention, at least one of the first and second substrates may be a transparent substrate, and at least one of the first and second electrodes may be a transparent electrode.

 In an embodiment according to the manufacturing method of the present invention, the first substrate and the second substrate are each transparent substrate, and the first electrode and the second electrode may each be transparent electrode.

 In an embodiment according to the manufacturing method of the present invention, the first structure is a transparent substrate.

The first substrate may further include a transparent electrode positioned on the first substrate, a first electrode and a charge carrier, and the second structure is located on the second electrode, the second electrode, and absorbs more than 800 nm of light to absorb electrons and holes. The inorganic light absorbing layer and the bonding layer may be further included. In an embodiment according to the manufacturing method of the present invention, the inorganic light absorbing layer may be a Group 4 semiconductor, a Group 3-5 semiconductor, a Group 2-6 semiconductor, a Group 4-6 semiconductor, or a metal chalcogenide semiconductor.

 In one embodiment according to the manufacturing method of the present invention, the device may be a light emitting device, a memory device, a light emitting device or a thermoelectric device.

 The present invention includes devices manufactured by the above-described manufacturing method.

 [78] The present invention relates to a light emitting device manufactured by the above-mentioned manufacturing method, a memory device manufactured by the above-mentioned manufacturing method, a photovoltaic device manufactured by the above-mentioned manufacturing method (solar cell), and a thermoelectric manufactured by the above-mentioned manufacturing method. It includes an element.

 The present invention includes a binding method of binding at least two structures.

 [80] The binding method according to the present invention includes a) containing i) at least one of the following substances:

 A first structure comprising a first surface layer and a second surface layer containing at least one of the materials i—V) independent of the first surface layer are laminated so that the first structure and the lower surface layer are in contact with each other. And b) applying the thermal and physical forces to the laminate on which the first structure and the second structure are laminated to bind the first structure and the second structure.

 [81] i) Radical / organic hybrid perovskite compounds

 [82] ii) organic halides

 [83] iii) metal halides

 [84] iv) organic hybrid perovskite compounds precursors

[85] V) metal halide precursors

 The present invention includes a method for producing an inorganic / organic hybrid perovskite compound film.

 According to one embodiment of the present invention, a method for preparing an organic / organic hybrid perovskite compound film includes i-v) a first structure comprising a first surface layer containing at least one substance, and a first surface layer. Layering a second structure comprising at least one material containing at least one material, and laminating the first surface layer and the second surface layer so as to be in contact with each other; and b) the first structure and the second structure. Applying heat and physical forces to the stacked laminates.

 [88] i) organic / organic hybrid perovskite compounds

 [89] ii) organic halides

 [90] iii) metal halides

 [91] iv) organic hybrid organic perovskite precursors

[92] V) metal halide precursors

 [93] The present invention includes a solar cell manufacturing laminate which combines with each other to form a solar cell. Specifically, the present invention is a solar cell manufacturing laminate which is formed by binding together as a whole by heat and physical forces. It includes.

[94] A solar cell manufacturing laminate according to an embodiment of the present invention is formed on a first substrate or a crab substrate. A first structure comprising a first electrode positioned on the first electrode, an electron carrier located on the first electrode, and a first surface layer containing at least one of the following materials; and a second substrate positioned on the second substrate and the second substrate. Independently of the electrode and the bran U surface layer i to v) a second structure comprising a second surface layer containing at least a substance, wherein the first surface layer of the first structure and the second surface layer of the second structure It is a laminate laminated to abut.

 [95] i) organic / organic hybrid perovskite compounds

 [96] ii) organic halides

 [97] Hi) metal halides

 [98] iv) organic hybrid organic perovskite compounds precursors

[99] V) metal halide precursors

 In the solar cell manufacturing laminate according to one embodiment of the present invention, the second structure may further include a hole transporter located on the second electrode.

The solar cell manufacturing laminate according to an embodiment of the present invention may be a tandem structure solar cell manufacturing laminate.

 According to one embodiment of the present invention, a tandem structured solar cell manufacturing laminate includes a first substrate, a transparent substrate, a transparent electrode positioned on a first substrate, an electrode based on a first electrode, a charge carrier positioned on the first electrode, and i ~ v) a first structure including a first surface layer containing at least a substance, and a second electrode, a second electrode, and an inorganic light absorbing layer and an inorganic light absorbing layer, which absorb electrons of more than 800 mn to generate electrons and holes. A second structure comprising a bonding layer located and a second surface layer containing at least one of i-v) independent of the lower surface layer, the second surface of the first surface layer and the second structure of the first structure. It is a laminated laminate laminated so that the surface layers abut one another.

 [103] i) organic / organic hybrid perovskite compounds

 Ii) organic halides

 [105] iii) metal halides

 [106] iv) organic hybrid organic perovskite compounds precursors

[107] V) metal halide precursors

 [108] In the tandem structured solar cell manufacturing laminate according to one embodiment of the present invention,

 The inorganic light absorbing layer of the second structure includes a semiconductor substrate having an emitter layer and a back surface field (BSF) layer forming a back field, and the second electrode is electrically connected to the BSF layer of the semiconductor substrate. A contact insect may be located on the layer and the structure 2 may further include a second charge carrier located on the junction layer.

 [109] In the tandem structured solar cell manufacturing laminate according to one embodiment of the present invention,

 The inorganic light absorbing layer of the second structure includes a metal chalcogenide compound, and the second structure further comprises 12 engines, a buffer layer located on the inorganic light absorbing layer, and a second charge carrier. The second substrate, the second electrode, and the inorganic Light absorbing layer, buffer layer, bonding layer, second charge carrier, and

 The second surface layer can be arranged sequentially.

[110] The present invention is a laminate for manufacturing solar cells described above (for tandem structured solar cells (Including laminates) wherein the first and second surface layers are converted into a single inorganic / organic hybrid perovskite compound layer and comprise a solar cell in which the first and second structures are bonded to each other.

 [1 11] According to the present invention, a solar cell includes a first electrode, a first charge carrier, and a free / organic hybrid, which are sequentially stacked between a first substrate and a second substrate, and the first and second substrates facing each other. And a perovskite compound layer, a second charge carrier and a second electrode.

 [1 12] In the solar cell according to an embodiment of the present invention, the first charge carrier and nearly 12

 At least one of the charge carriers is a porous charge carrier, and the inorganic / organic hybrid perovskite compound layer fills the pores of the porous charge carrier and can cover the porous charge carrier.

 [113] In the solar cell according to one embodiment of the present invention, the first charge carrier and the system 2

 All charge carriers are porous charge carriers, and inorganic / organic hybrids.

 The perovskite compound layer fills both the pores of the first charge carrier and the pores of the second charge carrier and may have a structure interposed between the first charge carrier and the second charge carrier.

 In a solar cell according to an embodiment of the present invention, the first substrate and the second substrate are each transparent substrate, and the first electrode and the second electrode may each be transparent electrodes.

 In a solar cell according to an embodiment of the present invention, the first electrode is connected to the first substrate.

 The direct contact with the second substrate may be performed, and the second electrode may be directly contacted with the second substrate.

 The present invention includes a solar cell having a four-terminal tandem structure.

 [1 17] A solar cell having a four-terminal tandem structure according to an embodiment of the present invention is a transparent electrode which is sequentially stacked between a first substrate and a second substrate, and a first substrate and a second substrate, which face each other. 1 electrode, 1st charge carrier, organic / organic hybrid

 Inorganic / organic hybrid perovskite compound based solar cells comprising a perovskite compound layer, a second charge carrier and a transparent electrode, and an inorganic light absorber based solar cell that absorbs light above 800 nm to produce electrons and holes 4 terminal tandem structure in which the inorganic / organic hybrid perovskite compound based solar cell is located on the light receiving side and the inorganic light absorber based solar cell receives the light through the inorganic / organic hybrid perovskite compound based solar cell Of solar cells.

 Effects of the Invention

 A device manufacturing method according to an embodiment of the present invention can manufacture a device that is dense, has excellent crystallinity, and is provided with a high quality, high quality, inorganic / organic hybrid perovskite compound film having a coarse grain size.

In addition, the manufacturing method of the device according to an embodiment of the present invention is fast and simple It is a process, a large-area process, and a continuous process, and has the advantage of being a commercial method for mass production of high quality devices at low cost.

 In addition, the method for manufacturing a device according to an embodiment of the present invention is that the process factors affecting the film quality of the organic / organic hybrid perovskite compound film are extremely simple, with only heat and physical force (pressure). With two easily controllable process factors, the film quality of the organic / organic hybrid perovskite compound film is controlled, resulting in device fabrication with superior reproducibility and reliability.

 In addition, according to one embodiment of the present invention, a method for manufacturing a device is performed by manufacturing a high quality, dense inorganic / organic hybrid perovskite compound film in a very low temperature and low temperature process. For example,

 Flexible substrates such as polyethylene terephthalate substrates, organic materials such as organic hole carriers, etc.) have the advantage of being free from thermal damage. With these advantages, the method for manufacturing a device according to an embodiment of the present invention is very suitable for the manufacture of flexible devices. have.

 In addition, the device manufacturing method according to an embodiment of the present invention, in order to produce a high quality, dense film-type inorganic / organic hybrid perovskite compound film, the use of a volatile organic solvent can be eliminated or minimized Therefore, there are more environmentally friendly fair advantages.

 In addition, a method for manufacturing a device according to an embodiment of the present invention, the organic / organic hybrid perovskite compound provided in the device by the first substrate of the first structure and the second substrate of the second structure. As the membrane is protected from the external environment (eg moisture), there is an advantage in that the lifetime, stability and durability of the device can be improved to a level that is acceptable without a separate encapsulation process.

 Furthermore, there is an advantage in that a transparent device including a transparent solar cell can be manufactured by a simple method of adopting the substrates and electrodes of the first and second structures as the transparent substrate and the transparent electrode.

 In addition, a method for manufacturing a device according to an embodiment of the present invention, such as a coating film in which particles of the inorganic / organic hybrid perovskite compound is simply coated.

 A high quality dense film can be produced from the surface layer, and thus can have very good commercial properties. In other words, the method for manufacturing a device according to an embodiment of the present invention is a low density film having a very rough surface, a dispersed film or a porous particle having a very rough surface. By using the membrane, there is an advantage that a high-quality dense membrane with high density and large grains can be produced.

In addition, the manufacturing method of the device according to an embodiment of the present invention,

A simple method of patterning and printing inks or slurries containing particles of hybrid perovskite compounds can realize a high quality patterned dense film, which provides a significant increase in the degree of freedom in device design. It is an extremely simple process of applying patterned printing-stacking-thermal and physical forces, and has the advantage of enabling devices with highly patterned designs. In addition, the manufacturing method of the device according to an embodiment of the present invention, the organic / organic hybrid perovskite compound by a simple change of the design of the lower components of the surface layer of the first structure or the lower 12 structure There is an advantage in that hybridization between one device and another is based on the action of the membrane.

 In detail, when manufacturing a solar cell according to an embodiment of the present invention, by using both the first electrode and the second electrode as a transparent electrode, it is possible to manufacture a semi-transparent or selective wavelength-transmissible solar cell, BIPV It can be easily used for building intergrated photovolatics or for silicon, thin-film positive cells and four-terminal tandems.

 [129] Furthermore, a group 4 semiconductor including silicon in a structure of 1 or 12 structures

 By forming a solar cell structure or a chalcogenide-based solar cell structure such as CIGS, there is an advantage that it is easy to manufacture a solar cell having a two-terminal tandem structure.

 [130] The production method of the inorganic / organic hybrid perovskite compound film according to one embodiment of the present invention is a low-cost, quick and simple process, has a large-area process, has the advantages of continuous processing, from low quality surface insects, High quality non-organic hybrid with fine, excellent crystallinity and large grain size

 There is an advantage that the perovskite compound film can be manufactured.

 In the binding method according to an embodiment of the present invention, the two structures to be bound are physically formed by a high quality inorganic / organic hybrid perovskite compound film by a simple method of applying thermal and physical forces. It has the advantage of being firmly fixed at all.

 A solar cell manufacturing laminate according to one embodiment of the present invention is a solar cell having a high quality light absorbing layer provided by a simple method of applying heat and pressure to a laminate in which a first structure and a second structure are laminated. There is an advantage to manufacturing.

 [133]

 Brief description of the drawings

1 is a scanning electron microscope photograph of the cross section of the surface layer in Example 1, [135] Figure 2 is a scanning electron microscope photograph of the cross section of the perovskite compound film converted from the surface layer in Example 1 And

FIG. 3 is a scanning electron micrograph of the surface layer prepared in Example 3, and FIG. 4 is a scanning electron micrograph of the cross section of the perovskite compound film converted from the surface layer in Example 3. Is,

FIG. 5 is a scanning electron micrograph of the surface layer prepared in Example 4, and FIG. 6 is a scanning electron micrograph of the cross section of the perovskite compound film converted from the surface layer in Example 4. Is,

7 is a glass-perovskite compound film prepared in Example 6-glass and PET-Perovskite Compound Membrane-A diagram showing the measurement of the permeability of PET samples.

FIG. 8 shows the X-ray diffraction pattern of the perovskite compound precursor prepared in Example 7. Simultaneously, PbI ₂ (DMSO) ₂ , MAI (CH ₃ NH ₃ I), and Pbl ₂ were measured. A diagram showing an X-ray diffraction pattern.

 9 is a diagram showing an X-ray diffraction pattern of a powder and a thin film of a metal halide precursor material prepared in Example 8,

FIG. 10 is a diagram showing an X-ray diffraction pattern of the perovskite compound layer prepared in Example 8, together with an X-ray diffraction pattern of a conventionally known FAPbI ₃ powder.

 [144]

 Mode for Carrying Out the Invention

 The present invention will be described in detail below with reference to the accompanying drawings. The drawings below are provided as examples to fully convey the concept of the present invention to those skilled in the art. Thus, the present invention is presented as follows. The present invention may be exaggerated to clarify the spirit of the present invention, and the present invention may be exaggerated to clarify the idea of the present invention, unless otherwise defined in the technical and scientific terms used. In the following description and in the accompanying drawings, descriptions of known functions and configurations that may unnecessarily obscure the subject matter of the present invention are omitted.

 [146] The present invention provides a method for manufacturing a device having an inorganic / organic hybrid perovskite compound (hereinafter referred to as a perovskite compound) film. In another aspect, the present invention provides a method for manufacturing a solar cell. The present invention also provides a method for producing a perovskite compound film. The present invention also provides a method for binding two structures, each having a perovskite compound film as a medium. The present invention also includes a laminate for producing a solar cell, which can manufacture a solar cell comprising a perovskite compound film as a light absorption layer.

 [147] The manufacturing method provided by the present invention provides a method for manufacturing a target device, in which the perovskite compound film and other well-known basic components required for the intended operation of the intended device are already formed in the first structure and the second structure. It can be specified in a way.

 [148] The manufacturing method provided by the present invention is a surface layer and a high quality perovskite compound film, regardless of the structure or material type of the components constituting the first and second structures other than the surface layer. Therefore, it can be specified by the method for producing a perovskite compound film.

[149] The manufacturing method provided by the present invention provides a method for fabricating a first surface layer and a second structure of a first structure. As the second surface layer is converted into a single, integral perovskite compound film, and the first structure and the second structure are bound together, the first structure and the second structure are transported through the perovskite compound film. Can be specified by the binding method.

 [150] The present invention also provides a device component capable of manufacturing a device including a perovskite compound film. The device component of the present invention includes a first structure in which other basic components, which are required for the operation of the device, are known. And a laminate in which the first structure and the second structure are laminated so that the surface layer of the first structure and the surface layer of the second structure come into contact with each other. The present invention is not limited to the type of device. A solar cell manufacturing part (laminate), which is a representative example of a device including a perovskite compound film, is provided.

 [151] Specifically, the present invention is an organic / organic hybrid perovskite compound film.

 It includes a method of manufacturing the device provided.

 [152] A method for fabricating a device having an inorganic / organic hybrid perovskite compound film in accordance with the present invention includes: a) a first structure comprising a first surface layer containing at least one of the following substances: Independently from one surface layer i to v) laminating a second structure comprising a second surface layer containing at least a substance, the first surface layer and the second surface layer to abut, and b) the first structure 2 applying a thermal and physical force to the laminate in which the structure is laminated.

 [153] i) organic / organic hybrid perovskite compounds

 [154] ii) organic halides

 [155] iii) metal halides

 [156] iv) organic hybrid organic perovskite compounds precursors

[157] V) metal halide precursors

 [158] Specifically, the present invention is an organic / organic hybrid perovskite compound film.

 It includes a method of manufacturing a solar cell provided with a light hop layer.

[159] According to the present invention, a method for manufacturing a solar cell includes a) i to _V ) at least one substance.

 A first structure comprising a first surface layer containing a first surface layer and a second structure comprising a second surface layer containing at least one of the first surface layer independently of the first surface layer, the first surface layer and the second surface layer Laminating to abut, and b) applying thermal and physical forces to the laminate in which the first and second structures are laminated.

 [160] Specifically, the present invention is an organic / organic hybrid perovskite compound film

 It includes a method of manufacturing.

[161] The method for producing an inorganic / organic hybrid perovskite compound film according to the present invention includes the following i-v) a first structure comprising a first surface layer containing at least one substance, and independent of the first surface layer. i-v) laminating a second structure comprising a second surface layer containing at least a material, wherein the first surface layer and the second surface layer are in contact with each other, and b) a laminate having the first structure and the second structure laminated thereon. Applying heat and physical forces. [162] i) organic / organic hybrid perovskite compounds

[163] ii) organic halides

[164] iii) metal halides

 [165] iv) organic hybrid organic perovskite compounds precursors

[166] V) metal halide precursors

 [167] Specifically, the present invention provides an organic / organic hybrid perovskite compound film.

 Interfacing the two structures.

 [168] The binding method according to the present invention includes a) i to v) containing at least one substance.

 A first structure comprising a first surface layer, and a second structure comprising a second surface layer containing at least one of the materials i-v independently of the first surface worm, wherein the first surface layer and the second surface layer are in contact with each other. Laminating, and b) applying the thermal and physical forces to the laminate on which the first structure and the second structure are laminated to bind the first structure and the second structure.

 [169] i) Radical / organic hybrid perovskite compounds

 [170] ii) organic halides

 [171] iii) metal halides

 [172] iv) organic hybrid organic perovskite compounds precursors

[173] V) metal halide precursors

 [174] The method of manufacturing a device, a method of manufacturing a solar cell, a method of manufacturing a perovskite compound film, and / or a bonding method, wherein the application of thermal and physical forces in step b) gives a low surface layer ratio. The two surface layers can be converted to a single inorganic / organic hybrid perovskite compound film.

 In this case, the conversion to a single inorganic / organic hybrid perovskite compound film may mean that the interface (contact surface) between the first and second surface layers disappears in the laminate by the application of thermal and physical forces. Specifically, the first surface layer, in the grain micro-structure of a silver / organic hybrid perovskite compound, which comprises a single membrane / organic hybrid perovskite compound film Challenge 2 The area between the surface layer (contact surface) and the other area has the same organizational structure, which means that the area where the surface between the first surface layer and the second surface layer existed is not distinguished. 'Switching to a single inorganic / organic hybrid perovskite compound film' is a homogeneous grain-structure of the grain-inorganic hybrid organic perovskite compound film. It can mean having the organization.

[176] In other respects, the 'conversion to a single inorganic / organic hybrid perovskite compound film' is achieved by at least densification in the first and second surface layers of the laminate, combining the first and 12 surface layers together. In particular, 'conversion to a single inorganic / organic hybrid perovskite compound film' means that densification and particle growth in the first and second surface layers of the laminate It may mean that a single dense film is produced from the first and second surface layers. Furthermore, the conversion to a single inorganic / organic hybrid perovskite compound film is achieved by densification, nucleation of the crystals (recrystallization). And growth, which may mean that a single dense film is made from the first surface layer and the second surface worm.

 [177] The method of manufacturing the above-described device, the manufacturing method of the solar cell, organic / organic hybrid

 The fabrication method of the perovskite compound film, the bonding method, and / or the components (laminates) for manufacturing the device and the detailed configuration of the solar cell will be described. In detail, the 'combination method' or the 'solar cell manufacturing stack' is specifically described. Unless stated to the extent that one aspect of the present invention is defined, such as a sieve, a 'manufacturing method', and the like, the above descriptions are to be applied to all aspects provided by the present invention. Where applicable to an aspect as a whole, the 'one embodiment according to the present invention' may be prerequisite or without particular limitation, and when described in a configuration more suitable for a specific embodiment, the 'one embodiment according to one embodiment of the present invention' Pretend to be sharp.

 [178] i) Inorganic / organic hybrid perovskite compound, ii) Organic halide, iii) Metal halide, iv) Organic / organic hybrid perovskite, independently contained in the first or second surface layer Compound precursors, V) metal halide precursors are described above.

 [179] i) Inorganic / organic hybrids contained in the surface layer (first surface layer or second surface worm)

 The perovskite compound contains an organic cation (A), a metal cation (M) and a halogen anion (X) and can mean a compound having a perovskite structure.

 [180] M is located at the center of the unit cell in the perovskite structure, and X is

It is located at the center of each side of the unit cell to form an octahedron structure with M as the center, and A can be located at each corner of the unit cell. Again, MX ₆ octahedron In this corner-shearing three-dimensional network, the A organic cations may be in the middle.

 In the following description, i) the organic / organic hybrid perovskite compound contained in the surface layer is referred to as a perovskite compound.

 The perovskite compound may satisfy Formula 1, Formula 2 or Formula 3.

 [183] (Formula 1)

[184] AMX ₃

 [185] In Formula 1, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, Μ is a divalent metal silver, X is a halogen ion, wherein the halogen ions are I-, Br, F- and C1-. One or more can be selected from.

[186] (Formula 2) [187] A (M _{1 -a} N _a ) X ₃

 [188] In Formula 2, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, Μ is a divalent metal ion, Ν is a monovalent metal ion and a trivalent metal ion is a doped metal ion selected at least one. a is a real number with 0 <a ≦ 0.1 and X is a halogen ion. The halogen ion can be one or more selected from I-, Br, F- and C1-.

 [189] In Chemical Formula 2, a monovalent metal ion wherein the doped metal is silver is an alkali metal ion.

The alkali metal ion may be selected from one or more of Li +, Na ⁺ , K +, Rb + and Cs ⁺ ions.

In Formula 2, the trivalent metal ion of the doped metal is AP ⁺ , Ga ³⁺ , In ³⁺ , TP ⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ³⁺ , Cr ³⁺ , V ³⁺ and Ti ^{3+ may} be selected from one or more than two.

 As shown in Chemical Formula 2, when the monovalent metal ion and / or the trivalent metal ion are doped, the electrical properties of the perovskite compound may be controlled to n-type or p-type. Specifically, the monovalent metal may be doped with silver so that the perovskite compound may have p-type. In addition, the perovskite compound may have n-type, so that the perovskite compound may have n-type. Ions are similar to those doped with adapters in conventional silicon semiconductors, and trivalent metals are similar to those doped in silver conventional silicon semiconductors, where both monovalent and trivalent metal ions can be doped. By a larger amount of metal ions

 Of course, the electrical properties of the perovskite compound can be controlled.

 [192] (Formula 3)

[193] A (N ' _1-b N) X ₃

 [194] In Formula 3, A is a monovalent cation, A is an organic ammonium ion,

Amidinium group silver or organic ammonium silver and amidinium silver, Ν ¹ is a monovalent metal silver, Ν ² is a trivalent metal silver, and b is

 It is a real number with 0.4 <= b <= 0.6, and X is a halogen ion.

In Formula 3, the monovalent metal silver silver alkali metal silver silver. The alkali metal ion may be selected from one or more of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ ions.

In Formula 3, the trivalent metal is silver Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Sc ³⁺ , Υ ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ³ One or more can be selected from ⁺ , Cr ³⁺ , V ³⁺ and Ti ³⁺ ions.

 Formula 3 may mean that the divalent metal ion (M) in Formula 1 is replaced with monovalent and trivalent metal ions.

 At this time, similar to the above-described formula (2), by adjusting the relative element ratio of the monovalent metal ions and trivalent metal ions in the range of 0.4≤b≤0.6,

 The electrical properties of the perovskite compound can be controlled to n-type, neutral and p-type.

In Formula 1, Formula 2 or Formula 3, the organic ammonium ion is represented by Formula 4 to Can satisfy 5

 [200] (Formula 4)

[201] R, -NH ₃ ⁺

[202] In Formula 4, ^^ represents C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20

 Aryl

 [203] (Formula 5)

[204] R ₂ -C, H ₃ N ₂ ⁺ -R ₃

In Formula 5, R ₂ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20

Aryl and R ₃ is hydrogen or C 1 -C ₂₄ alkyl.

 In Chemical Formula 2 or Chemical Formula 3, the amidinium-based ions may satisfy the following Chemical Formula 6.

[207] (Formula 6)

In formula (6), R 4 to R _s are independently of each other hydrogen, alkyl of C 1 -C 24, cycloalkyl of C 3 -C 20 or aryl of C 6 -C 20.

In Formula 1, Formula 2 or Formula 3, A is an organic ammonium silver,

 It may be an amidinium group ion or an organic ammonium ion and an amidinium ion. In the case of both organic ammonium ion and amidinium ion, the charge mobility of the perovskite compound is greatly improved. You can do it.

[211] When A contains both organic ammonium ions and amidinium ions, the total molar number of monovalent organic cations is 1, and contains 0.7 to 0.95 amidinium ions and 0.3 to 0.05 organic ammonium ions. That is, in Formula 1, Formula 2, or Formula 3, A can be A ^ A ¹ ^^, where A ^{a is an} amidinium ion, A ^b is an organic ammonium ion, and X is 0.3 to 0.05. The molar ratio between amidinium ions and organic ammonium ions, i.e., 0.7 to 0.95 moles of amidinium ions: from 0.3 to 0.05 moles of organic ammonium, can absorb very wide wavelengths of light, It is the range in which faster movement and separation of excitons and faster movement of optoelectronics and light holes can be achieved.

R of Chemical Formula 4, R ₂ to R ₃ of Chemical Formula 5 and / or R ₄ to R ₈ of Chemical Formula 6 may be appropriately selected depending on the use of the perovskite compound.

[213] In detail, the unit cell size of the perovskite compound is perovskite.

This affects the bandgap of the compound. Accordingly, R ₁ of Formula 4 may be considered to have a suitable bandgap for the perovskite compound film such as the light emitting layer, the semiconductor layer, the light absorbing layer, and the charge storage layer _. R ₂ ᅳ R ₃ of Formula 5 and / or of Formula 6 may be appropriately regulated, which is related to a semiconductor device or an optical device. It is a fact of fact for workers.

[214] As an example, it can have a bandgap energy of 1.5 to 1.1 eV, which is suitable for use as a solar cell that absorbs sunlight in a small unit cell. Thus, a suitable 1.5 to 1 Λ eV is suitable for use as a solar cell. When considering the band gap energy, in formula (4), it may be alkyl of Rr C1-C24, specifically C1-C7 alkyl, more specifically methyl. In addition, in Formula 5, ¾ may be C1-C24 alkyl, R ₃ may be hydrogen or C1-C24 alkyl, specifically R ₂ may be C1-C7 alkyl, R ₃ may be hydrogen or C1-C7 alkyl, More specifically, ¾ can be methyl and R ₃ can be hydrogen. In addition, in Formula 6, R 4 to R _{8 may} be independently of each other hydrogen, amino or C 1 -C ₂₄ alkyl, specifically hydrogen, amino or C 1 -C 7 alkyl, more specifically hydrogen, amino or methyl, and more specific. ¾ is hydrogen, amino or methyl, and may be R ₅ to R _8. Specific and non-limiting example, amidinium-based ions are formamidinium (NH ₂ CH = NH ₂ ⁺ ) ion,

Acetic amidinyl nium _{(acetamidinium, NH 2 C (CH} 3) = NH 2 +) or

Guamidinium, NH ₂ C (NH ₂ ; NH ₂ ⁺ ).

As described above, specific examples of the organic cat (A) are examples of the use of the perovskite compound film, that is, the application to the light absorbing layer of sunlight, and the design of the wavelength band of the light to be absorbed and emitted. When used as the light emitting layer of the device, the design of the emission wavelength band, when used as a semiconductor device of the transistor in consideration of the energy band gap and threshold voltage (R ₂ ~ R ₃ and (or ¾ of formula 6 may be appropriately selected.

In Formula 1 or Formula 2, M may be a divalent metal ion. In one specific example, M may be Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ^{J +} , It may be one or more metal ions selected from Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ .

 In Formula 1, Formula 2 or Formula 3, X is a halogen anion.

 Anions may be selected from one or more of I-, Br, F- and C1-. Specifically, halogenated silver is iodide (1-), chlorine ion (C1-) and bromine is (Br) or It may contain more than one selected ion. More specifically, the halogen anion may contain iodine and bromine ions. The crystallinity and moisture resistance of the perovskite compound when the halogen anion contains both iodide and bromide Can improve.

In some embodiments, in Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, X may be X y) X ^b y, and X ^a and X ^B may be different halogenated silver (iodine silver (1), chlorine silver (C1-). ) And different halogen atoms selected from br ions (Br), and y may be a real number of 0 <y <l. More specifically, in Formula 1, X may be X y) X ^b _y , and X ^a Iodine ions, X ^B is bromine silver, y may be a real number of 0.05 ≦ y ≦ 0.3, specifically 0.1 ≦ y ≦ 0.15, i.e., deterioration by moisture is significantly prevented and low temperature processes below 100 ° C In order to have excellent crystallinity, halogen anions, iodides and When all the ions are contained, the total molar number of the anions can be set to 1, which can contain iodine ions of 0.7 to 0.95 and bromine ions of 0.3 to 0.05.

[219] Based on the foregoing, specific and non-limiting, where M is Pb ^2+.

As an example of a perovskite compound, the perovskite compound may be selected from CH ₃ N¾PbI _x Cl _y (number of real _numbers 0 ≦ x ^ 3, number of real numbers 0 ≦ _y ≦ 3 and x + y = 3), CH ₃ NH ₃ PbI _x Br _y (0≤x≤3 Real, 0≤y≤3 Real and x + y = 3), CH ₃ N¾PbCl _x Br _y (0≤x≤3 Real, 0≤y≤3 Real and x + y-3), C NH 3 PbI x F y (0≤x≤3 room number, room number 0≤y≤3 and x + y = 3), NH 2 CH = NH 2 PbI x Cl y ( 0 <x <3 persons, 0 <y <3 persons, and x + y = 3), NH ₂ CH = NH ₂ PbI _x Br _y (0 <x <3¾), 0 ≦ _y ≦ 3 And x + y = 3), NH ₂ CH = NH ₂ PbCl _x Br _y (0 ≦ _x ≦ ₃ real number, 0 ≦ _y ≦ 3 real number and x + y = 3), NH ₂ CH = NH ₂ PbI _x F _y (real number 0 ≦ x ≦ 3, real number 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ CH = NH CHg NH Pba _d DBry x is 0 <χ <1 real number, y is 0 < y <l true number), NH ₂ CH = NH 2 _(1-x) CH ₃ NH _3x Pb (I _{(1. y)} Br _y ) ₃ (x is 0,05 ≦ x ≦ 0.3, y is 0.05 ≤ y ≤ 0.3), N¾ a ^ CH. CH ^ H ^ Pb ^ wBr _x Mx is 0.05≤x≤0.3 real number, NH ₂ C (CH ₃ ) = NH ₂ PbI _x Cl _y (real number 0≤x≤3, real number 0≤y≤3) and χ + γ = 3), ΝΗ ₂ (α¾) = ΝΗ ₂ Ρ¾Βιν (real number of 0≤χ≤3, real number of 0≤y≤3 and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbCl _x Br _y (0≤x≤3 Real Number, 0≤y≤3 Real Number and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbI _x F _y (0≤x≤3 Real Number , Real numbers of 0 ≦ y ≦ 3 and x + y = 3, NH ₂ C (CH 3) = NH _{2 (1. X)} CH ₃ NH 3 _X Pb (I _(1-y) Br _y ) ₃ (xfe 0 <<1 person number, y is 0 <y <l person number), NH ₂ C (CH ₃ ) = NH _20-x ) CH ₃ NH _3x Pb (I _{(1 .y)} Br _y ) ₃ (x is 0.05 ≤ x ≤ 0.3, where y is

0.05 ≦ y ≦ 0.3 real number), NH ₂ C (CH ₃ ) = CH _{2 <1} . _x) CH ₃ NH _3i Pb (I _{(1. x)} Br _x ) ₃ (x is a real number with 0.05 ≦ _x ≦ 0.3), NH ₂ C (N¾) = NH ₂ PW _x Cl _y (0 ≦ _x ≦ 3 Number, real number with 0 ≦ y ≦ 3 and x + y = 3, NH ₂ C (NH ₂ ) = NH ₂ PbI _x Br _y (real number with 0 ≦ _x ≦ 3, real number with 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (N¾) = NH ₂ PbCl _x Br _y (0 < _x ≦ ₃ real number, 0 ≦ _y ≦ 3 real number and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PW _x F _y (Number of real numbers 0 ≦ x ≦ 3, Number of real numbers 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (NH ₂ ) = NH _{2 (1-x)} CH ₃ NH _3x Pb (I _{(1. Y)} Br _y ) ₃ (x is a real number with 0 <χ <1, y is a real number with 0 <y <l), NH ₂ C (NH ₂ ) = NH _{2 (1-x)} CH ₃ NH _3x Pb (I _(1-y) Br _y ) ₃ (x is

0.05≤x≤0.3 real number, y is 0.05≤y≤0.3 real number) or NH ₂ C (NH ₂ ) = CH _{2 (1 .X)} CH ₃ NH 3 _x Pb (I _{(1. X} ) B _rx ) ₃ (x is a real number of 0.05≤x≤0.3).

 [220] Inorganic / organic hybrid perovskite contained in surface layer in the description below

 Compound precursors are collectively referred to as perovskite compound precursors. Reference may be made to all the contents described in International Patent PCT-KR2014-012727 of the present applicant, relating to organic / organic hybrid perovskite compound precursors. Includes the contents described in International Patent PCT-KR2014-012727.

 In detail, the iv) perovskite compound precursor contained in the surface layer (first surface layer or second surface layer) is a precursor of the perovskite compound described above, and the monovalent organic cation (A), It may include metal cations (M), halogen anions (X), and heterogeneous molecules (GM). Perovskite compound precursors may also be measured using X-ray radiation measurements using Cu-Ka rays (Θ). In the -2Θ method), peak peaks can be detected at diffraction angles 2Θ between 6.2 and 6.8 °, between 7 and 7.5 °, and between 8.9 and 9.5 °.

[222] The precursor material of perovskite compound is that GM is A organic cat, M metal cation and X. It may be an adduct formed in combination with a perovskite compound containing a halogen anion. In the crystal structure, the perovskite compound precursor may be amorphous, crystalline, or a mixture of amorphous and crystalline.

[223]. In the perovskite compound precursors, the monovalent organic cationic, metal ions and halogen anions are similar to the monovalent organic cations (A), metal ions (M) and halogen anions (X) previously described in the perovskite compound. Can be the same.

The perovskite compound precursor may be an adduct of the above-described perovskite compound and a heterogeneous molecule (GM).

In detail, the perovskite compound precursor may satisfy the following Formula 7, Formula 8, or Formula 9.

[226] (Formula 7)

[227] AM (GM) „X ₃

 [Formula 7] In Formula 7, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, M is a divalent metal ion, X is a halogen ion, GM is a heterogeneous molecule, η is 0 <n <3 to be.

[229] (Formula ⁸ )

_{[230] A (M ,. a} N a) (GM) n X 3

 In Formula 8, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, Μ is a divalent metal ion, Ν is a doped metal ion selected from at least one of monovalent and trivalent metal ions, a is a real number with 0 <a ≦ 0.1, X is a halogen or silver, GM is a heterogeneous molecule, and η is a real number with 0 <n <3.

[232] (Formula ⁹ )

 [233] ACNS ^ XGM) ^

 [234] In Formula 9, A is a monovalent cation, A is an organic ammonium ion,

Amidinium group ions or organic ammonium ions and amidinium-based ions, Ν ¹ is a monovalent metal silver, Ν ² is a trivalent metal ion, b is

 It is a real number with 0.4 <b≤0.6, X is a halogen silver, GM is a heterogeneous molecule, and n is a real number with 0 <n <3.

In Formula 7, Formula 8, and Formula 9, except for GM, A, M, N, N ¹ , N ² , X, a and b are as described above based on Formula 1, Formula 2 or Formula 3 and Can be the same. In addition, in Formula 7, Formula 8, and Formula 9, except for GM, A, M, N, N ¹ , W, X, a and b are perovskite compounds based on Formula 1, Formula 2 or Formula 3 above This includes all of the above.

 [236] In the perovskite compound precursor, GM silver organic cations (A) and metals

The cation (M, N, N ¹ , N ² ) may be non-covalently bonded to one or more selected cations, wherein the non-covalent bonds are ionic, coordination, hydrogen or van der Waals May include bonds by force.

In perovskite compound precursors, GM may contain one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bream and iodine, including unshared electron pairs.

[238] That is, GM is composed of organic cations (A) and / or metal cations (M, N, N ¹ and / or N ² ).

 It may be a molecule containing oxygen, nitrogen, fluorine, chlorine, bromide, or iodine containing a non-covalent pair of non-covalent electrons.

 [239] In one embodiment, GM is one or more of oxygen, nitrogen, fluorine, chlorine, bromine and iodine

 It may be a solvent containing the element selected and dissolving the perovskite compound. Accordingly, the perovskite compound precursor may be a solvent compound of the perovskite compound and a solvent dissolving it. As is known, the solvent compound may be a molecule or ion of a solute (perovskite compound), It can mean a higher order compound that is formed between molecules or ions of a solvent.

 [240] Perovskite Compound When the precursor is a solvent compound between the perovskite compound and a solvent that dissolves it, there is an advantage in that the GM is removed homogeneously and quickly at low temperature, and the perovskite compound is manufactured.

As described above, the perovskite compound constituting the solvent compound may satisfy the above Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3. In Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, A is A ^ A ^. A ^a is an amidinium-based ion, A ^b is an organic ammonium ion, X can be a real number from 0.3 to 0.05), and independently of this, X is X _y) X ^b _y (X a iodide silver, is bromine ion and, y is a real number of 0.05 to 0.3, the number of days specifically αι≤ _χ ≤ο.ΐ5 room number).

 [242] In the perovskite compound precursor that is a solvent compound, the heterogeneous molecule

 Ν, Ν-dimethylacetamide, 1,4-dioxane, diethylamine, ethylacetate, tetrahydrofuran,

 Pyridine, methanol, ethanol,

 Dichlorobenzene (l, 2-dichlorc) benzene, glycerine and

 One or more may be selected from dimethyl sulfoxide (DMSO) and Ν, Ν-dimethylformamide (DMF).

 In the perovskite compound precursor, heterogeneous molecules are removed and converted into crystalline perovskite compounds by the energy applied to the perovskite compound precursor.

 In other words, since the perovskite compound precursor is a non-covalent compound between the perovskite compound and GM, pure peroxide is removed from the precursor by means of energy application, atmosphere control, or pressure reduction. It can be converted to a lobite compound.

[245] The perovskite compound precursor may be manufactured and used or a conventionally known material may be used. Specific and non-limiting examples are as follows. Perovskite compound precursors can be prepared by injecting a perovskite compound (or organic cationic silver, metal cationic silver and halogen anions) and a dissolved solution of heteromolecules into the nonsolvent.

 More specifically, in the case where the perovskite compound precursor is a solvent compound, organic cations, metal cations, and halogen ions according to the stoichiometric ratio of the perovskite compound or perovskite compound may be added to the solvent containing heterogeneous molecules. Dissolve

The perovskite compound precursor can be prepared by the step of preparing the perovskite compound solution, dropping the perovskite compound solution into the non-solvent, and recovering and drying the solids obtained by the drop. In this case, the nonsolvent does not dissolve the perovskite compound and may mean an organic solvent that is not compatible with the solvent. At this time, the nonsolvent means that the perovskite compound does not dissolve at 20 ^° C. Organic solvents having a solubility of less than 0.1 M, specifically less than 0.01 M, and more specifically less than 0.001 M, may be used as the non-solvent soluble solvent (perovskite compound-solvent compound). In other words, it is heterogeneous and non-combustible, meaning that the mixture is separated from the nonsolvent and perovskite solution in a static state where no physical stirring is performed. Examples of nonsolvents include non-polar organic solvents, and non-polar organic solvents include pentine, nuxenes, cyclonuxenes,

 1,4-dioxene, benzene, rollo <¾1, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1,2-dichlorobenzene, tert-butyl alcohol,

And one or more organic solvents selected from 2-butanol, isopropanol and methyl ethyl ketone, but are not limited to these.

 The metal halides contained in the surface worms (first surface layer or second surface layer) may mean compounds of metal ions and halogenated silver.

 In detail, the metal halide is represented by Formula 1, Formula 2, or Formula 3 above.

In the above-described perovskite compounds, the compounds of metal cations (Μ, Ν, Ν ¹ and / or Ν ² ) and halogen ions (X) can be defined.

 That is, the metal halide may satisfy the following Formula 10, Formula 11 or Formula 12.

 [250] (Formula 10)

[251] ΜΧ ₂

 In Formula 10, Μ is a divalent metal ion and X is a halogen ion. At this time, the halogen ions may be selected from one or more of I-, Br, F- and C1-.

[253] (Formula 11)

[254 i _{(M ,. a N a) X} 2

In Formula 11, M is a divalent metal ion, N is a doped metal ion selected from at least one of a monovalent metal ion and a trivalent metal ion, a is a real number having 0 <a≤0.1, and X is halogen Wherein the halogen ion is one or more of I-, Br, F- and C1- Can be chosen.

In Formula 11, the monovalent metal ion, which is a doping metal ion (N), includes an alkali metal ion. The alkali metal ion is one or more of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ ions. Can be chosen.

In Formula 11, the trivalent metal ion as the doping metal ion (N) is Al ³⁺ ᅳ Ga ³⁺ , In ³⁺ , TP ⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , One or more may be selected from Fe ³⁺ , Ru ³⁺ , Cr ³⁺ , V ³⁺ and Ti ³⁺ ions.

 When metal halides are doped with monovalent metal ions or with more monovalent metal ions than trivalent metal ions, ρ-type perovskite compounds can be prepared by the reaction of metal halides with organic halides. In addition, the metal halide contains more trivalent metal ions or more trivalent metal ions than monovalent metal ions.

When doped, ^η- type perovskite compounds can be produced by reaction of metal halides and organic halides.

 [259] (Formula 12)

[260] (N _b N ² _b ) X ₂

[Formula 12] In Formula 12, N ¹ is a monovalent metal ion, Ν ² is a trivalent metal ion, b is

 It is a real number with 0.4 <= b <= 0.6, and X is a halogen ion.

In Formula 12, the monovalent metal ion (N ¹ ) includes an alkali metal ion. The alkali metal ion may be one or more selected from Li ⁺ , Na% K Rb ⁺ and Cs ⁺ ions.

In Formula 12, the trivalent metal ion is Al ³⁺ , Ga ³⁺ , In ³⁺ , TP ⁺ , Sc ³⁺ , Y ³⁺ , La ³⁺ , Ce ³⁺ , Fe ³⁺ , Ru ³⁺ One or more may be selected from among Cr ³⁺ , V ³⁺ and Ti ³⁺ ions.

 Formula 12 may mean that the divalent metal ion (M) of Formula 10 is replaced with monovalent and trivalent metal ions.

 At this time, similar to the above-described formula (11), by adjusting the relative element ratio of monovalent metal ions and trivalent metal silver in the range of 0.4≤b≤0.6,

 The electrical properties of perovskite compounds produced by reaction with organic halides can be controlled to n-type, intrinsic or p-type.

M and X of Formula 10 may be the same as M and X described above based on Formula 1, ¾1, 1 ^, ^ and a of Formula 11 are represented by Μ, N, Χ and a may be the same or similar, and, in Formula 12, W, X and b may be the same as N ⁱ , N ² , X and b described above based on the formula (3). And in Chemical Formula 12, M, N, ΙΦ, N ² , X, a, and b are M, N, N ¹ , N ² , X, in the perovskite compound based on Formula 1, Formula 2, and Formula 3 above. It includes all of the foregoing with respect to a and b.

 [267] V) Metal halide precursors contained in the surface layer (first surface layer or second surface layer) are heterogeneous, with metal cations and halogen anions forming metal halides.

It may be a compound comprising a molecule (heterogeneous molecule or guest molecule, hereinafter referred to as GM '). In detail, the metal halide precursor may be a compound in which a heterogeneous molecule is non-covalently bonded with the metal halide (MX ₂ ) of the metal cation and the halogen anion constituting the inorganic / organic hybrid perovskite compound. Bonds, coordination bonds, hydrogen bonds, or bonds by van der Waals forces.

 [269] Again, metal halide precursors are metal halide-heterogeneous molecules.

 It may be an adduct of halogenated metal and quest molecule.

 Structurally, the metal halide precursor may be a structure in which a heterogeneous molecule is inserted between layers of a metal halide having a layered structure, wherein the heterogeneous molecule may include a single molecule or a polymer.

 The metal halide precursors can be converted into perovskite compounds by the intramolecular exchange between the heterogeneous molecules contained in the metal halide precursors and the organic halides.

 [272] in detail, in metal halide precursors, in combination with metal halides

 Heterogeneous molecules are removed and at the same time, the organic halides

 Metal halides can be reacted to form perovskite compounds.

[273] The heterogeneous molecules of the metal halide precursors are extremely easily removed when perovskite compounds are formed, resulting in the MX ₆ octahedron.

 It occurs during the nucleation and growth of the perovskite compound upon conversion to the perovskite compound without disturbing the formation of the perovskite structure in which A is located in the corner-shearing three-dimensional network. volume

 Changes (volume difference between metal halide precursors and perovskite compounds) can be suppressed and the movement (diffusion) of organic halides can be improved.

 The metal halide precursor may be a compound in which a metal halide and a heterogeneous molecule are noncovalently bound, and specifically, a compound of an oxygen, nitrogen, or a heterogeneous molecule including oxygen and nitrogen containing a metal halide and a non-covalent electron pair. have.

 Based on the above formula, the metal halide precursor may satisfy the following Chemical Formula 13, Chemical Formula 14 or Chemical Formula 15.

 [276] (Formula 13)

[277] MX ₂ (GM ') _n

In Formula 13, M is a divalent metal cation, X is one or two or more halogenated silvers selected from C1-, Br, F and I-, and GM 'is a heterogeneous non-covalent bond with MX ₂ Molecule, n is a real number from 0.5 to 50.

[279] Perovskite compounds can be produced by molecular exchange between heterologous molecules of metal halide precursors and organic halides. Accordingly, volume change after molecular exchange reaction (metal halide precursors and perovskite) N is 0.5 to 5, specifically n is 0.5 to 2, more specifically n is 0.5 to 1.5 so as to suppress the difference in volume from the compound) and to guarantee enhanced organic halide transfer (diffusion). Can be In MX l of Chemical Formula 13, Μ is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ² One or more of the metal ions may be selected from ⁺ , Pb ²⁺ and Yb ²⁺ , and X may be selected from Ch Br, F- and I-.

 [281] (Formula 14)

_{[282] (M ,. a N} a) X 2 (GM ') n

In Formula 14, M is a divalent metal ion, Ν is a monovalent metal ion and a trivalent metal ion, and at least one doped metal ion is selected, a is a real number having 0 <a≤0.1, and X is halogen Ions, GM 'is _a guest molecule that covalently binds to (M ^ N _a ) X ₂ , n is 0.5 to 50 real numbers, preferably n is 0.5 to 5, specifically n is 0.5 to 2 More specifically, n may be between 0.5 and 1.5.

 [284] (Formula 15)

_{[285] (NS. B N2} 5) X 2 (GM ') n

[Formula 15] In Formula 15, N ¹ is a monovalent metal ion, N ² is a trivalent metal ion, b is

A real number of 0.4 ≦ b ≦ 0.6, X is a halogen ion, GM ′ is a guest molecule covalently bonded with (Ν ^ Ν) Χ ₂ , n is a real number of 0.5 to 50, preferably n is 0.5 To 5, specifically n is 0.5 to 2, more specifically n may be 0.5 to 1.5.

In Formula 13, Formula 14, and Formula 15, except for GM ', M, N, N', N ² , X, a, and b are perovskite based on Formula 1, Formula 2, or Formula 3 above. The compound may be the same as described above. In addition, in Chemical Formula 13, Chemical Formula 14 and Chemical Formula 15, GM ′, ^！ ， ^^ ， ^ ，;? And ！！ Or in the perovskite compound based on formula (3), all of which is described above in relation to Μ, Ν, Ν ', Ν Β ^ and b.

 [0072] GM ', a heterogeneous molecule inserted between layers of a layered metal halide, may be oxygen, nitrogen, or a molecule containing oxygen and nitrogen containing a lone pair of electrons, and may be monomolecular and molecular.

 As a specific example, the heterogeneous molecule GM 'which is non-covalently bonded to the metal halide may be oxygen, nitrogen, or a monomolecular to polymer containing oxygen and nitrogen containing a non-covalent pair of electrons. Non-covalently heterologous molecules include dimethylsulfoxide (DMSO),

 Ν, Ν-dimethylformamide (N.N-dimethylformamide DMF),

 N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP),

 2,2'-bipyridine, 4,4'-bipyridine-Ν, Ν'-dioxide (4,4'-bipyridine, 4,4'-bipyridine-N, N ' -dioxide), pyrazine, 1,10-pananthrin

 Any molecule capable of forming a compound by non-covalent coupling with a metal halide such as (1,10-phenanthroline), 2-methylpyridine or poly (ethylene oxide) is possible.

[290] Good diffusion of heterogeneous molecules intercalated between layers of layered metal halides In terms of removal and provision of an easy diffusion path to organic halides, metal halide precursors can be combined with metal halides and solvents that dissolve metal halides.

 It is preferable to be a solvate.

 [291] When the metal halide precursor is a solvent compound of a metal halide and a solvent that dissolves the metal halide, the organic solvents can be quickly and easily diffused and removed by the strong volatility of the solvent. A fast and easy site exchange with the gas can occur, allowing the production of perovskite compound films with very coarse grains.

 In the case where the metal halide precursor is a solvent compound, the metal halide precursor may be a compound in which a heterogeneous molecule, which is a solvent of the metal halide and the metal halide, is non-covalently bonded. In one embodiment, the heterogeneous molecule is combined with oxygen, nitrogen, or oxygen. It may be a solvent that contains nitrogen and dissolves metal halides.

 [293] Based on the above formula, GM 'of 13, 14 or 15 is

It may be a solvent (solvent molecule) that contains oxygen, nitrogen, or oxygen and nitrogen, and dissolves metal halides (MX ₂ , (M _{1 -a} N _a ) X ₂ or (NV _b NV) X ₂ ).

 [294] Non-covalently bound metal halides and solvent molecules soluble in metal halides

Solvates can have a layered structure of metal halides (MX _2, (M _a N _a ) X ₂ or (N ¹ ) in which solvent molecules are intercalated. It can have extremely good reactivity with organic halides.

 [295] As a specific example of a heterologous molecule which is a solvent, dimethyl sulfoxide (Dimethylsulfoxide,

 DMSO), Ν, Ν-dimethylformamide (Ν, Ν-dimethylformamide DMF), and

 One or two or more in N-methyl-2-pyrrolidone (NMP). The material of choice. For better metal halide precursors,

 May be a compound of a metal halide and dimethyl sulfoxide.

 In the case of metal halide precursors, perovskite compounds are formed by the molecular exchange between heterogeneous molecules of metal halide precursors and organic halides, and there is almost no volume change after reaction and physical deformation due to reaction. And roughness increase can be prevented. Also, by very easy and fast molecule exchange reaction

 As the perovskite compound is formed, it can be produced in the form of an extremely thick thick film.

 [296] Metal halide precursors may be manufactured and used or known materials.

 It can be purchased and used. As a specific and non-limiting example,

 Metal halide precursors can be prepared by instilling non-solvent solutions of metal halides (or metal cations and halogen anions) and dissimilar molecules.

 More specifically, when the metal halide precursor is a solvent compound,

A metal halide solution is prepared by dissolving metal transition silver and halogen ions according to the stoichiometric ratio of a metal halide or a metal halide in a solvent which is a heterogeneous molecule. The step, dripping the metal halide solution into the nonsolvent; recovering and drying the solid phase obtained by the drop; can produce the metal halide precursor, wherein the nonsolvent does not dissolve the metal halide. It can mean an organic solvent that does not have a solvent and incompatibility, which means that it does not dissolve metal halides at 20 ° C under 1 atm, solubility of metal halides is less than 0.1 M, specifically less than 0.01 M, and more specific. as can be means an organic solvent of less than 0.001 M. meaningful cost-solvent (a metal halide solvent ^compound, two kinds of molecules case is water) solvent for dissolving the metal halide does not have the waheun Mars with the non-solvent and the metal halide solvents cargo solution In general, this may mean that the layers are separated in a static state without physical stirring. For example, non-solvents include non-polar organic solvents, and non-polar organic solvents may be pentine, nucleus, etc. ， Cyclonucleene, 1,4-dioxene, benzene, toluene, triethyl amine, chlorobenzene, ethylamine, ethyl ether, chloro product, ethyl acetate, acetic acid, 1,2-dichlorobenzene, tert- One or more organic solvents may be selected from butyl alcohol, 2-butanol, isopropanol and methyl ethyl ketone, but the invention is not limited by non-solvents.

 Ii) The organic halide contained in the surface layer (the first surface layer or the second surface layer) may mean a compound of monovalent organic cations (A) and halogen anions (X), and may be represented by Formula AX.

 In other words, the organic halide may be represented by Formula 16 below.

 [300] (Formula 16)

 [301] AX

 [Formula 16] In Formula 16, A is a monovalent cation, A is an organic ammonium ion,

 Amidinium group ions or organic ammonium ions and amidinium-based ions, and X is a halogen ion.

 In Chemical Formula 16, A and X may be the same as the monovalent organic ions A and halogen ions X described above based on Chemical Formula 1. In addition, in Chemical Formula 16, A and X may be represented by Chemical Formula 1, Chemical Formula 2 or In the perovskite compound on the basis of the formula (3) includes all the above-mentioned with respect to A and X. In addition, A in Formula 16

 Perovskite compounds include all of the foregoing based on Formula 4, Formula 5 or Formula 6.

 In other words, in Chemical Formula 16, the monovalent organic ion (A) may be a monovalent organic ion such as an amidinium group ion, an organic ammonium silver, or an ammonium silver and an organic ammonium silver.

 In detail, the organic halide can satisfy the following formula (17) or (18).

 [306] (Formula 17)

[307] (R, -NH ₃ ⁺ ) X

Ri in Formula 17 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 Aryl, X is a halogen ion selected from one or more of C1-, Br, F- and I-.

[309] (Formula 18)

[310] (R ₂ -C ₃ H ₃ N ₂ ⁺ -R ₃ ) X

[311] In Formula 18, R ₂ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20

Aryl, R ₃ is hydrogen or C 1 -C ₂₄ alkyl, and X is a halogen ion selected from one or more of C 1-, Br, P and I-.

In a non-limiting example, considering the absorption of sunlight, R 17 in Formula 17 may be C 1 -C 24 alkyl, specifically C 1 -C 7 alkyl, more specifically methyl. In Formula IS, R ₂ May be C 1 -C ₂₄ alkyl and R ₃ may be hydrogen or C 1 -C ₂₄ alkyl, specifically R ₂ may be C ₁ -C 7 alkyl and R ₃ may be hydrogen or C 1 -C 7 alkyl, more specifically R ₂ may be methyl and R ₃ may be hydrogen.

 In detail, the amidinium-based silver may satisfy the following formula (19).

[314] (

In formula (19), R 4 to ¾ are independently of each other hydrogen, alkyl of C 1 -C 24, cycloalkyl of C 3 -C 20, or aryl of C 6 -C 20. In Formula 19 to R _{8 may} be independently of each other, hydrogen, amino or C1-C24 alkyl, specifically, hydrogen, amino or C1-C7 alkyl, more specifically hydrogen, amino or methyl, more specifically ^ cattle, the amino or methyl and R ₅ to ¾ gagak each hydrogen days. More specifically, and as a non-limiting example, an amidinyl you umgye ions formamidinium nium _{(foraiamidinium, NH 2 CH = NH} 2 +) ions, acetic amidinyl nium may be mentioned _{(acetamidinium, NH 2 C (CH} 3) = NH 2 +) or guar MIDI nium _{(Guamidinium, NH 2 C (NH} 2) = NH 2 +) round.

 In detail, in the formula (16), when the monovalent organic ions include both organic ammonium ions and amidinium-based ions, the organic halide can satisfy the following formula (20): Organic ammonium ions and amidini If the silver content contains all silver, the charge mobility of the perovskite compound can be improved significantly.

 [318] (Formula 20)

[319], _-Χ) Α ^ Χ

[Formula 20] In Formula 20, A ^b is a monovalent organic ammonium ion, and A ^a is an amidinium-based

 Is an ion, X is a halogen silver, and X is a real number of 0 <χ <1, wherein a halogen ion can be selected from one or more of I-, Br, F- and C1-.

 [321] When the organic halide comprises a monovalent organic cation containing an amidinium group ion and an organic ammonium ion, in response to a metal halide,

Containing amidinium group ions and organic ammonium ions Perovskite compounds can be prepared, which can absorb light in a very wide wavelength range, but also allow faster exciton transfer and separation, faster photoelectron and light hole movement. For this, better X can be 0.3 to 0Ό5, specifically, A is A _x) A ^b _x (A ^a is

Amideium ions, _Ab is an organic ammonium ion, and X may be a real number of 0.3 to 0.05.

 [322]

 [323] The surface layer (the first surface layer or the second surface layer) may be formed of at least one of the aforementioned i to v) materials.

 It can be a single layer containing, i ~ v) a single layer containing at least two materials, or i ~ v) at least two materials each layered and laminated.

 [324] The surface layer containing at least one of the aforementioned i to v (first surface layer or

 The lower surface layer) may mean the component that is exposed to the atmosphere by being located at the top or the outermost of the components that make up the structure (first or second structure) ie the surface layer is exposed to the surface of the structure. It can mean a layer (the layer that forms the surface).

[325] The 'layer' of the surface layer (first surface layer or second surface layer) means that at least one of the substances i to _v described above in a given region forms and forms the surface, i.e. At least one substance exists in a certain area and is called the surface layer according to the surface of the structure. Accordingly, the term 'layer' in the surface layer is not limited to the meaning of dense film and should not be interpreted. It is also limited by the meaning of a film that covers all one surface of other components that make up a structure, such as a frozen substrate.

 It should not be interpreted.

 [326] It is also important to note that at least one of the i-v) forms and forms the surface.

 At least one of i-v) is embedded in a component other than the surface layer constituting the structure (the first structure or the second structure), and it is also included if some of the protruded portions form the surface layer. Shall.

 In this case, at least one of the i-v) regions in which the material exists and forms the surface is converted to the organic hybrid perovskite compound film, at least the first surface layer and the second surface layer, thereby converting the organic / organic hybrid. If the first structure and the second structure can be physically connected together through the perovskite compound film, it is also possible to manufacture a device having an organic / organic hybrid perovskite compound film. Of course, the position and shape of the area where the surface layer is located can be properly designed in consideration of the position or shape of the organic / organic hybrid perovskite compound film required for the device to operate normally or effectively.

 In addition, the surface layer may be patterned or unpatterned.

By patterning, it means that the surface layer is located only in the area intended to have the designed shape. As an example of patterning, several strip shapes are arranged apart from each other. Mesh shapes, regularly spaced dots (not limited to their shape, such as round or square, but not limited in size), but not limited to the desired inorganic / organic hybrid perovskite. Of course, it can be patterned to conform to the shape of the compound film. If the surface layer is patterned, the first surface layer and

 The second surface layer can be patterned into shapes that are opposite to each other. The shape that is opposite to each other means that the second surface layer has a pattern that is symmetrical (line symmetrical) with the pattern of the first surface layer. This dominant shape can be readily understood when considering that the first and second surface worms are laminated to one another and then converted to a single inorganic / organic hybrid perovskite compound film.

 [329] The first surface layer comprises i) inorganic / organic hybrid perovskite compounds described above, ii) inorganic / organic hybrid perovskite compounds precursors, iii) metal halide precursors, iv) organic halides and V. ) I-v) of metal halides may contain at least one substance. The first surface worm may be a dense membrane, a porous membrane or a laminate thereof.

 As a specific example, the first surface layer may contain the above-mentioned perovskite compound. More specifically, the first surface layer may be formed of the above-described perovskite compound.

 As a specific example, the first surface layer may contain the above-mentioned perovskite compound precursor. More specifically, the first surface layer may be formed of the upper perovskite compound precursor.

As a specific example, the first surface layer may contain the metal halide precursors described above. More specifically, the first surface layer may comprise the metal halide precursors described above.

 As a specific example, the first surface layer may contain the organic halides described above. More specifically, the first surface layer may be composed of the organic halides described above.

 As a specific example, the first surface layer may contain the metal halide described above. In more specific example, the first surface layer may be made of the metal halide described above.

 [335] As a specific example, the first surface layer may comprise the metal halides described above and the above-described metal halides.

 . Organic halides may be included. In a more specific example, the first surface layer may consist of a mixture of the metal halides described above and the organic halides described above.

 [336] The second surface layer is independent of the first surface worm, i) free / organic hybrid perovskite compound, i) free / organic hybrid perovskite compound precursor, iii)

 It may contain at least one of metal halide precursors, iv) organic halides and V) metal halides i to v).

 [337] The second structure with the second surface layer comprising: i) zero / organic hybrid perovskite.

 Compound, ii) organic / organic hybrid perovskite compound precursor, iii)

Metal halide precursors, iv) organic halides and V) i-v) increase in metal halides may mean structures having surface areas containing at least one substance. The second surface layer may be a dense film, a porous film or a laminated film thereof. [338] The second surface layer comprises i) inorganic / organic hybrid perovskite compounds, ii) inorganic / organic hybrid perovskite compound precursors, iii) metal halide precursors and IV) organic halides, V. It may contain at least one of the i-v) metal halides.

 As a specific example, the second surface layer may contain the perovskite compound described above. More specifically, the second surface layer may consist of the perovskite compound described above.

 As a specific example, the second surface layer may contain the perovskite compound precursor described above. More specifically, the second surface layer may consist of the perovskite compound precursor described above.

As a specific example, the second surface layer may contain the metal halide precursor precursor described above. In more specific example, the second surface layer may be the metal halide precursor precursor described above.

 As a specific example, the second surface layer may contain the organic halides described above. More specifically, the second surface layer may consist of the organic halides described above.

 As a specific example, the second surface layer may contain the metal halide described above. More specifically, the second surface layer may consist of the metal halide described above.

 [344] As a specific example, the second surface layer may contain the above-described metal halides and the above-mentioned organic halides. More specifically, the second surface layer may be a mixture of the above-mentioned metal halides and the above-mentioned organic halides. Can be

 [345] Considering the material of the first surface layer, i to v) at least one substance in the first surface layer and i to v) at least one substance in the second surface layer are as follows. Can be.

 [346] Substances contained in the first surface layer—a pair of substances in the second surface layer

 [347] perovskite compounds-perovskite compounds

 [348] perovskite compounds-perovskite compound precursors

 [349] perovskite compound precursors-perovskite compound precursors

 [350] metal halide precursors -organic halides

 [351] organic halides-metal halide precursors

 [352] organic halides-metal halides

 [353] metal halides-organic halides

 [354] In the above-described material pairs, although the first surface layer and the second surface layer both contain perovskite compounds or perovskite compound precursors, the specific materials contained in each surface layer may be the same, or It may be different.

 As a specific example, when both the first surface layer and the second surface layer contain a perovskite compound, the first surface layer and the second surface layer both satisfy Formula 1, Formula 2, or Formula 3. Specific composition (A, M and / or X) may differ from one another.

[356] As a specific and non-limiting example, the first surface layer may contain an n-type perovskite compound. The second surface layer may contain a p-type perovskite compound.

 [357] As a specific and non-limiting example, both the first surface layer and the second surface layer

When the perovskite compound is contained, the perovskite compound contained in the first surface layer and the perovskite compound contained in the second surface layer are independent of each other, and the number of CH ₃ NftPbl ^ CI _y CO x S Real numbers with 0 ≦ y ≦ 3 and x + y = 3), CH ₃ NH ₃ PbI _x Br _y (real numbers with 0 ≦ _x ≦ ₃ , real numbers with 0 ≦ _y ≦ 3 and x + y = 3), CH ₃ NH ₃ PbCI _x Br _y (0≤x≤3 Real Number, 0≤y≤3 Real Number and x + y = 3), α¾ΝΗ ₃ ΡΜ _χ ΐ; 0≤χ≤3 Real Number, 0≤y≤3 Real Number And x + y = 3), NH ₂ CH = NH ₂ PbI _x Cl _y (number of real _{numbers 0} ≦ _x ≦ ₃ 수 ₀ ≦ _y ≦ 3 number and x + y = 3), NH ₂ CH = NH ₂ PbI _x Br _y (real number 0≤x≤3, real number 0≤y≤3 and x + y = 3), NH ₂ CH = NH ₂ PbCl _x Br _y (0≤x≤3 real number, 0≤y≤3 Phosphorus and x + y = 3), NH ₂ CH = NH ₂ PbI _x F _y (0≤x≤3 phosphorus, 0≤y≤3 phosphorus and x + y = 3), NH ₂ CH = NH 2 ₀ _ _x) CH ₃ NH _3x Pb (I _(1-y) Br _y ) ₃ (x is 0 <χ <1 real number, y is 0 <y <l real number), NH ₂ CH = NH 2 ₀ _ _x) CH ₃ NH _3x Pb (I ₍₁ - _y) Br _y ) ₃ (x is the number of 0.05≤x≤0.3, y: 0.05≤y≤0.3 Number), N¾ CH = CH _{2 (} i. _X) CH ₃ NH _3x Pb (I _(1-x) Br _x ) ₃ (x is 0.05 <χ <0 · 3 real number), NH ₂ C (CH ₃ ) = NH ₂ PbI _x Cl _y (0≤x≤3 real number, 0≤y≤3 real number and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbI _x Br _y (0≤x≤ 3 persons, 0≤y≤3 persons and x + y = 3), NHaCCCHs ^ NHJbCLBr _y O x S, 0≤y≤3 persons and x + y = 3), NH ₂ C (C¾) = NH ₂ PbI _x F _y (real number 0≤x≤3, real number 0≤y≤3 and x + y = 3), NH ₂ C (CH ₃ ) = NH _{2 (1-x)} C¾NH _3x Pb ( I _(1-y) Br _y ) ₃ (x is 0 <χ <1 real number, y is 0 <> single number), NH ₂ C (CH ₃ ) = NH _{2 (1} . _x) CH ₃ NH _3x Pb (I _(1-y) Br _y ) ₃ (x is a real number with 0.05≤χ≤0.3, y is

0.05 <y <0.3 real number), NH ₂ C (CH ₃ ) = CH ₂ _ _x) CH ₃ NH _3x Pb (I _(1-x) Br _x ) ₃ (x is 0.05 <x <(). 3) Real), NH ₂ C (NH ₂ ) = NH ₂ PbI _x Cl _y (real number 0≤x≤3, 0≤y≤3 real and x + y = 3), N¾C (NH ₂ ) = NH ₂ PbI _x Br _y (a real number 0 ≦ x ≦ 3, a real number 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PbCl _x Br _y (0 ≦ _x ≦ ₃ real number, Real numbers of 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (NH ₂ ) = N¾PbI _x F _y (real _{numbers of} 0 ≦ _x ≦ 3, real _{numbers of} 0 ≦ _y ≦ 3 and x + y = 3) , NH ₂ C (NH ₂ ) = NH _{2 (1-x)} CH ₃ NH _3x Pb (I _{(1. Y} ) Br _y ) ₃ (x is a real number where 0 <χ <1, y is 0 <) < Single person), NH ₂ C (NH ₂ ) = NH _{2 (1-x)} CH ₃ NH _3x Pb (I _(1-y) Br _y ) ₃ (x is

0.0 ⁵ ≦ x ≦ 0.3, and y is 0.05 ≦ y ≦ 0. ³ persons) or NH ₂ C (NH ₂ ) = CH _{2 (1} _ _X) CH ₃ NH Pbd _d . Br ^ x may be 0.05).

 In addition, the perovskite compound contained in the first surface layer and the second surface layer contained in

 When the perovskite compound is a solid solution, the perovskite contained in the first surface layer is formed so that a more desirable and specific substance and composition of perovskite compound can be prepared based on the formula (1). It is, of course, possible to design materials of the perovskite compound contained in the compound and the second surface layer or the relative amounts of the first and second surface layers.

[359] Although the first surface layer and the second surface layer both contain perovskite compounds, specific examples are described above, but the perovskite compound-perovskite compound precursor and perovskite compound precursor are described. -Perovskite compound precursors, metal halide precursors-Organic halides, organic halides-Metal halide precursors or organic halides-Even if the material pairs of metal halides, the first surface layer and the second surface layer are All containing perovskite compounds In the same way as the case, the material of the first surface layer and the composition of the perovskite compound for the purpose of combining the composition of the material of the first surface layer with the material of the second surface layer (GM and GM 'are not considered to be removed). Of course, the thickness and the material and thickness of the second surface layer can be controlled. This means that, by the application of thermal and physical forces, the material of the first surface layer and the material of the second surface layer are homogeneously converted into a single perovskite compound. Because of that.

 Specifically, the material and composition of the perovskite compound converted from the first surface layer and the second surface layer, so as to satisfy the material and composition of the perovskite compound described above based on the formula (1), (2) or (3), Of course, the material and the thickness of the surface layer and the material and the thickness of the second surface layer can be controlled. In one specific, non-limiting example, the final conversion from the surface layer is achieved.

The composition of the perovskite compound _{CH 3 NH 3 PbI x Cl y} (0≤x≤3 room number, room number 0≤y≤3 and x + y = 3), CH 3 NH 3 PbI x Br y (0 ≤ x ≤ 3 real number, 0 ≤ y ≤ 3 real number and x + y = 3), CH ₃ NH ₃ PbCl _x Br _y (0 ≤ _x ≤ ₃ real number, 0 ≤ _y ≤ ₃ real number and x + y = 3), CH ₃ NH ₃ PbI _K F _y (0≤x≤3 real number, 0≤y≤3 real number and x + y = 3), NH ₂ CH = NH ₂ PbI _x Cl _y (0≤x ≤ 3 real numbers, 0 ≤ y ≤ 3 real numbers and x + y = 3), NH ₂ CH = N¾PbI _x Br _y (0 ≤ _x ≤ 3 real _numbers , 0 ≤ y ≤ 3 real numbers and x + y = 3 _{), NH 2 CH = NH 2} PbCl x Br y (0≤x≤3 room number, room number 0≤y≤3 and x + y = 3), NH 2 CH = NH 2 PbI x F y (0≤x Real numbers ≤ 3, real numbers 0 ≤ y ≤ 3 and x + y = 3), NH ₂ CH = NH _{2 (1-x)} CH ₃ NH _3x Pb (I ₍ . _Y) Br _y ) ₃ (x is Real number with 0 <χ <1, y is 0 <y <l real number), NH ₂ CH = NH _{2 (lx)} CH ₃ NH _3x Pb (I _(1-y) Br _y ) ₃ ( _X is

0.05≤x≤0.3 real number, y is 0.05≤y≤0.3 real number), NH ₂ CH = CH _2n-x) CH ₃ NH _3x Pb (I _(l . _{] 0} Br _x ) ₃ (x is 0.05≤ NH ₂ C (CH ₃ ) = NH ₂ PbI _x Cl _y (real number 0 ≦ _x ≦ 3, real number 0 ≦ y <3 and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbI _x Br _y (0≤x≤3 real number, 0≤y≤3 real number and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbCl _x Br _y (0≤ x≤3 people, 0≤y≤3 people, and x + y = 3, NH ₂ C (CH ₃ ) = NH ₂ PbI _x F _y (0≤x≤3 people, 0≤y≤3 people Number and x + y = 3), NH ₂ C (CH ₃ ) = NH _{2 (1} _ _x) CH ₃ NH _3x Pb (I ( ₎ Br _y ) ₃ (x is a real number with 0 <χ <1, y Is 0 <y <l), NH ₂ C (CH ₃ ) = NH _{2 (} , _.x) CH ₃ NH _3x Pb (I _{(1. Y)} Br _y ) ₃ (x is 0.05 <x <0.3) Where y is 0.05 <y <0.3 real number), NH ₂ C (CH ₃ ^ CH wCHgNH Pb ^ wBr ^ x is 0.05 ≦ x ≦ 0.3 real number), NH ₂ C (NH ₂ ) = NH ₂ PbI _{: [} Cl _y (0 ≦ x ≦ 3 real number, 0 ≦ _y ≦ 3 real number and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PbI _x Br _y (0 ≦ _x ≦ ₃ real number, 0≤y≤3 room number and x + y = 3), NH 2 C (NH 2) = NH 2 PbCl x Br y (0≤x≤3 room number, 0≤y≤3 room And x + y = 3), NH 2 C (NH 2) = N PbI x F y (0≤x≤3 room number, room number 0≤y≤3 and x + y = 3), NH 2 C (NH ₂ ) = NH _{2 (1-x)} CH ₃ NH _3x Pb (I _{(1 .y>} Br _y ) ₃ (x is 0 <χ <1 real number, y is 0 <y <l real number), NHzQNH ^ NHawCftNH Pb ^ Bi Mx is a real number with 0.05≤x≤0.3, y is

0.05 ≦ _y ≦ 0.3 real number) or NH ₂ C (NH ₂ ) = CH _{2 (} ,. _X) CH ₃ NH _3x Pb (I _0-i0 : Br _x ) ₃ (x is

Of course, the material and thickness of the first surface layer and the material and thickness of the second surface layer can be adjusted to satisfy 0.05≤x≤ (). 3 real number), whereby the first and second surface layers have the same composition. It is, of course, possible to prevent the composition of the inorganic / organic hybrid perovskite compound film produced according to the thickness of the first surface layer and the second surface layer from changing. The first surface layer and the second surface layer may be independent of each other, and may be a dense film, a porous film, or a laminated film thereof, wherein the porous film contains at least one of i ~) and the particles forming the film (grain). These can include island structures that are not connected in series.

 The thickness of the first surface layer and the thickness of the second surface layer can be appropriately adjusted in consideration of the thickness of the inorganic / organic hybrid perovskite compound film required in the device to be manufactured. The thickness and the thickness of the second surface layer may be independently lnm to ΙΟμηι, but the present invention is not limited thereto. As an example of a solar cell, the thickness of the first surface layer and the thickness of the second surface layer are independently lnm to ΙΟμπι. More specifically, it may be 10 nm to 2 μιη, more specifically 10 nm to 5 μηι.

 In the structure (the first structure or the second structure), the surface layer comprises i-v) a coating material (coating film), i-v) containing at least one substance containing at least one substance. Porous membranes, i to v) may contain dense membranes or combinations thereof containing at least one substance.

 [364] Particularly, even if the surface layer itself is not dense, such as a coated (or coated film) or porous membrane with dispersed particles, the first and second surface layers may be converted into a dense inorganic / organic hybrid perovskite compound film. In other words, only the first and second surface layers are formed by simply applying the particles containing at least one material to form the first surface layer and the second surface layer, and a high quality, dense inorganic / organic hybrid perovskite compound film is produced. Commercial utility can be very large.

 [365]

 [366] Hereinafter, a structure except for the surface layer (the first surface layer or the second surface layer) (the first structure or

 The second structure), and the surface layer (first surface layer or second surface worm)

 The manufacturing method is described above.

 [367] The surface layer may be coated with a dispersion of a solution or surface layer material (particulate matter) in which the material of the surface layer is dispersed, or by printing ink or slurry in which the material of the surface layer is dissolved or dispersed, or a material of the surface layer in the substrate. That is, the surface layer may be formed by coating or printing a substrate, a solution, a sultry or an ink (dispersion) containing at least one of the substances, or physically at least one of the above substances. Or by chemical vapor deposition.

 [368] At this time, the coating of the solution or ink may be performed by a coating method which is commonly used in the application of liquid or disperse phase. Specifically, the coating may be a dip coating, a spin coating or a casting. Printing, inkjet printing, electrostatic hydraulic printing, micro-contact printing, imprinting, gravure printing, reverse offset printing or gravure set printing.

[369] Deposition can be performed using physical or chemical deposition. Specific examples include sputtering, electron-evaporation, evaporation (including thermal evaporation), pulsed laser deposition, Plasma assisted chemical vapor deposition, light assisted chemical vapor deposition, thermal chemical vapor deposition, low pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, high temperature chemical vapor deposition, low temperature

 It can be carried out using chemical vapor deposition or the like. However, in electronic materials in which the surface layer is used with a perovskite compound, a coating or deposition method commonly used to form a film or structure of a perovskite compound is used. Of course it can be formed.

 [37] i to v) Even when the surface layer is formed of a very heavy powder layer using dispersed ink or slurry, at least one of the particles is converted into a dense perovskite compound film according to the method provided by the present invention. In such a case, the surface layer may be prepared by mixing the particulate phase of at least one of the substances i to v with a nonsolvent to produce an ink or slurry, and then printing or spreading it on a substrate. Non-polar organic solvents; non-polar organic solvents include pentine, nucleene, cyclonuxene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate ， Acetic acid,

 1,2-dichlorobenzene, tert-butyl alcohol, 2-butanol, isopropanol and

 One or more organic solvents selected from methyl ethyl ketone may be mentioned, but are not limited to these.

[371] i) to V) a method of forming a surface layer by applying a solution (surface layer preparation solution) in which one or more substances selected are selected, and coating of a single solvent solution (surface layer preparation solution) with different vapor pressures. Application of a mixed solvent (surface layer preparation solution), or two-stem application in which a nonsolvent is sequentially applied after applying a solution in which at least one material selected from i) to V) is dissolved. While two-step application is advantageous for the manufacture of dense surface layers, it should be recognized that the present invention also includes surface layers having porous structures or uneven structures such as pillars. As a specific example of the two-step application, the surface layer manufacturing solution can be introduced into the spin center's rotation center, and the rotational speed and the non-solvent application can be achieved. The surface layer is manufactured at the rotation center of the spin coating considering the size of the device to be manufactured. The time interval between when the solution is added and when the nonsolvent is added can be properly adjusted, but in one specific and non-limiting example, the nonsolvent can be introduced 1 to 100 seconds after completion of the surface layer preparation solution. The nonsolvent used for the two-step application may be a nonpolar organic solvent, preferably a nonpolar solvent having a dielectric constant (ε; relative dielectric constant) of 20 or less and substantially a dielectric constant of 1 to 20. Non-solvents are pentane, nuxene, cyclonuxene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid One, two or more of 1,2-dichlorobenzene, tert-butyl alcohol, 2-butane, isopropanol and methyl ethyl ketone may be selected, but not limited thereto.Surface layer preparation method using more detailed solution coating The applicant's published patent No. 2014-0035285, published patent No. 2014-0035284 or This invention may be carried out with reference to Published Patent No. 2014-0035286, the present invention encompasses the entire contents of the present applicant's published Patent No. 2014-0035285, published Patent No. 2014-0035284 and published Patent No. 2014-0035286 .

 As described above, the surface layer may be deposited with the substance or

 It can be formed by the application or printing of a dispersion (including ink), but the surface layer can be formed in the step of producing the perovskite compound precursor.

 In detail, the surface layer may be ii) perovskite compound precursor material or

 iii) In the case of containing metal halide precursors, it can be done in a single process during the manufacture of the precursors and the formation of the surface layer.

 [373] If the perovskite compound precursor is a solvent compound, the perovskite compound; or the organic cationic species according to the stoichiometric ratio of the perovskite compound is a metal cation and a halogen ion; After the perovskite compound solution is prepared by dissolving it in a medium, the perovskite compound solution is applied onto the substrate on which the surface layer is to be formed, and the non-solvent is reapplied onto the coating film to prepare the surface layer containing the precursor material. In other words, the sequential application and drying of the perovskite compound solution and the non-solvent in which the perovskite compound is dissolved in the solvent, which is a heterogeneous solvent, can produce the perovskite precursor precursor and simultaneously form a surface layer. At this time, the non-solvent which is sequentially applied may be a non-polar organic solvent, as described above.

 [375] More specifically, when the metal halide precursor is a solvent compound,

 A metal halide solution is prepared by dissolving a metal halide or a halogen ion according to the stoichiometric ratio of a metal halide or a metal halide in a heterogeneous molecule (GM ') solvent, and then a metal halide solution on a substrate to form a surface layer. The surface layer containing the metal halide precursor can be prepared by applying the non-solvent to the coating film and reapplying the non-solvent, i.e., the sequential application of the metal halide solution and the non-solvent in which the metal halide is dissolved in a heterogeneous solvent. By drying, a surface layer can be formed at the same time as the metal halide precursor is produced. The nonsolvent applied sequentially can be a nonpolar organic solvent, as described above.

 [376] ii) perovskite compound precursors or iii) metal halide precursors.

In the preparation of the containing surface layer, the drying can be carried out at a temperature between room temperature and 90 ° C., stably from room temperature to 70 ^° C., and more stably between room temperature and 50 ° C. Such low temperature drying is carried out with GM combined with perovskite compounds. Alternatively, it is possible to prevent damage to the surface layer by removing GM 'which is not combined with other heterogeneous solvents and perovskite compounds without removing GM' which is combined with metal halides or GM 'which is not combined with metal halides. However, if the solvent is highly volatile, the coating process, such as spin coating, is carried out and practical drying can be achieved.

[377] When the surface layer contains the perovskite compound of i), Surface layers can be formed by using perovskite compound precursors or metal halide precursors. In this case, a dense, low surface finish surface layer can be produced in a simple, low-cost process.

 Ii) An example in which a surface layer containing a perovskite compound is manufactured using a perovskite compound precursor is described.

 [379] Perovskite Compounds Using precursor materials to form perovskite compounds

 In the case of forming the surface layer containing, the substrate is coated with a solution in which the perovskite compound precursor is dissolved or a dispersion or ink in which the perovskite compound precursor is dispersed, and then dried to form a precursor layer. Later, by removing the GM from the bulb, the bulb layer can be converted to the surface layer.

 [380] Alternatively, perovskite compounds or perovskite compounds

 Heterogeneous organic cations, metal cations and halogen ions according to stoichiometric ratios

 After preparing perovskite solution by dissolving in molecular (GM) phosphorus solvent,

 The precursor layer containing the perovskite compound precursor can be prepared by applying a solution of perovskite precursor to the substrate on which the surface layer is to be formed, and reapplying the non-solvent to the coating film. (GM) phosphorus solvents include Ν, Ν-dimethylacetamide, 1,4-dioxane, diethylamine, ethylacetate, tetrahydrofuran,

 Pyridine, methanol, ethanol, 1,2-dichlorobenzene

 (Dichlorobenzene), glycerine (glycerin) and dimethyl sulfoxide (DMSO) and

 One or more may be selected from N, N-dimethylformamide (DMF). The nonsolvent may also be a nonpolar organic solvent as described above.

 [381] The perovskite precursor layer containing the perovskite compound precursor

In order to convert to the surface layer of the compound, it is possible to remove the GM of the bulb by applying energy to the bulb layer. The applied energy may be thermal energy, light energy, vibration energy, etc. The magnitude of the applied energy is perovskite The bond between the compound and the GM is broken and the GM can be volatilized. For example, the precursor layer formed by heating the substrate to 100 ^° C. or more can be converted into a perovskite compound. In addition, if the bulb layer is heated above 130 ° C, it can be converted to perovskite compound in a very short time.In practice, the bulb layer can be converted to 100 to 150 ° C, preferably 130 to 150 ^° C. By heating, the bulb layer can be converted into a perovskite compound layer (surface layer).

 [382] iii) Perovskite compounds are prepared using metal halide precursors.

 An example in which the surface layer containing is produced is described above.

 [383] The surface layer comprises a) a first film containing the first base metal halide precursor.

And b) reacting the first film with an organic halide to produce a surface layer containing a perovskite compound. At this time, the manufacturing method of the metal halide precursor and the first membrane are the same or similar to those described above.

[384] The first membrane of step a) is a coating of dissolved solution of metal halide precursors,

 Metal halide precursors can be formed by the dispersion of dispersed dispersions (inks) or metal halide precursors. Double, application, and especially liquid phase coatings can form dense films with low cost, simple equipment and processes, Commercially preferred.

 [385] When the first film is manufactured by using the coating method, the first film is prepared by the first solution or the metal halide containing a metal halide precursor and a solvent (first solvent) that dissolves the metal halide precursor. It can be carried out by coating and drying a dispersed dispersion (ink) with a precursor. The first solvent that dissolves the metal halide precursor is a solvent that dissolves the metal halide precursor and is easily volatile and removable. As a specific and non-limiting example,

 Ν, Ν-dimethylformamide (N, N-Dimethylformamide, DMF),

 Gamma-butyrolactone (GBL),

 I-methyl-2-pyridone (l-Methyl-2-pytOHdinone),

 Ν, Ν-dimethylacetamide or a mixed solvent thereof.

 The coating of the first solution may be a coating method commonly used to coat and dry the liquid phase to form a film. Specific examples include spin coating, but the present invention is limited by the coating method of the first solution. It is not.

 In this case, when the metal halide precursor is a solvent compound, the metal halide precursor is dissolved by dissolving metal cations and halogen ions according to the stoichiometric ratio of the metal halide or metal halide in a heterogeneous molecule (GM ') phosphorus solvent. After the solution is prepared, the first film can be prepared by applying the metal halide solution onto the substrate on which the surface layer is to be formed and by reapplying the non-solvent to the coating film.

 [388] In other words, the sequential application and drying of a metal halide solution and a non-solvent by dissolving a metal halide in a heterogeneous solvent may produce a metal halide precursor and simultaneously form a first membrane. The solvent is

 Dimethylsulfoxide (DMSO),

 Ν, Ν-dimethylformamide (Ν, Ν-dimethylformamide DMF),

 Ν-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, ΝΜΡ),

 2,2'-bipyridine, 4,4'-bipyridine, Ν, Ν'-dioxide (4,4'-bipyridine, 4,4'-1 1: 1 (11) ^-^^-(0 ^ (1 ， pyrazine (?) ^) ， 1,10-pananthrin

 (1,10-phenanthroline), 2-Methylpyridine or poly (ethylene oxide), and the non-solvent applied sequentially may be a nonpolar organic solvent, as described above.

[389] The thickness of the first layer may be lnm to Ιμιη, specifically, 5 nm to 800 rnn. More specifically 300 nm to 800 run, more specifically 300 to 600 nm. Ιμηι is an extremely thick membrane of metal halide precursors

 Reactivity (replacement with organic halides) can be implemented as it occurs very quickly and easily.

After application of the first solution on the substrate, drying of the first membrane may be carried out. The drying does not damage the membrane and the temperature is low enough to allow easy volatilization of the solvent. As a specific example, the drying may be performed at a temperature of between 90 ° C. and stable at 70 ^° C. However, if the solvent is highly volatile, a coating process such as spin coating may be performed and practical drying may occur. As a matter of course, such drying may be selectively performed if necessary, and of course, drying may be performed at low temperatures so that the GM 'bound to the metal oxide is not removed from the first membrane.

 In the step of producing a perovskite compound membrane by reacting the first membrane with an organic halide, the organic halide is the same or similar to that described above.

 [392] The reaction between the first membrane and the organic halide may be solid reaction, liquid reaction, vapor reaction, or a mixed reaction thereof or a sequential reaction thereof, depending on the state of the organic halide reaction. GM's and precursors to precursors

 As the substitution reaction between the organic halides is extremely easy and active, the perovskite compound film can be prepared by an easy method of simply applying an organic halide-dissolved solution on the first membrane. In the step of applying a solution containing an organic halide to the first film, the first film is

 It can be converted into a perovskite compound film.

 As a specific and practical example, after forming the first film, the perovskite is coated with a second solution containing a solvent (second solvent) that dissolves the organic halide and organic halide on the first film. Compound films can be prepared.

 [394] However, in order to prevent the lower membrane from dissolving again when the second solution is applied,

 It is better to choose a solvent in which the organic halide solution does not dissolve the metal halide precursor. In this respect, 12 solvents that dissolve organic halides are t-butyl alcohol, 2. -Butanol, 2-Butanol, Isobutyl alcohol, 1-Butanol, Isopropanol, 1-Propanol, Ethanol and Ethanol More than one can be selected from.

 [395] The application of the second solution is also a coating method commonly used for coating and drying the liquid phase to form a film. Specific examples include spin coating, but the present invention is limited by the application method of the second solution. It doesn't work.

 [396]

 [397] The first structure may include a first substrate capable of supporting the first surface layer.

The second structure may comprise a second substrate capable of supporting the second surface layer, ie The first structure may comprise a first substrate and a first surface layer located on the first substrate and forming a surface (one surface). The second structure is also located on the second substrate and on the second substrate and the surface thereof. It may comprise a second surface layer to form.

 [398] In the macroscopic shape, the first or second substrate (hereinafter referred to as substrate) may be the shape of a wafer or film, taking into consideration the physical shape of the designed electronic device, optical device or sensor. This may be patterned.

 Physically, the substrate may be a rigid substrate or a flexible substrate.

 [400] Physically, the substrate is selected from semiconductors, ceramics, metals, polymers or these

 The above materials may be stacked layers, which may be laminated layers.A non-limiting example of a specific laminated body, different semiconductor materials may be layered, stacked laminates, and different ceramic materials may be stacked. Sieves, semiconductors, and metals each form a layer, and a stacked layer, a semiconductor, and a ceramic layer each have a layered layer.

 [401] A non-limiting example of a semiconductor substrate (first substrate or second substrate), silicon (Si),

 Group IV semiconductors containing germanium (Ge) or silicon germanium (SiGe)

 Group 3-5 semiconductors including gallium arsenide (GaAs), indium phosphorus (InP) or gallium phosphorus (GaP) Group 2-6 semiconductors including cadmium sulfide (CdS) or zinc telluride (ZnTe)

 Group 4-6 semiconductors, including lead sulfide (PbS), or two or more materials selected from them, each layer may be a stacked laminate. As one non-limiting example of a ceramic substrate (either a first substrate or a second substrate), Semiconductor oxides, semiconductor nitrides, semiconductor carbides, metal oxides, metal carbides, metal nitrides, or two or more materials selected from them, each layer may be a laminated laminate, wherein semiconductor oxides, semiconductor nitrides, or semiconductor carbides May comprise Group 4 semiconductors, Group 3-5 semiconductors, Group 2-6 semiconductors, Group 4-6 semiconductors, or mixtures thereof.

 As a non-limiting example of the second substrate, a transition metal, a metal or a combination thereof, including a noble metal, may be Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb. , Ta, Cr, Mo, W, Mn, Te, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, or mixtures thereof. , Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Al, Ga, In, TI, Ge, Sn, Pb, Sb, Bi, Po or mixtures thereof Non-limiting examples of flexible polymer substrates (first substrate or second substrate) include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), poly Propylene (PP), triacetylcellose (TAC), polyethersulfone (PES), polydimethylsiloxane (PDMS) or combinations thereof.

 [402] Crystallographically, the substrate (the first substrate or the second substrate) is monocrystalline, polycrystalline or

It may be amorphous, or a mixed phase with common crystalline and amorphous phases. If the substrate is a laminate of two or more layers, each layer may be independently monocrystalline, polycrystalline, amorphous, or mixed phases. In one embodiment, the substrate (the first substrate or the second substrate) may be a semiconductor substrate (including a wafer) such as a Si substrate; a Si semiconductor substrate having a surface oxide film or a silicon on substrate (SOI).

Semiconductor substrates (including wafers) on which semiconductor oxide layers, such as substrates, are laminated; Si semiconductor substrates (including wafers) such as Si semiconductor substrates with metal thin films and surface oxide films or Si semiconductor substrates with patterned metal films formed therein (including wafers); amorphous oxide substrates such as glass or Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP),

 Triacetylcellose (TAC), polyethersulfone (PES) or

 Flexible polymer substrates such as polydimethylsiloxane (PDMS).

 At this time, the first structure is composed of the first substrate and the first surface layer, the second structure

 Even if it consists of a second substrate and a second surface layer, it should be recognized that the first surface layer and the second surface layer can be converted into an organic / inorganic hybrid perovskite compound film according to the idea of the present invention. Substrate

 It also includes the case where the surface layer consists only.

 [405] A substrate (a first substrate or a second substrate) may be provided to physically support the surface layer and to physically handle the structure, and to serve as a transfer member for transferring the physical force to the surface layer. However, if the components provided under the first surface layer or the second surface layer can serve as these substrates, the substrates may not be provided. In one example, pn junctions in the surface layer lower components may be used. A semiconductor substrate or a multilayer inorganic thin film formed may be present.

 [406] According to the basic structure of a device having an organic / inorganic hybrid perovskite compound film, such as an electronic device such as a transistor, a light emitting device for generating light, a memory device, a light emitting device (solar cell), etc., system 1 The lower component of the first surface layer of the structure and the lower component of the second surface layer of the second structure may be appropriately modified, i.e., in known device structures, around organic / inorganic hybrid perovskite compound films, Underlying components may be formed under the first surface layer of the first structure, and overlying components may be formed under the second surface layer of the crab structure.

[407] For example, when the device to be manufactured is a light emitting diode having an organic / inorganic hybrid perovskite compound film as a light emitting layer, the basic structure of the light emitting diode is roughly an electrode-an n-type semiconductor (electron transporter)-light emitting layer- P-type semiconductor (hole transporter)-According to the second electrode, the first structure can have the structure of the first substrate-the first electrode-n-type semiconductor-the first surface worm, the second structure is the system 2 substrate-second Electrode-type P-semiconductor-the second surface layer may have the structure. As described above, when the n-type semiconductor or the p-type semiconductor can serve as a substrate, the first structure is n-formed with the first electrode formed. It may have a structure of a type semiconductor-first surface layer, the second structure is a structure of the p-type semiconductor-second surface layer on which the second electrode is formed. Of course you can.

 For example, when the device to be manufactured is a resistance change type memory using an organic / inorganic hybrid perovskite compound film, the basic structure of the resistance change type memory is a first electrode, a semiconductor, and a second electrode. The first structure may have a structure of a first substrate-first electrode-first surface layer, and the second structure may have a structure of a second substrate-second electrode-second surface layer. The first electrode may be metal strips spaced apart in one direction, and the second electrode may be metal strips spaced apart in one direction so as to be orthogonal to the metal strips of the first electrode. When the two structures are stacked so that they meet the surface worm, the first surface worm and the second surface layer may each be patterned so that they are located only in the region where the metal strip of the first electrode and the metal strip of the second electrode cross each other (including orthogonal). Yes, of course.

 [409] As described above, an electronic device such as a transistor, a light emitting device for generating light, a memory device, a photovoltaic device (solar cell), and the like, are those in the related fields. It is obvious that by designing and modifying the first surface layer lower component of the structure and the second surface layer lower component of the second structure as appropriate for the device, i.e. the electronic device, optical device or In the basic structure necessary for driving such as a sensor, a desired device can be manufactured by forming other structures (structures) other than the perovskite compound film between the substrate and the surface layer.

 [410]

 [411] More specifically, the use of organic / inorganic hybrid perovskite compounds with commercially important oil / inorganic hybrid perovskite compounds in solar cells provided with light absorbers will be described in more detail.

 [412] The structure example of the first structure and the second structure is described in detail by assuming that the structure providing the hole movement path is the second structure, and the structure providing the electron movement path is the first structure. When the first structure provides a hole moving path, the first structure may have a structure of a second structure described below, and likewise, the second structure may have a structure of the first structure described above.

 The first structure may include at least a first substrate, which is a support for supporting the first surface layer. The first structure may also be a perovskite compound of a device (such as a solar cell) to be manufactured on the first substrate. In some embodiments, the first structure may further include a first substrate; a first electrode positioned on the first substrate; and an electron carrier positioned on the first electrode.

 That is, the first structure may include a laminate in which a first substrate, a first electrode, an electron carrier, and a first surface layer are sequentially stacked.

The first substrate may be a rigid substrate or a flexible organ. In one embodiment, the first substrate may be a rigid substrate including a glass substrate or polyethylene terephthalate (PET); polyethylene naphthalate (PEN): Polyimide (PI); Polycarbonate (PC); polypropylene (PP); triacetylcellose (TAC);

 It may be a flexible substrate including polyether sulfone (PES) or the like. However, it is a matter of course that the present invention cannot be limited by the type of the first substrate.

The first electrode may be a conductive electrode that is ohmic-conjugated with an electron carrier.

 Any material that is commonly used as an electrode material of a front electrode or a back electrode in a solar cell can be used.

 In the case of an electrode material, the first electrode may be one or more materials selected from gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and combinations thereof. When the first electrode is a transparent electrode, the first electrode is fluorine-containing tin oxide (FTO; Fouorine doped Tin Oxide), indium doped tin oxide (ΠΌ; Indium doped Tin Oxide), ZnO, CNT (carbon nano-lube), graphene It may be a non-mechanical conductive electrode such as (Graphene), or may be an organic conductive electrode such as PEDOT: PSS. If you want to provide a transparent solar cell, the electrode (first electrode and second electrode) and the substrate (first substrate and low It is preferable that both the transparent electrode and the transparent substrate are used. Also, when the electrode (first electrode or second electrode) is an organic mechanical conductive electrode, it is better than when providing a flexible solar cell or a transparent solar cell.

 The first electrode may be formed by depositing or applying a substrate electrode material.

 It can be formed using physical vapor deposition or chemical vapor deposition and can be formed by thermal evaporation. Coating is applied to the substrate by dissolving the electrode material or the dispersion of the electrode material on the substrate. This can be done either by drying or optionally by thermally treating the dried film. However, of course, the first electrode can be formed using the method used to form the front electrode or the back electrode in a conventional solar cell.

 The electron transporter located on the first electrode may be an electron conductive organic layer or an inorganic layer. The electron conductive organic material may be an organic material used as an n-type semiconductor in a conventional organic solar cell. ， Electroconductive organic material is fullerene (C60, C70, C74, C76, C78, C82, C95),

PCBM ([6,6] -phenyl-C61butyric acid methyl ester)) and C71-PCBM, C84-PCBM, PC ₇₀ BM ([6,6] -phenyl C ₇₀ -butyric acid methyl ester)

 Fulleren-derivative, polybenzimidazole (PB I),

 It may include PTCBI (3,4,9, 10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ (tetra uorotetracyanoquinodimethane), or a mixture of these stones. It may be an electron conductive metal oxide used for the transfer. In one embodiment, the electron conductive metal oxide may be an n-type metal oxide semiconductor. Non-limiting example of n-type metal oxide semiconductor, Ti oxide, Zn oxide, In oxide, Sn oxide,

W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, A1 oxide, Y oxide, Sc oxide, Sm oxide ， One or more materials selected from Ga oxides, In oxides and SrTi oxides may be mentioned, and their mixtures or composites thereof may be mentioned.

[419] In its structure, the electron transporter may be a porous layer (porous membrane) or a dense layer (dense film). The dense electron transporter may be a film of an electron conductive organic material or a film of an electron conductive inorganic material described above. The porous electron transporter consists of particles of the above-mentioned electron-conducting inorganic material, and can be a sclera. The thickness of the electron transporter can be 50 nm to ΙΟμπι, specifically, 50 nm to 100Onm.If the electron transporter is porous, its specific surface area is It can be 10 to 100 m ² / g, and the average diameter of the metal oxide particles forming the electron transporter can be 5 to 500 ran. The porosity (walking porosity) of the porous electron transporter is 30% to 65%, specifically It can be 40% to 60%.

 [420] In the case where the electron carrier has a porous structure, between the first electrode and the electron carrier

 The electron transport film may be further equipped. The electron transport film may serve to prevent direct contact between the light absorber and the first electrode, and at the same time, to transport electrons. The electron transport film may be formed on an energy band diagram or in a porous manner.

 It is acceptable if the electrons are spontaneously movable from the metal oxide to the first electrode through the electron transfer film. In one non-limiting and specific example, the electron transfer film may be a metal oxide thin film, and the metal oxide of the metal oxide thin film may be a metal of the porous metal oxide. The oxide may be the same material as the oxide. In detail, the metal oxide thin film may be formed of Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide. It may be one or more selected from Yr oxides, La oxides, V oxides, A1 oxides, Y oxides, Sc oxides, Sm oxides, Ga oxides, In oxides, SrTi oxides, ZnSn oxides, their complexes and their complexes. The thickness of the electron transport film can be substantially greater than lOnm, more substantially lOnm to lOOnm, and more substantially 50nm to lOOnm.

 The electron transporter may be formed by application or deposition. Specifically, the electron transporter may be dried by applying a solution in which the electron transporter material is dissolved or a dispersion (or slurry) in which the electron transporter material is dispersed, or selectively heat-processing the dried product. Can be manufactured. Deposition can be formed using physical vapor deposition or chemical vapor deposition.

 [422] The porous electron transporter, for example, is more specifically described, the electron transporter

Slurry containing metal oxide particles may be applied over the first electrode, dried and heat-treated. The coating of the slurry may be carried out by screen printing; Spin coating (Spin coating); bar-coated (Bar coating); gravure-coated ^'(Gravure coating); It can be carried out by one or more methods selected in Blade coating; and -Roll coating.

However, the electron transporter can be formed using a method of forming a porous electron transporter of a metal oxide known from a conventional dye-sensitized solar cell or an organic solar cell. Yes, of course.

 The first surface layer may refer to an area exposed from the first structure to the surface in contact with the atmosphere when viewed from the lamination direction based on the lamination direction from the electron carrier to the first substrate. The first structure with the first surface layer comprises: i) organic / organic hybrid perovskite compound, ii) organic / organic hybrid perovskite compound precursor, iii) metal halide precursor, iv) organic halide and V) can mean a structure in which the surface area containing at least one of the metal halides i to v) exists.

 The first surface layer may be a dense film, a porous film, or a red-filled film of an idol, or may be a coating film coated on the surface of an electron transporter. The porosity (apparent porosity) of the porous film may be greater than 0 to 65%.

 In detail, when the electron transporter is a dense layer, the first surface layer may be a dense film, a porous film, or a laminated film thereof positioned on the electron transporter dense layer.

 [427] In detail, in the case where the electron transporter is a porous layer, the first surface layer is a coating film coated on the surface of the electron transporter including pores by the pores, the pores of the electron transporter, filling the pores of the electron transporter, and covering the electron transporter. It may be a porous film covering the electron transporter or a lamination film of the dense and porous membranes filling the pores of the electron transporter.

 In this case, the porous membrane may include an island structure in which the particles (grains) forming the membrane are not continuously connected to each other, i.e., i to v, a material of the first surface layer containing at least one substance. When the pore-filled structure is collectively referred to as a composite layer, it is made of a material of the first surface layer, and the protrusion structure projected on the composite layer may also belong to the category of the porous membrane. Such an protrusion structure is disclosed in the present application. Patent Publication No. 2014-0035284 or Publication Patent

 Including the pillar structure described in 2014-0035286, the present invention is disclosed in Korean Patent Publication No. 2014-0035285, Patent Publication No. 2014-0035284 or published patent

 It should be recognized that the information contained in heading 2014-0035286 is incorporated in its entirety.

 [429] The thickness of the first surface layer is the light absorber designed for the solar cell to be manufactured (or

 The amount or thickness of the light absorbing layer) may be appropriately adjusted.

 As a specific and non-limiting example, the thickness of the first surface layer positioned on the electron transporter of the dense film structure may be lnm to ΙΟμπι.

 In another specific and non-limiting example, in the case of a porous electron transporter, the surface layer fills the pores of the electron transporter and covers the upper part of the electron transporter, and may have a structure of a sclera, a dense film, or a lamination film thereof. At this time, the thickness of the film covering the upper part of the electron carrier may be lmn to ΙΟμπα.

 The first surface layer can be manufactured using the above-described manufacturing method of surface worms.

[433] The second structure comprises i) inorganic / organic hybrid perovskite compounds described above, ii) inorganic / organic hybrid perovskite compounds precursors, iii) metal halide precursors, iv) It may be a structure having a second surface layer containing at least one of the organic halides and i) v) of the metal halides.

 The second structure may include a second substrate, which is a support for supporting at least the second surface layer of the system. The second structure may also be a perovskite compound of an element (such as a solar cell) to be manufactured on the second substrate. The components located under the phosphor absorber may be preformed. In one embodiment, the second structure may have a structure of a second substrate, a second electrode on the second substrate, and a second surface layer on the second electrode. The second structure may have a structure including a second substrate; a second electrode positioned on the second substrate; a hole carrier positioned on the second electrode; and a second surface layer positioned on the hole carrier.

 The second substrate may be a rigid substrate or a flexible substrate. Further, the second substrate may be a transparent substrate. In one embodiment, the second substrate may include a glass substrate.

 Rigid substrates or polyethylene terephthalate (PET);

 Polyethylene naphthalate (PEN): polyimide (PI); polycarbonate (PC);

 It may be a flexible substrate including polypropylene (PP); triacetylcellose (TAC); polyethersulfone (PES) and the like. However, of course, the present invention cannot be limited by the type of the second substrate. .

 [436] The second electrode may be a conductive electrode that is ohmic-contacted with the hole carrier.

 Any material that is commonly used as an electrode material of a front electrode or a back electrode in a solar cell may be used. As one non-limiting example, the second electrode may be a back electrode.

 In the case of an electrode material, the second electrode may be one or more materials selected from silver, silver, platinum, paraffins, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide and combinations thereof. For example, when the second electrode is a transparent electrode, the second electrode is fluorine-containing tin oxide (FTO; Fouorine doped Tin Oxide), indium doped tin oxide (ΠΌ; Indium doped Tin Oxide), ZnO, CNT (carbon nano-lube) ), It may be an inorganic conductive electrode such as graphene, and may be an organic conductive electrode such as PEDOT: PSS. In order to provide a transparent solar cell, the second electrode is preferably a transparent electrode, and the second electrode is an organic machine. Conductive electrodes are better than when providing flexible solar cells or transparent solar cells.

 [437] The second electrode may be formed by vapor deposition or application on a rigid substrate or a flexible substrate. The deposition may be performed by using physical vapor deposition or chemical vapor deposition. It can be formed by thermal evaporation. The coating can be carried out by applying a solution of the electrode material or a dispersion of the electrode material to the substrate, followed by drying or optionally thermally treating the dried film. Of course, the two electrodes can be formed using the method used to form the front electrode or the back electrode in a conventional solar cell.

In the case where the second structure includes a hole transporter, the hole transporter may be an organic hole transporter, an inorganic hole transporter, or a stack thereof. [439] When the hole transporter includes an inorganic hole transporter, the inorganic hole transporter may be a p-type semiconductor, an oxide semiconductor, a sulfide semiconductor, a halogenated semiconductor, or a combination thereof having hole conductivity.

Examples of oxide semiconductors include NiO, CuO, CuA10 ₂ , CuGa0 ₂ , and examples of sulfide semiconductors include PbS and halogenated semiconductors such as Pbl ₂ , but the present invention is an inorganic hole. It is not limited by the carrier material.

 [441] The hole transporter may be a porous layer (porous membrane) or a dense layer (dense membrane). A dense hole transporter may be a dense film of a p-type semiconductor as described above, and the porous hole transporter may be a p-type semiconductor. It is composed of particles, and it has a hole transporter of the porous membrane at the same time as the electron transporter of the porous membrane, and the pore angle of the hole transporter of the electron transporter is filled by the light absorber perovskite compound. A structure in which a film of a perovskite compound may be interposed between an electron transporter and a hole transporter is a device including a solar cell, in which a laryngeal structure in which a first structure and a second structure are independently manufactured with each other according to an embodiment of the present invention is bonded. Is a structure that can be implemented by the features that are manufactured.

[442] The thickness of the inorganic hole transporter may be 50 n to ΙΟμηι, specifically lOrnn to lOOOnm, more specifically 50nm to lOOOnm. If the major transporter is porous, its specific surface area may be 10 to 100 m ² / g. The average particle diameter of the p-type semiconductor particles forming the hole transporter can be 5 to 500 rmi. The porosity (apparent porosity) of the porous hole transporter can be 30% to 65%, specifically 40% to 60%.

 [443] When the hole transporter includes an organic hole transporter, the organic hole transporter may include an organic hole transporter, specifically, a single molecule and a molecular organic hole transporter (hole conducting organic material). Organic used in conventional non-conductor-based solar cells using quantum dots as dyes

 If it is a hole transport material, it can be used. However, perovskite compound

 Polymer organic hole transport materials are preferred in terms of energy matching and stability with light absorbers.

 [444] A non-limiting example of a monomolecular to small molecular organic hole transport material,

 Pentacene, coumarin 6,

 3- (2-benzothiazolyl) -7- (diethylamino) coumarin), zinc phthalocyanine (ZnPC), copper phthalocyanine (CuPC), titanium oxide phthalocyanine (TiOPC),

 Spiro-MeOTAD (2,2 ', 7,7'-tetrakis (N, N-p-dimethoxyphenylamino) -9,9'-spirobifluorene), F16CuPC (copper (II)

 1,2,3,4,8,9,10,11, 15,16,17,18,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and

One or more of N 3 (cis-di (thiocyanato) -bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) -ruthenium ⁽ n)), but is not limited thereto. .

[445] The organic hole transport material is preferably a polymer (hole conducting polymer).

py⁾⁾⁾,, ^thⁱo^llene vⁱn^lene

py ⁾⁾⁾ ,, ^t h ⁱ o ^ll ene v ⁱ n ^l ene

^{¾pp J yJ f yyyy) X (} ()) (() ,, 33oee F3o3dodecs l oc tl t h i ohene f DTo l dec lt h i hnDDT> l 4 --- yppypyypyyy)) ()) ((: - ( ,, 3O5eoe30ooc ^{tl ti} oee PT2th ^l hex ^l xhn ^l ene v ⁱ n ^l ene pT ^l hhn ------ "yyypypy ^y yx ^{) (lf} , ^t oc ^t oe veHPFVo ^l me ^t ox d ⁱ meh ^ll x ^l hn ^l ene ⁱ n ^l en ME2 ^h ---- For example, the hole transporter may include one or more selected additives from tertiary butyl pyridine (TBP), lithium bis (trifluoro methanesulfonyl) imide (LiTFSI), and tris ( ^2- (lH-pyrazol-l-yl) pyridine) cobalt (ni). And may contain from 0.05 mg to lOOmg additive per lg organic hole transport material. However, the present invention may not be limited by the presence or absence of an additive in the hole transporter, the type of additive and the content of the additive. .

 [448] The hole transporter is an inorganic hole transporter which is a dense film of the p-type semiconductor described above; Inorganic hole transporter which is composed of p-type semiconductor particles; inorganic hole transporter of porous membrane and inorganic hole transporter which is dense membrane; or inorganic hole transporter of dense or porous membrane and organic hole transporter which is dense membrane May contain;

 The hole carrier forming step may be performed by applying and drying a solution containing an organic hole transport material (hereinafter, referred to as an organic hole transport solution) when the hole transport material is organic. The application can be carried out by spin coating. The solvent used for the formation of the hole carrier can be any solvent in which the organic hole transport material is dissolved. However, the hole carrier can be used to form an n-type organic layer or a p-type organic layer in organic solar cells. Of course, it can be formed using the method used.

 The hole carrier forming step may be formed by application or deposition when the hole carrier is an inorganic p-type semiconductor. Specifically, a solution in which the electron carrier material is dissolved or a dispersion (or slurry) in which the electron carrier material is dispersed may be formed. It may be applied by drying or optionally by heat treatment of the dried product. Deposition may be formed using physical vapor deposition or chemical vapor deposition.

 [4 1] For example, the porous hole transporter, more specifically, the hole transporter

 A slurry containing p-type semiconductor particles on the second electrode may be coated, dried and heat treated. The slurry may be coated by screen printing; Spin coating; Bar coating; Gravure coating; It can be carried out by one or more methods selected in Blade coating; and -Roll coating.

 After forming the hole carrier, the second structure can be manufactured by forming a surface layer using the above-described method of manufacturing the surface worm on the hole carrier.

 [453] For example, manufacturing a solar cell using the first structure and the second structure includes the use of a device.

 Although a specific example of the manufacturing method is provided, of course, the device manufactured in the present invention cannot be limited to the solar cell.

 [454]

[455] In an example of the above-described perovskite compound-based solar cell, only the first substrate, the second substrate, and the first electrode and the second electrode are implemented by the transparent substrate and the transparent electrode (transparent conductive material), In this case, the perovskite compound-based transparent solar cell is conventionally used for non-perovskite compound-based. The four-terminal tandem structure can be realized by simply stacking them on top of the solar cell.

 In addition to the stacked structure of each of the individually operated solar cells, the fabrication of devices using the first and second structures provided in the present invention is performed with other devices not based on the perovskite compound.

 Very advantageous for hybridization.

 [457] That is, the first surface layer of the lower 11 structure and the second surface worm of the second structure are single and integral.

 It is converted into an organic / organic hybrid perovskite membrane, and with the first structure

 As the second structure constitutes a device, the perovskite-based device is formed by forming another conventional device under the surface layer (the first surface layer or the second surface layer) of the structure (the first structure or the second structure). Hybrids between different devices can be made extremely easy.

 [458] The lower surface layer of a structure, for example a two-terminal tandem type battery

 A specific example of hybridization between a perovskite compound-based device and a non-perovskite compound-based device is described above by changing components. However, an example of a 2-terminal tandem type positive battery is described. It provides an example of effective hybridization and, at the same time, provides a clear understanding of the complexation with conventional non-perovskite compound-based devices. Based on the specific hybridization example, the hybridization with various non-perovskite compound-based devices will be easily implemented.

 [459] Hereinafter, the ratio to be combined with a perovskite compound-based solar cell

 Hybridization is described above on the basis that the components of the perovskite compound based solar cell are formed in the second structure.

 [460] Perovskite compounds, compared to other solar cell light absorber materials

 It absorbs light of relatively short wavelengths to produce photoelectrons and light holes. Therefore, when combined, the perovskite compound-based solar cell is located on the light receiving side, and the non-perovskite compound-based solar cell is based on the perovskite compound The light absorbing layer (first light absorbing layer) of the perovskite compound is preferably located at the bottom of the solar cell. Specifically, the light absorbing layer (second light absorbing layer) of the non-perovskite compound located at the bottom is at least 800 nm. It is preferable to include a light absorber that absorbs light in the above wavelength band to generate photoelectrons and light holes.

In this aspect, the first structure includes a first substrate, a transparent substrate, a first electrode, a transparent electrode positioned on the first substrate, a charge carrier (electron carrier or hole carrier) located on the first electrode, and a charge carrier positioned on the first electrode. In other words, the second structure, which includes the basic structure of the device to be compounded, is located on the second electrode and the second electrode, and includes an inorganic light absorbing layer and an inorganic light that absorb electrons of more than 800 nm to generate electrons and holes. It may comprise a bonding layer located on the absorbent layer and a second surface layer located on the bonding layer. [462] The first surface layer and the second surface layer are laminated so that the first surface layer and the second surface layer contact each other, and then energy and physical forces are applied to the first surface layer and the second surface layer.

 By converting to perovskite compound film,

 Crab 2 Electrode-Inorganic Light Absorption Layer-Bonding Layer-Perovskite Compound Membrane

 A solar cell having a two-terminal tandem structure comprising a light absorption layer-a charge carrier-a transparent electrode-a transparent substrate can be manufactured.

 More specifically, the first structure includes a first substrate that is a transparent substrate, a first electrode that is a transparent electrode positioned on the first substrate, a first charge carrier disposed on the first electrode, and a first surface layer located on the first charge carrier. Together with the first structure, the second structure is located on the second electrode, the second electrode, and is located on the inorganic light absorbing layer, the inorganic light absorbing layer, which absorbs light of 800 nm or more to generate electrons and holes. The bonding layer, the second charge carrier located on the junction layer, and the second surface layer located on the second charge carrier may include a first charge carrier and a second charge carrier to move the complementary charges to each other. If the charge carrier is an electron carrier that moves electrons, the second charge carrier may be a hole carrier that moves holes.

 The inorganic light absorbing layer may be a non-perovskite compound based light absorbing layer.

Specifically, the inorganic light absorbing layer may be a baseless conductive layer. The inorganic semiconductor of the baseless conductive layer may be a group 4 semiconductor including silicon (Si), germanium, silicon germanium (SiGe), and the like; Gallium Arsenide (GaAs), Phosphorus (InP), Gallium Phosphorus (GaP), Gallium Indium Phosphorus (GaInP ₂ ),

 Group 3-5 semiconductors, including indium gallium arsenide (InGaAs), etc .; Group 2-6 semiconductors, including cadmium sulfide (CdS) or zinc telluride (ZnTe); or Group 4-6, including lead sulfide (PbS) Metal chalcogenide semiconductors including semiconductors, copper-sulphur-chalcogen compounds, copper-sulphurium-gallium-chalcogen compounds, and the like.

 [465] Crystallographically, the inorganic light absorbing layer may be monocrystalline, polycrystalline or amorphous.

 [466] The inorganic light absorbing layer may be a layer of a single non-conductive material, but is not limited thereto. The inorganic light absorbing layers of different materials may have a random structure in which the inorganic light absorbing layer itself is joined through a tunneling junction. Yes, of course.

 [467] The light absorption layer may have a p-n junction or a p-i (intrinsic) -n junction structure.

 Intrinsic semiconductors containing quantum dots may also be provided as light absorbing layers. For example, intrinsic semiconductor layers containing quantum dots may include Si, Ge, SiGe,

 Phosphide (P) compound semiconductor, arsenide (As) compound semiconductor, or

 The quantum dots of the nitride-based (N) compound semiconductor may be formed. The semiconductor layer containing such quantum dots may be manufactured by using a quantum dot forming method commonly used in the field of inorganic solar cells. Self-assembled quantum dot method such as self-assembled quantum dots can be used.

The bonding layer is a layer which bonds the inorganic light absorbing layer and the light absorbing layer of the perovskite compound to each other. The bonding layer is generally used for bonding between different light absorbing layers in band gaps in a known tandem structured solar cell. Material and thickness. As is known, the bonding layer may be a conductive layer or a tunnel bonding layer. More specifically, the bonding layer may be a thin light-transmissive metal layer such as Aii, Ag, Al, Cu, Sn: In ₂ 0 ₃ (ITO), Oxide transparent conductive layers such as Sb: Sn0 ₂ (ATO), Al: ZnO (AZO), carbon layers such as graphene, graphene oxide, etc.,

 PEDOT: An organic conductive layer such as PSS, or an amorphous oxide semiconductor layer such as titanium oxide, molybdenum oxide, or a composite layer thereof, but is not limited thereto. The thickness of the bonding layer is about a5 nm to 50 nm. The thickness of the layer is substantially 0.5 nm to 20 nm.

[469] Hereinafter, an embodiment for hybridization with a solar cell based on a pn junction such as silicon is provided. However, this embodiment provides a practical example for hybridization with a solar cell based on a pn junction. For a clearer understanding of hybridization, the practitioner working in tandem-type solar cells can easily implement hybridization with various solar cells, including pin junction-based solar cells, based on the following practical examples. It is obvious that it can be done.

 The first structure is a first substrate, which is a transparent substrate, and a transparent electrode disposed on the first substrate.

 And a first charge carrier positioned on the front electrode (first electrode), the front electrode (first electrode) and providing a path for the movement of photocurrent, and a first surface layer positioned on the first charge carrier.

 In addition, the two structures electrically connect to the semiconductor substrate having the back surface field (BSF) layer forming the emitter layer and the backfield, and the BSF layer of the semiconductor substrate.

 A second layer, which may include a back electrode (second electrode), a junction layer located on the emitter layer, a second charge carrier located on the junction layer, and a second surface located on the second charge carrier providing a path of light current May contain a worm.

 [472] As a specific example, the semiconductor substrate is doped with a first conductive impurity on the surface thereof.

 The first conductive layer may be formed, and the second conductive layer may be formed by doping the second conductive impurity to the opposite surface of the surface on which the first conductive layer is formed. The second conductivity type is the first conductivity layer.

 If the emitter layer, the lower 12-conductor layer may be BSF-filled.

 If the emitter layer, the first conductive layer may be BSF-filled.

 [473] If the first conductivity type is P type, the second conductivity type takes over, which is complementary to the first conductivity type.

 N type, and the first conductive type is N type, the second conductive type is P type. In addition, when the first conductive type impurity is a donor type impurity, the second conductive type impurity is an adapter type impurity and the first type conductive impurity The second conductive impurity is a donor-type impurity in the case of the ear impurity impurity. As is known, for example, a silicon semiconductor may be boron (B) or aluminum (A1), and a donor impurity. Silver phosphorus (P) or germanium (Ge).

In detail, the first structure is a transparent substrate, the first substrate is a transparent electrode located on the first substrate, And a first charge carrier positioned on the front electrode (first electrode), the front electrode (first electrode) and providing a hole transport path, and a first surface layer located on the first charge carrier. The structure is an n-type semiconductor substrate or an n-type semiconductor on which a p-type impurity layer is doped on the surface to form a p-type emitter layer, and an n-type impurity is doped on an opposite surface of the surface on which the p-type emitter layer is formed. A back electrode electrically connected to the BSF layer of the substrate, a junction layer on the p-type emitter layer, a second charge carrier located on the junction layer and providing an electron transport path, a second charge carrier located on the second charge carrier It may include a surface layer.

 [475] Independently of this, in detail, the first structure is positioned on the front electrode (first electrode) and the front electrode (first electrode), which are transparent electrodes positioned on the first substrate and the first substrate, which are transparent substrates. It may include a first charge carrier providing a path and a first surface layer located on the first charge carrier. In addition, the system structure 2 is doped with n-type impurities on the surface to form a π-type emitter layer, and η type. Ρ-type semiconductor organs doped with ρ-type impurities on the opposite side of the surface where the emitter layer is formed, and the back electrode electrically connected to the ρ-type semiconductor based BSF layer on which the ρ-type BSF layer is formed. And a second charge carrier located on the junction layer, a second charge carrier located on the junction layer and providing a hole migration path, and a second surface layer located on the second charge carrier.

 As is known, a dielectric film such as an antireflection film and / or a passivation film may be formed on the surface of the substrate on which the BSF layer of the semiconductor substrate is formed.

 The electrode (second electrode) penetrates through the dielectric film through a biased through phenomenon and the BSF layer

As an example of a silicon solar cell, the dielectric film may be a silicon nitride film, a silicon nitride film containing hydrogen, a silicon nitride film containing hydrogen, a silicon oxynitride film, or silicon. It may be a single film selected from an oxide film, A1 ₂ 0 ₃ film, MgF ₂ film, ZtiS film, MgF ₂ film, Ti0 ₂ film, and Ce0 ₂ film or a film in which two or more selected films are laminated.

 The back electrode may include a conductive material and a glass frit, and representative examples of the conductive material include silver (Ag), copper (Cu), titanium (Ti), gold (Au), tungsten (W), and nickel ( Ni, Cr, Molybdenum (Mo), Platinum (Pt), Lead (Pb), Pallium (Pd) and their alloys can be selected from one or more of these materials. Glass frit forms solar cell electrodes. Lead glass containing bismuth oxide, lead-free glass containing boron oxide, and the like, which are commonly used in the present invention.

 The formation of the emitter layer or the BSF layer can be formed by doping the semiconductor substrate with impurities, as is commonly known in the semiconductor manufacturing process. As is known, the doping of impurities involves the presence of a gas containing impurities to be doped. This can be accomplished by using a solid source or a spray-on diffusion source containing the impurity to be doped or the semiconductor substrate.

 [479] The back electrode provides electrode material on a semiconductor substrate on which an emitter layer and a BSF layer are formed.

It can be formed by application, and the coating of electrode material is ink jet printing, masking, This can be done via stencils or screen printing, etc.

 The dielectric film, which is an antireflection film and / or a passivation film, may be further formed on the BSF layer, and the electrode material is applied on the dielectric film in the form of an air bone structure or an interdigitate structure, and the like, followed by thermal treatment. Of course, it can be drilled and electrically connected to the BSF layer.

The bonding layer is used to bond the inorganic light absorbing layer and the light absorbing layer of the perovskite compound to each other, and may be a material generally used in conventional tandem structured solar cells. Thin translucent metal layers such as Al, Cu, oxide transparent conductive layers such as Sn: In203 (ITO), Sb: Sn02 (ATO), Al: ZnO (AZO), graphene, graphene oxide Carbon layers, such as PEDOT: organic conductive layers such as PSS, or titanium oxides, molybdenum

 Amorphous oxide semiconductor insects such as oxides, or composite layers thereof, and the thickness of the bonding layer may be () .5 nm to 50 nm, and practically 0.5 nm to 20 nm. However, the present invention is not limited by the material and thickness of the bonding layer.

 As a matter of course, the bonding layer may be formed through physical deposition or chemical deposition.

 Hereinafter, an embodiment for hybridization with a solar cell based on a metal chalcogenide compound is provided.

[482] The first structure is a transparent substrate that is a transparent electrode positioned on a first substrate and a first substrate.

 And a first charge carrier positioned on the front electrode (first electrode), the front electrode (first electrode) and providing a path for the movement of photocurrent, and a first surface layer positioned on the first charge carrier.

The second structure includes a second substrate, a second electrode on the second substrate, an inorganic light absorbing layer of the metal chalcogenide compound on the second electrode, a buffer layer on the inorganic light absorbing layer, and a bonding layer on the buffer layer. ， _2nd charge carrier, _2nd charge carrier on the junction layer

 The second surface layer may be located. Further, the second structure may be further provided with a circular insect between the buffer layer and the bonding layer.

 In detail, the first structure is a transparent electrode disposed on the first substrate and the first substrate.

 It may include a first charge carrier located on the front electrode (first electrode), a front electrode (first electrode), and a first charge carrier positioned on the first electrode and providing a movement path of the electrons.

 Together with the first structure, the second structure includes a second substrate, a second electrode disposed on the second substrate, an inorganic light absorption layer of the metal chalcogenide compound positioned on the second electrode, a buffer layer located on the inorganic light absorption layer, and a buffer layer. And a second charge carrier located on the junction layer, a second charge carrier located on the junction layer and providing a path of movement of holes, and a second surface layer located on the second charge carrier.

 The metal chalcogenide compound may mean a chalcogenide compound of at least one element selected from copper and group 12 to 14. Specifically, the metal chalcogenide compound

May contain copper-indium-gallium-chalcogen compounds or copper-zinc-tin-chalcogen compounds More specifically, the metal chalcogenide compound is CIGS (Cu-In-Ga-Se or

1인실수), CuIn_xGa_1-x(Se_yS_1-y)₂ (0≤χ≤1인실수， 0≤y≤l인실수)， CuzZn_xSn^Se^O x^인실수)， Cu₂Zn_xSn,._xS₄ (0≤χ≤1인실수)또는

인실수， 0≤y≤l인실수)일수 있으나，이에한정되는것은아니다. Cu-In-Ga-S), CIGSS (Cu-In-Ga-Se-S), CZTS (Cu-Zn-Sn-Se or Cu-Zn-Sn-S) or CZTSS (Cu-Zn-Sn-Se More specifically, the metal chalcogenide compound is CuIn _x Ga _1-x Se ₂ (real number 0≤x≤l),

CuIn _x Ga _1-x (Se _y S _1-y ) ₂ (0≤χ≤1 thread, 0≤y≤lperson), CuzZn _x Sn ^ Se ^ O x ^ number , Cu ₂ Zn _x Sn ,. _x S ₄ (real number 0≤χ≤1) or

Number, which can be 0≤y≤l), but it is not limited thereto.

 The second electrode may be a conductive material that is ohmic-conjugated with a metal chalcogenide compound and, as is known, may be molybdenum or molybdenum doped with a doping element such as Na, K, Ag, Sb, A1, and / or Cu. have.

 The buffer layer serves to prevent annihilation by electrons and holes recombination in a metal chalcogenide-based solar cell and to reduce the band gap difference between the conventional window layer and the light absorption layer of the metal chalcogenide compound. The buffer layer is combined with the light absorbing layer to perform the above-mentioned roles in conventional metal chalcogenide-based solar cells.

Any material located between the window layer (transparent electrode layer) may be used. In one specific and non-limiting example, the buffer layer is 45, 2:11 (0,5), 156, 5 ₃ ,: 1 ^^ (() ≤: ) (≤1, () ≤3 / <1, 乂 and y are real) and Zn ^ M) (0 <χ <1, x is real), but may include, but are not limited to No. The thickness of the buffer layer is not particularly limited, but may be 10 nm to 1000 nm, specifically 30 nm to 800 nm.

 [488] Junctions are based on conventional metal chalcogenide-based solar cells

 It may be implemented using a material used as a window layer (transparent electrode layer), or after forming a window layer between the bonding layer and the buffer layer of the second structure, a metal layer may be used as the bonding layer.

 [489] Specifically, the bonding layer of the conventional metal chalcogenide-based solar cell

For the material of the window layer, the bonding layer is ZnO, aluminum-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), boron-doped zinc oxide (BZO), indium tin oxide (ITO), fluorinedoped tin If a window layer is further provided between the bonding layer and the buffer layer of the second structure, the bonding layer is a thin light-transmissive metal layer such as Au, Ag, Al, Cu, Sn: ln ₂ 0 ₃ (ITO), Oxide transparent conductive layers such as Sb: Sn0 ₂ (ATO), Al: ZnO (AZO), carbon layers such as graphene, graphene oxide, organic conductive layers such as PEDOT: PSS, or titanium Amorphous oxide semiconductor layers such as oxides, molybdenum oxides, or composite layers thereof, and the thickness of the bonding layer may be 0.5 nm to 50 nm, and practically 0.5 nm to 20 nm, but is not limited thereto. .

 [490] The second electrode is usually deposited, specifically sputtering,

Evaporation, chemical vapor deposition (CVD), spin coating, or spray coating may be used on the substrate. The light-absorbing layer of the metal chalcogenide compound can be formed using a known method, for example, evaporation,

 It can be prepared using sputtering + selenization, electrodeposition, ink printing to apply and semi-sinter the powder or colloidal precursor ink, or spray pyrolysis.

 [491] The buffer layer, optionally the window layer (transparent electrode layer), and the bonding layer are independent of each other,

It can be formed through methods including chemical bath deposition (CBD), electron beam coating, sputtering and chemical vapor deposition, but in the manufacturing of semiconductors or solar cells, it is possible to form films using gas, liquid or dispersed phases. Of course, you can use any known method to do this.

 [492] Semiconductor Solar Cells and Metal Chalcogenide Based Based on p-n Junctions

 In solar cells, the system 1 charge carriers of the system 1 structure and the second charge carriers of the second structure can be compared to the electron carriers and hole carriers described above.

 If the charge carrier (or second charge carrier) is a charge carrier that provides a hole transport path, the first charge carrier (or second charge carrier) may correspond to the hole carrier described above, and the first charge carrier (or system). If the second carrier is a charge carrier that provides an electron transport path, the first carrier (or the second carrier) can be used for the electron carrier described above, provided that the first carrier is used for the hole carrier. In this case, the second charge carrier can be referred to the electron transporter, and if the first charge carrier is to the electron transporter, the second charge carrier can respond to the hole transporter. Emitters on semiconductor substrates can be p-type emitters when referring to carriers, and emitters on semiconductor substrates can be n-type emitters when the first charge carriers correspond to electron carriers.

 In addition, the surface layer (first surface layer or the second surface layer) disposed on the first charge carrier (or second charge carrier) may be applied to the surface layer located on the electron carrier or hole carrier described above. -Semiconductor with Emitter Pack and BSF Layer

 The structure of the substrate-bonded layer can correspond to the substrate described above.

 The structure of the substrate, the second electrode, the metal chalcogenide compound, the buffer layer, and the bonding layer may correspond to the substrate described above.

 [494] Accordingly, in the embodiments of the tandem structure, the structure, the material and the manufacturing method of the transparent substrate, the transparent electrode, the first charge carrier, the first surface layer, the second charge carrier and the second surface worm are described above. All of the above descriptions are included in one example of a solar cell comprising a compound film as a light absorbing layer.

 [495]

[496] The first structure and the second structure are laminated, and the 11 surface layers of the first structure and the 12 surface layers of the second structure are laminated so as to be in contact with each other, and thermal and physical forces are applied to the laminated structure of the first structure and the second structure. This results in the binding of the first and second structures and the conversion of the first and second surface layers into a single perovskite compound film. Can be.

[497] When heat is applied to the laminate of the first structure and the second structure without applying physical force, there is a limit that it is difficult for the first surface filling system and the second surface layer to be converted into a dense single layer, and the temperature is less than 250 ° C. There is a limit to conversion into dense monolayers through low temperature processes below 200 ^o C. In addition, when physical forces are applied to the laminates of the first and second structures without the application of thermal energy, It is difficult to overcome the activation energy required for densification or particle growth of the materials, so that there is practically no limit to converting the first and second surface layers into a dense monolayer.

 That is, by applying heat and physical forces simultaneously, the first surface layer and the second surface layer are

It can be converted to a single, high-quality, dense layer of perovskite compound, which can be implemented at temperatures below 250 ^° C, specifically below 200 ° C.

 [499] The physical force applied to the laminated body of the first structure and the second structure is preferably a compressive force, and preferably a one-way compressive force. The one direction of the one-way compression force is the same as the stacking direction of the first structure and the second structure (including both the direction from the first substrate to the second substrate and the direction from the second substrate to the first substrate). Can mean. This one-way compressive force is a state where the surface layer (first surface layer or second surface layer) is already interfacing with the surface layer and underlying components of the structure, and when two-way or isotropic compression forces are applied in different directions. Rather, it can have a detrimental effect, such as damaging the layer of converted vesicle compound.

 [500] The application of this one-way compressive force can be represented by pressing,

 The configuration of applying heat and physical forces to the laminate of the first structure and the second structure can be represented by the configuration of hot pressing the stacked bodies of the first structure and the second structure.

 That is, by hot pressing the laminate of the first structure and the second structure,

 It is possible to bind the second structure with a single piece of water, convert the first surface layer and the second surface layer into a single perovskite compound layer, and fabricate a device having a high-quality, dense perovskite compound layer. Pressing can be performed by placing a laminate between two heatable and opposing plates, each having a heating element generating joule heat, and then applying a compressive force to the laminate through the heated plate.

 [502] Specifically, the first surface layer of the first structure and the second surface layer of the second structure are hot pressed to form the first surface layer, the second surface layer itself, and the first surface layer and the second surface layer.

In the entire area of the interface (contact surface), crystal growth and densification of materials contained in the surface layer (first surface layer or second surface layer) can be extremely active. Accordingly, the interface between the first surface layer and the second surface layer is substantially disappeared. Any single film can be made, dense film can be made and coarse perovskite compounds A film made of grain can be produced.

 [503] Specifically, the substance contained in the first surface layer-the substance pair of the substance contained in the second surface layer, the perovskite compound-the perovskite compound, and the perovskite compound by hot pressing Growth and densification occur, and the first surface layer

 The interfacial surface of the second surface layer disappears, and the first surface layer and the second surface layer can be changed into a single layer.

 [504] Specifically, the substance contained in the first surface layer-the substance pair of the substance contained in the second surface layer, the perovskite compound-the perovskite compound precursor material (or

 In the case of perovskite compound precursors (perovskite compound precursors), the GM of the perovskite compound precursors is diffused and removed by hot pressing, and nucleation, growth and densification of the perovskite compounds are carried out. Occurs, and the first surface layer and the second surface layer can be changed into a single entity.

 [505] Specifically, the material pair of the material contained in the first surface layer-the material contained in the second surface layer, the metal halide precursor precursor-in the case of organic halides, by hot pressing, the GM 'of the metal halide precursor material This can be diffused or replaced with organic halides, nucleation, growth and densification of the perovskite compound occur, and the first and second surface worms can be transformed into a single layer.

 [506] Specifically, in the case of a substance pair of a substance contained in the first surface layer-a substance pair of a substance contained in the second surface layer, and a metal halide-organic halide, the organic halogenide and the metal halide are directly diffused by hot pressing. In response, nucleation, growth and densification of the perovskite compound occur, and the first and second surface layers can be changed into a single layer.

 In the manufacturing method of the present invention, not only a high quality light absorbing layer is manufactured, but also a high quality light absorbing layer can be manufactured at an extremely low process temperature.

 [508] In particular, hot pressing may be performed at temperatures below 250 ° C. In practice, hot pressing may be performed at 50 to 250 ° C., more practically at 100 to 200 ° C. Such low temperatures may be applied to low temperature processes. In addition to reducing the manufacturing costs involved, in the manufacture of the device using the first and second structures, the other components of the device are free from thermal damage, i.e. by the low temperature hot pressing described above, As lobesite compounds can be produced,

 Materials with very poor heat resistance, such as polyethylene terephthalate, can also be used as the first and / or second substrate.

 [509] Effective provision of nucleation and / or growth drivers and induction of effective densification

In terms of pressure, hot pressing can be from 1 MPa to 100 MPa, preferably from 5 MPa to lOOMPa, more preferably from lOMPa to lOOMPa, and even better from lOMPa to 70 MPa. These pressures allow for easy volatilization of the heterogeneous molecules (GM or GM ') contained in the metal halide precursors or perovskite compound precursors, and promote excessive compaction while promoting densification and crystal growth of the light absorbing layer. By Physical damage to other components such as porous electron carriers can be prevented.

[510] In the hot pressing of the first structure and the second structure, the hot pressing of the first structure and the second structure may be performed in a vacuum to atmospheric pressure atmosphere. Specifically, the hot pressing may be performed in an atmosphere of 0.01 to 1 atm. At this time, the atmosphere in which the hot pressing is performed may be in the air.

 [51] Although hot pressing may be performed at atmospheric pressure, the reduced pressure atmosphere may be a heterogeneous molecule contained in a metal halide precursor or a perovskite compound precursor (GM or

It is more desirable to promote volatilization of GM ').

[512] The time during which hot pressing is performed is sufficient to allow the surface layer to be stably converted to a perovskite compound layer.

It can be performed for 20 minutes, but is not limited to this.

The present invention includes devices manufactured by the above-described manufacturing method.

The present invention includes a layer of perovskite compound prepared by the above-described manufacturing method.

The present invention includes a solar cell manufacturing laminate.

 [16] The laminate for manufacturing solar cells applies only heat and physical force to the laminate.

 Just by converting the first surface layer and the second surface layer into a single perovskite compound layer, a solar cell can be manufactured.

 In detail, the solar cell manufacturing laminate includes a first structure and a second structure, wherein the first structure includes a first substrate, a first electrode positioned on the first substrate, an electron carrier positioned on the first electrode, and A first surface layer, the second structure comprising a second substrate, a second electrode positioned on the second substrate, and a second surface layer, wherein the first surface layer of the first structure and the second surface layer of the second structure are interfacing with each other. In other words, it may be a laminated laminate. In other words, it may be a laminate laminated such that the first surface layer of the first structure and the second surface worm of the second structure are in contact with each other.

 [518] In the solar cell manufacturing laminate, a hole transporter is formed between the second electrode and the second surface layer.

 In this case, the second electrode may be in direct contact with the second surface layer. In this case, the perovskite compound layer formed from the first surface layer and the second surface layer plays a role of the hole transporter together with the role of the light absorber. Can be done simultaneously

 [519] However, the hole carrier is not intentionally excluded from the solar cell manufacturing laminate, and the second structure includes the second substrate, the second electrode on the second substrate, the hole carrier on the second electrode, and the hole carrier. The superposition may include a second surface layer.

[520] The hole transporter, the electron transporter, independently of each other, may be organic or inorganic, and may be a porous film or a dense film. When the electron transporter includes an inorganic electron transporter of the porous film, by application of heat and physical force 1 When the surface layer and the second surface layer are converted to a single perovskite compound layer, the perovskite compound can occlude pores of the porous electron transporter (inorganic electron transporter of the porous membrane), or the first surface layer itself is the porous electron transporter. Filling the pores and covering the surface of the porous electron transporter Of course, independantly, if the hole transporter contains an inorganic hole transporter of the porous membrane, the first surface impingement and the second surface layer may have a single perovskite by the application of thermal and physical forces. The perovskite compound can occupy the pores of the porous hole transporter (inorganic hole transporter of the porous membrane) when it is converted to the compound layer, or the second surface filler fills the pores of the porous hole transporter and the surface of the porous hole transporter Of course, there may be a layer covering the.

 [521] In the case where both the electron transporter and the hole transporter have a porous structure,

 By applying a physical force, the perovskite compound fills the pores of the electron transporter and the hole transporter, respectively, and the perovskite compound layer can be formed in the form of a dense membrane positioned between the porous electron transporter and the porous hole transporter. This structure is a structure in which the dense film of the perovskite compound is provided between the hole transporter and the electron transporter, and the perovskite compound penetrates the pores of the hole transporter and fills the pores, and the electron transporter also fills the pores. This structure is good because it can widen the contact area between the electron carrier and the light absorber and the hole carrier and the light absorber.

 The present invention includes a random type battery manufacturing laminate.

 [523] A tandem solar cell manufacturing laminate includes a first structure and a second structure,

 The first structure includes a first substrate, which is a transparent substrate, a first electrode, a charge carrier, and a first surface layer, which is a transparent electrode disposed on the first substrate, and the second structure is located on the second electrode, the second electrode, and has a light of 800 nm or more. An inorganic light absorbing layer that absorbs and generates electrons and holes; It can be a stacked stack. In other words, the U surface layer of the first structure and the twelve surface layers of the second structure may be laminated to be in contact with each other.

 The inorganic light absorbing layer may be a semiconductor layer or a metal chalcogenide layer on which a p-n junction is formed.

 As an example of the inorganic light-absorbing layer of the semiconductor layer in which the pn junction is formed, the inorganic light-absorbing layer of the second structure may include a semiconductor substrate having a back surface field (BSF) layer forming an emitter layer and a back field. In this case, the second electrode may be electrically connected to the BSF layer of the semiconductor substrate, and the bonding layer may be positioned on the emitter layer. In addition, the second structure may further include a second charge carrier located on the bonding layer.

More specifically, the tandem-type positive electrode manufacturing laminate includes a low eleven structure and a second structure, wherein the first structure includes a first substrate which is a transparent substrate and a front electrode which is a transparent electrode positioned on the first substrate. Electrode), a first charge carrier positioned on the front electrode (first electrode) and providing a path of photocurrent transfer, a first surface layer located on the first charge carrier, and the second structure comprises an emitter layer and a back electric field. A semiconductor substrate having a back surface field (BSF) layer formed thereon, and electrically connected to the BSF layer of the semiconductor substrate. Lamination comprising a back electrode (second electrode), a junction layer located on the emitter layer, a second charge carrier located on the junction layer and providing a transfer path of photocurrent, and a second surface layer located on the second charge carrier. The sieve may be a laminate laminated such that the first surface layer of the first structure and the second surface layer of the second structure contact each other.

 [527] More specifically, the first structure of the tandem-type positive electrode manufacturing laminate includes a first substrate which is a transparent substrate, a front electrode (first electrode) which is a transparent electrode positioned on the first substrate,

 A first electrode positioned on the front electrode (first electrode) and providing a hole migration path

 The first carrier may include a charge carrier (hole carrier) and a first surface layer positioned on the first charge carrier. In addition, the second structure may be doped with p-type impurities on the surface to form a p-type emitter layer and a p-type emitter. A junction layer located on an n-type semiconductor substrate having an n-type impurity doped on an opposite surface of the layered surface and a back electrode electrically connected to a BSF layer of an n-type semiconductor substrate and a p-type emitter layer. And a second charge carrier (electron carrier) located on the junction layer and providing an electron transport path, and a second surface layer located on the second charge carrier.

 In more detail, the first structure of the tandem-type positive electrode manufacturing laminate is a first substrate which is a transparent substrate, a front electrode (first electrode) which is a transparent electrode positioned on the first substrate;

 A first electrode located on the front electrode (first electrode) and providing a movement path of electrons

It may include a charge carrier (electron carrier) and a first surface layer located on the first charge carrier. In addition, the second structure is doped with n-type impurities on the surface to form an n-type emitter layer, and n-type emitter. P-type semiconductor substrate doped with a p-type impurity on the opposite surface of the layered surface, a p-type semiconductor substrate having a p-type BSF layer, a back electrode electrically connected to a ρ-type semiconductor based BSF layer, and a junction layer located on a _η- type emitter layer And a second charge carrier (hole carrier) located above the junction layer and providing a hole migration path, and a second surface layer located on the second charge carrier.

 [529] As an example of the inorganic light absorbing layer of the metal chalcogenide compound, the inorganic light absorbing layer of the second structure may include a metal chalcogenide compound. The second structure may further include a buffer layer disposed on the second substrate, the inorganic light absorbing layer, and The second charge carrier may be further included, and the second substrate, the second electrode, the inorganic light absorbing layer, the buffer layer, the bonding filler, the second charge carrier, and the second surface insect may be sequentially arranged.

 [530] In detail, the tandem solar cell manufacturing laminate includes the first structure and the second structure.

The first structure includes a first substrate that is a transparent substrate, a first charge that is positioned on a front electrode (first electrode) and a front electrode (first electrode) that is a transparent electrode disposed on the first substrate, and provides a path for the movement of photocurrent. A carrier, a first surface layer overlying the first charge carrier, the second structure comprising a second substrate, a second electrode overlying the second substrate, an inorganic light absorption layer of a metal chalcogenide overlying the second electrode, inorganic A buffer layer overlying the light absorption layer, a buffer layer overlying the junction layer, a second charge carrier over the junction layer, a second surface layer over the second charge carrier, the laminate comprising a first surface layer and a first surface layer of the first structure. The second surface layer of the two structures may be a laminate laminated in contact with each other. A two-layer structure can be further provided with a window layer between the buffer layer and the junction layer.

 [531]

 The present invention includes a solar cell manufactured by the above-described manufacturing method.

 [533] A solar cell according to an embodiment of the present invention includes a first electrode, a first electrode, and a first substrate, which are sequentially laminated between two substrates facing each other, a first substrate, a second substrate, and a first substrate and a second substrate.

 It may include a charge carrier, an inorganic / organic hybrid perovskite compound layer, a second charge carrier, and a second electrode. The first and second substrates facing each other are manufactured using the manufacturing method provided by the present invention. As a structural feature of the cell, the first structure and the second structure, which are solar cell-independent structures, are bonded to each other and formed, which is a constitution required.

 In addition, in the solar cell according to the embodiment of the present invention, the first electrode may be directly in contact with the first substrate, and the second electrode may be in direct contact with the second substrate. The solar cell comprises a first structure including a first substrate on which a first electrode is formed, and a second structure including a second substrate on which a second electrode is formed.

 As it is bound and formed, it is a configuration that is expected.

 At least one of the first charge carrier and the second charge carrier is a porous charge carrier, and the organic / organic hybrid perovskite compound layer fills the pores of the porous charge carrier and can cover the porous charge carrier.

 In detail, a solar cell according to an embodiment of the present invention is formed on a first substrate and a first substrate.

 Located first electrode; Porous electron transporter located on the first electrode; Porous

 A light absorption layer comprising a layer of inorganic / organic hybrid perovskite compound, which is a dense film filling the pores of the electron transporter and covering the porous electron transporter; a second electrode on the light absorption layer; and a second substrate on the second electrode; have.

 [537] A solar cell according to an embodiment of the present invention is provided between a second electrode and a light absorption layer.

 The hole carrier may not be provided, and the second electrode may be located directly in contact with the light absorbing layer. When the second electrode is located directly in contact with the light absorbing layer, the dense film of the light absorbing layer plays a role of hole transport at the same time, It can be from lnm to ΙΟμηι, preferably from Ιμιη to ΙΟμιη.

 Independently of this, the solar cell according to the exemplary embodiment of the present invention may include a hole transporter positioned between the light absorption layer and the second electrode.

 [539] The hole transporter may be an organic hole transporter or an inorganic hole transporter.

 The hole carrier may be a dense membrane, a porous membrane, or a laminated membrane of the porous membrane and the dense membrane, wherein the inorganic hole carrier may be a hole carrier of the membrane and / or a hole carrier of the dense membrane, and the organic hole carrier may be a hole carrier of the dense membrane.

 [540] When the hole transporter includes an inorganic hole transporter of the porous membrane,

 Inorganic / organic hybrid perovskite compounds can occlude the pores of porous hole transporters.

That is, the solar cell according to the embodiment of the present invention comprises a first substrate; A first electrode; a porous electron transporter positioned on the first electrode; a light absorbing layer; a porous hole transporter positioned on the light absorbing layer; a second electrode; and a second substrate disposed on the second electrode; and the light absorbing layer comprises a porous electron. It can fill both the pores of the carrier and the pores of the porous hole transporter, and can include a dense / organic hybrid perovskite compound, which is a dense membrane located between the porous electron transporter and the porous hole transporter.The structure is free of inorganic / organic hybrid perovskite. The dense film of the compound is contained between the hole transporter and the electron transporter, but the perovskite compound film can be interpreted as a structure that fills the pores by infiltrating the pores of the hole transporter, and simultaneously fills the pores of the electron transporter. This structure is better because it can widen the contact area between the electron carrier and the light absorber and the hole carrier and the light absorber.

 The present invention includes a tandem structured solar cell manufactured by the above-described manufacturing method.

 [543] A 4-terminal random structured solar cell according to an embodiment of the present invention is described above.

 Perovskite compound-based solar cells and inorganic light absorbing layer-based solar cells, including perovskite compound-based solar cells receive light

 Two solar cells may have a stacked structure so that light is introduced into the inorganic light absorption layer based solar cell through the perovskite compound based solar cell.

 [544] At this time, in the perovskite compound-based solar cell provided in the 4-terminal tandem structured solar cell, the first substrate and the second substrate are each transparent, and the first electrode and the second electrode are each transparent. Perovskite compound-based solar cells can be provided as inorganic light-absorbing layer-based solar cells by transmitting light having a wavelength band of more than 800 mn of incident light.

 In detail, the perovskite compound-based solar cell provided in the four-terminal tandem structured solar cell is sequentially stacked between the first and second substrates, the first and second substrates, which are two transparent substrates facing each other. The first electrode may be a transparent electrode, a first charge carrier, an organic / organic hybrid perovskite compound layer, a second charge carrier, and a transparent electrode, which is a second electrode. For the material and the method of manufacture, see above.

 [546] The inorganic light absorbing layer-based solar cell of the four-terminal tandem structure solar cell,

Any conventional solar cell that absorbs more than 800 nm of wavelength band and generates light and produces photoelectrons and light holes can be combined with a perovskite compound based solar cell.

For example, the inorganic light absorbing layer-based solar cell is a single crystal silicon solar cell, polycrystalline silicon solar cell, amorphous silicon solar cell, thin film silicon solar cell, compound semiconductor solar cell (CIGS, CIS, CdTe, CdS, AnS, GaAs, GaAlAs, GalnAs, InP, GaP, GaAs / Ge, GaAs / Ge / Si, GaAlAs / Si, GaInP ₂ / GaAs, InGaP / InGaAs / Ge solar cell), dye-sensitized solar cell, quantum dot solar cell, oil -Inorganic Hybrid

Although the solar cell can be lifted, the present invention is not limited to the detailed types of inorganic light absorbing layer based solar cells. In a two-terminal tandem structured solar cell according to one embodiment of the present invention, the second electrode and the second electrode are positioned above the inorganic light absorbing layer and the inorganic light absorbing layer, which absorb electrons of more than 800 nm to generate electrons and holes. Bonding layer, located on the bonding layer

 A perovskite-based light absorbing layer comprising a perovskite compound layer, a charge carrier positioned on the perovskite-based light absorbing layer, a first electrode positioned on the charge carrier and a transparent electrode passing over the first electrode, and a first substrate on the first electrode. May contain

 In detail, a two-terminal tandem structured solar cell includes a semiconductor substrate having a back surface field (BSF) charge, which forms an emitter layer and a back electric field, and a BSF layer of a semiconductor substrate.

 Perovskite-based light absorbing layer, perovskite-comprising layer of perovskite compound, and a second electrode electrically connected, a junction layer on the emitter layer, a second charge carrier on the junction layer, and a second charge carrier on the junction layer The upper layer of the lobe-sky-based light absorbing layer may include a first charge carrier, a first electrode located on the first carrier, and a first substrate, which is a transparent electrode located on the first electrode, and a transparent substrate located on the first electrode.

 More specifically, the two-terminal tandem structured solar cell is electrically connected to an n-type BSF layer of a semiconductor substrate and an n-type BSF layer having a n-type back surface field (BSF) layer forming a p-type emitter layer and a backfield. Two electrodes, a junction layer positioned on the p-type emitter, an electron carrier located on the junction layer, a perovskite-based light absorption layer on the electron carrier, and including a perovskite compound layer, and a perovskite-based light absorption It may include a hole carrier positioned in a layer, a first electrode located on the hole carrier and a transparent electrode, and a first substrate located on the first electrode.

 More specifically, the two-terminal tandem structured solar cell is electrically connected to a p-type semiconductor substrate and a p-type BSF layer of a semiconductor substrate having a p-type back surface field (BSF) layer forming an n-type emitter layer and a backfield. Perovskite-based light-absorbing layer, perovskite-based light, including a second electrode connected to the second electrode, a junction layer located on the n-type emitter, a hole carrier located on the junction layer, a hole carrier located on the junction layer, and including a perovskite compound layer And an electron carrier positioned on the absorption charge side, a first electrode disposed on the electron carrier, and a transparent electrode positioned on the first electrode.

 A two-terminal tandem structured solar field according to one embodiment of the present invention;

 It is located on the second substrate, which is located on the second electrode and on the second electrode.

 Including an inorganic light absorbing layer, the buffer layer is located on the inorganic light absorbing layer, the bonding layer is located on the buffer layer, the bonding layer is located on the bonding layer, the perovskite-based light absorbing layer comprising a perovskite compound layer, perovskite-based light absorption filling position It may include a charge carrier, a first electrode positioned on the charge carrier and a transparent electrode located on the first electrode and a transparent substrate located on the first electrode.

 In detail, a two-terminal tandem structured solar cell is located on a second substrate and a second substrate.

Inorganic light absorbing layer containing metal chalcogenide compound on second electrode, second electrode, buffer layer on inorganic light absorbing layer, bonding layer on buffer layer, bonding layer on A second charge carrier located on the second charge carrier, a perovskite-based light absorbing layer comprising a perovskite compound layer, and a perovskite-based light absorbing layer positioned above the first charge carrier and the first charge carrier. And a first electrode, which is a transparent electrode, and a first substrate, which is a transparent substrate positioned on the first electrode.

 In detail, a two-terminal tandem structured solar cell is placed on a crab 2 substrate and a second substrate.

 Inorganic light absorbing layer containing metal chalcogenide compound on low electrode, second electrode, buffer layer on inorganic light absorbing layer, junction layer on buffer layer, second charge carrier on junction junction, second charge carrier on position And a perovskite-based light absorbing layer comprising a perovskite compound layer, and a perovskite-based light absorbing battery located above the first charge carrier, the first charge carrier, and the transparent electrode, the first electrode and the first electrode. The first charge carrier may be an electron transporter, and the second charge carrier may be a hole transporter. In addition, the two-terminal tandem structured solar cell may further comprise circular fillers located between the buffer layer and the junction layer.

 The two-terminal tandem structured solar cell can be manufactured by applying thermal and physical forces to the laminate described above, converting the first surface layer and the second surface layer into a single perovskite compound layer. In terminal tandem structured solar cells, substrates, electrodes, inorganic light absorbing layers, charge carriers (first charge carriers, second charge carriers),

 Details of the semiconductor substrate including the perovskite-based light absorption layer, the buffer layer, the window layer, the emitter layer, and the BSF layer can be referred to the above-described manufacturing methods and laminates, including all of them.

 [556]

 [557] (Manufacturing Example 1)

 [558] Preparation of organometallic halide solutions

[559] A solution of CH ₃ NH ₃ PbI _{3 at a} concentration of 0.8 M was determined using gamma butyrolactone as a solvent.

It was prepared by using a mixed solvent in which dimethyl sulfoxide was mixed at a volume ratio of 7: 3, and CH ₃ NH ₃ I and Pbl ₂ were dissolved in this mixed solvent in a 1: 1 molar ratio.

 [560]

 [561] (Example 1)

 [562] Perovskite Junction

[563] A fluorine-containing 25 × 25 mm CH ₃ NH ₃ PbI ₃ solution prepared in Preparation Example 1

The tin oxide coated glass substrate (FTO; F-doped Sn0 ₂ , 8 ohms / cm ² , Pilkington, hereinafter referred to as FTO substrate) was collectively applied (injected) and spin-coated at 3000 rpm. At 50 seconds of time, non-solvent toluene (lmL) was applied to the center of the spin of the spinning FTO substrate, followed by further spin coating for 5 seconds. After spin coating, 100 ° C The first surface layer, which is a perovskite compound film, was formed by treatment for 30 minutes at the degree of silver and atmospheric pressure. When the first surface layer was prepared, the main conversion diameter was 25 ° C and 25%. Relative humidity was maintained.

 A second surface layer was prepared on another FTO substrate in the same manner as the above method.

 [565] An FTO engine having a first surface layer formed thereon, and an FTO substrate having a second surface layer formed thereon;

The first surface layer and the second surface layer were laminated so as to be in contact with each other, and the lamellar was bonded for 10 minutes by applying a pressure of 50 MPa in a hot-press heated to 150 ° C. In order to observe the bonded state of one bonded membrane, an external force was applied, one _F TO substrate was removed, cut, and the cross-sections thereof were observed by scanning electron microscopy. At this time, the bonded two substrates were strongly bonded to each other. Only one board could be removed.

 FIG. 1 is a scanning electron micrograph of a cross section of a perovskite compound surface layer formed on a FTO substrate before hot pressing. FIG. 2 is a scanning electron micrograph of a cross section of the bonding film after hot pressing.

 [567] The perovskite compound film (first surface layer or second surface layer) before hot pressing

 It has a thickness of about 800 nm, and the grain boundary is observed on the cross-sectional observation image. However, when the cross-sectional observation image after the bonding process using hot pressing is found, the thickness of the bonded film is approximately 1.7 um. The thickness of the membrane (surface layer) is about twice that of the two membranes, and the junction between the two membranes is not observed at the intermediate position, indicating that there is a sufficient amount of foreign matter transfer between the two membranes. Grain boundary was not observed, resulting in active mass transfer into large grains.

 You can see that it has grown.

 [568]

 [569] (Manufacturing Example 2)

[570] Fabrication of porous Ti0 ₂ thin film substrate

[571] Glass substrates coated with fluorine-containing tin oxide (FTO; F-doped Sn0 ₂ , 8 ohms / cm ² ,

 Pilkington (hereinafter referred to as an FTO substrate (first electrode)) was cut to a size of 25 x 25 mm, and the end was etched to partially remove the FTO.

A 50 nm thick Ti0 ₂ dense film was prepared by spray pyrolysis as a metal oxide thin film on a cut and partially etched FTO substrate. The spray pyrolysis was performed by TAA (Titanium acetylacetonate): EtOH (l: 9 v / v%) The thickness was adjusted by repeating the method of spraying for 3 seconds and stopping for 10 seconds on a FTO substrate which was carried out on a hot plate maintained at 450 ° C.

[573] Ti0 ₂ powder with an average particle size (diameter) of 50 nm (1 wt.% Dissolved on Ti0 ₂ basis

Titanium eroxocomplex aqueous solution was prepared by hydrothermal treatment at 250 ° C. for 12 hours), and ethyl cellulose solution dissolved in ethyl alcohol at 10% by weight of ethyl cellulose was added, and 5 ml per lg Ti0 ₂ powder. Then, terpinol (terpinol) was added by mixing 5g per 1g Ti0 ₂ powder, and then ethyl alcohol was removed by distillation under reduced pressure to prepare Ti0 ₂ paste. Ti0 ₂ slurry was added to the prepared Ti0 ₂ powder paste (1 (Ti0 ₂ powder paste): 5 (ethanol) weight ratio) to prepare a Ti0 ₂ slurry for spin coating. A spin coating method using a thin film Ti0 ₂ weir j, Ti0 ₂ slurry for the spin coating of the FTO substrate

Coated (3000 rpm) and heat treated at 500 ⁰ C for 60 minutes, immersed the substrate in heat at 60 ° C in 30 mM TiCl ₄ aqueous solution, left for 30 minutes, washed and dried with deionized water and ethanol and dried again. The porous Ti0 ₂ thin film (porous electron transporter) was prepared by heat treatment at 30 ° C. for 30 minutes, wherein the thickness of the porous Ti0 ₂ thin film (porous electron transporter) was 100 nm, and the specific surface area of the prepared porous electron transporter was 33 m ² /. g, and the porosity (apparent porosity) was 50%.

[575] (Manufacturing Example ³ )

 [576] NiO layer manufacturing

[577] After cutting a glass tube coated with fluorine-containing tin oxide (FTO; F-doped Sn0 ₂ , 8 ohms / cm ² , Pilkington, hereinafter referred to as FTO substrate (first electrode)) to 25 x 25 mm, 4 mm The remaining portion of the FTO was removed so that four x 20 mm rectangular electrodes were placed.

A 50 nm thick NiO dense film was prepared on the cut and partially etched FTO substrate as a metal oxide thin film. The NiO dense film was prepared by spin coating a NiO solution on an FTO substrate and then heat treatment. NiO solution was prepared by adding 0.0589 g of Nikel nitrate hexahydrate and 12.5 μΐ of monoethanolamine to 2 ml of ethanol and stirring for 4 hours at 70 ° C. The solution was coated on the prepared FTO substrate at 3000 rpm and then at 250 ^° C. Heat treatment was performed for 30 minutes.

 [579]

 [580] (Example ¾

[581] Solar Cell Manufacturing

A CH ₃ NH ₃ PbI ₃ solution was prepared in the same manner as in Preparation Example 1, but a solution was prepared at a concentration of 0.5 M.

The perovskite solution prepared on the porous Ti0 ₂ film was applied (injected) at the center of rotation in a batch, and spin coating was started at 3000 rpm. When the spin coating time was 50 seconds, The non-solvent toluene lmL was once again applied (injected) at the center of rotation of the spinning FTO substrate, followed by further spin coating for 5 seconds.After the spin coating was performed, at 100 ° C and atmospheric pressure conditions. 30 minutes of treatment resulted in the formation of the perovskite compound membrane Lower 1 1 surface worm. In the preparation of the first surface worm, the main conversion mirror maintained a temperature of 25 ° C. and a relative humidity of 25%.

 A second surface layer was manufactured on the FTO substrate coated with the NiO film prepared in Production Example 3 in the same manner as the above method.

[585] The TKVFTO substrate having the first surface layer formed thereon and the NiO FTO substrate having the second surface layer formed thereon are laminated so that the lower 11 surface layer and the second surface layer come into contact with each other, at which time the electrodes can be connected to each other without bonding the front surface. Let the non-junction part of Ti0 ₂ / FTO substrate having a first surface layer and NiO / FTO substrate having a second surface layer formed thereon The laminates were bonded for 10 minutes at a pressure of 50 MPa in a hot-press heated up to 180 ^° C. on both sides.

The photovoltaic conversion parameters (AM 1.5G light irradiation conditions) of the perovskite solar cell fabricated by bonding were 23.2 mA cm ² for J _sc , 1.05 V for V _oc , and 63.8% for FF, which was 15.5% higher. Photoelectric conversion efficiency has also been shown.The feature is that the compressed perovskite solar cell formed in this way has a high transmittance of more than 50% in the long wavelength region of 800 nm or more, which is useful for tandem with crystalline silicon or metal chalcogenide-based solar cells. It can be seen that it can be used.

 [587] And in this embodiment having a structure in which both sides are made of glass

 The perovskite solar cell has high stability, which maintains efficiency of over 80% even after 1000 hours under AM 1.5G irradiation condition with the NiO side as the light-receiving surface, which is a high stability solar cell structure for commercialization of perovskite. It is also expected to be suitable for building integrated photovoltaics (BIPV) or in vehicles, as the color can be controlled by adjusting the band gap of the perovskite compound and the visible light transmission can also be controlled by thickness and band gap.

 [588]

 [589] (Example 3)

 [590] Producing fine films into fine films

 [591] The perovskite solution has a disadvantage in that it is difficult to produce a dense film when coating a single solution. Therefore, in order to manufacture a dense film, one or two steps must be added. This is to show that the dense surface layers fabricated with can be converted into dense membrane films.

[59] CH ₃ NH ₃ I and Pbl ₂ were dissolved in gamma butyrolactone single solvent in a 1: 1 molar ratio to prepare a 0.8 M CH ₃ N¾PbI ₃ solution. The surface worms were prepared by spin-coating at 3000 rpm each of the hole carriers prepared in Example 3. FIG. 3 is a photograph obtained by scanning electron microscopy of the surface layer formed on the electron transporter. As shown in FIG. It can be seen that the sky compound material does not form a dense film but is in an amorphous form (island structure, pillar structure) by superimposing two surface layers so that the surface insects touch each other and the upper and lower sides 180 °. The hot-press heated to C was bonded for 10 minutes by applying a pressure of 50 MPa. To observe the shape of the bonded perovskite, one board was removed by external force, cut and cut to its cross section. Observation with a scanning electron microscope C. At this time, the two substrates are bonded to each other strongly, and it was joint can not separate the one of the substrates must fall considerably large external force. The observed SEM image is shown in Fig.

As can be seen from the scanning electron micrograph of FIG. 4, it can be seen that the film, which was not compact before compression, was converted into a compact film after compression. Even if a low-quality surface layer is manufactured by using the method provided by the present invention, it can be seen that the high-quality, high-density perovskite compound is produced, and the commerciality and process availability of the present invention are very large.

 [594]

[595] (Example ⁴ )

 [596] Manufacture of Perovskite Powder in Dense Film

 [597] When the perovskite compound film is formed, the perovskite compound solution in which all the perovskite compounds are dissolved in the solvent is coated on a substrate, and when the solvent evaporates, the perovskite compound crystallizes through spontaneous crystallization. However, the perovskite powder has been mainly used. However, the perovskite powder layer can be formed by first preparing the perovskite powder and preparing a dispersed solution or slurry. Since this powder layer is not dense, there is a problem in the use of perovskite solar cells.However, a method of preparing a perovskite powder layer by preparing a solution or a slurry in which the perovskite powder is dispersed is made. Its processability makes it more suitable for industrial use, so the technology to form this dense layer of dense powder into a dense film has great significance for commercializing perovskite solar cells. This embodiment is intended to show that this intricate powder layer can be converted into a dense film.

[598] C¾NH ₃ I and the Pbl ₂ 1:., Was dissolved in a single solvent, the lactone of gamma-butyl-1 molar ratio was prepared PbI ₃ CH ₃ NH ₃ solution in toluene was added to 1.0M to the yiyongaek CH ₃ NH ₃ PbI _Three particles were precipitated, filtered and dried to prepare C¾NH ₃ PbI ₃ powder. The perovskite powder thus prepared was dispersed in ruene again, and this dispersion was spin-coated at 100 rpm on an FTO substrate. A scanning electron microscope photograph of one powder layer is shown in FIG. 5.

 [599] As can be seen in FIG. 5, the surface layer, as expected, has a dense film shape.

It is simply a powder spread on a substrate. These two surface layers are stacked on top of each other in a hot-press heated to 180 ⁰ C on both sides of the FTO substrate. The bonding was performed for 10 minutes under the pressure of MPa. To observe the shape of the bonded perovskite compound film, an external force was applied again to remove one substrate and cut the fractured surface.

 Scanning electron microscopy was observed. At this time, the two bonded substrates were strongly bonded to each other so that one board could be removed only by applying a large external force. The observed scanning electron microscope image is shown in FIG.

 [600] As shown in Fig. 6, the shape of the dense film is significantly different from that before the pressing.

It can be seen that a perovskite compound film is prepared. The perovskite compound powder is prepared, coated with dispersed solution, ink, and slurry using a simple coating process, and then easily pressed to a dense perovskite compound film by hot pressing. As a result of the formation of perovskite solar cells, the area It is expected to be easy for mass production.

 [601]

 [602] (Example 5)

 [603] junction between metal halide and organic halide and manufacture of solar cell

CH ₃ NH ₃ I powder was dissolved in an isopropanol solvent at a concentration of 0.25 M to prepare a CH ₃ NH ₃ I solution. Prepared in Preparation Example 2 CH ₃ NH ₃ prepared on a porous Ti0 ₂ membrane. The solution I was coated (injected) at the center of rotation, spin-coated at 3000 rpm, and heat-treated at 100 ^° C. for 1 minute to form a first surface layer, which is an organic halide film. A temperature of 25 ° C. and a relative humidity of 25% were maintained.

In order to form a metal halide film as a second surface layer, Pbl ₂ powder was used.

Dimethylformamide. (DMF; dimethylformamide) to dissolve a concentration of 1.0M in a solvent to prepare a solution ₂ Pbl batch applying the Pbl ₂ solution was fabricated on a FTO substrate NiO film formed thereon produced in Preparative Example 3 in the rotational center (injection Spin coating at 2000 rpm and heat treatment at 100 ° C. for 20 minutes to form a second surface layer, which is a metal halide film. In preparing the second surface layer, the main conversion mirror has a temperature of 25 ° C. and a relative humidity of 25%. Was maintained.

The Ti0 ₂ FTO engine having the first surface layer formed thereon and the NiO FTO substrate having the second surface layer formed thereon were laminated so that the first surface layer and the second surface layer were in contact with each other. A 5 mm unbonded section was provided. The top and bottom surfaces were heated for 10 minutes in a hot-press heated to 180 ⁰ C with a pressure of 50 MPa. The surface layer was observed to change into a black perovskite phase after bonding. The photoelectric conversion parameters of the fabricated perovskite solar cell were 21.8 mA / cm ² for J _sc , 1.02 V for _∞ and FF for FF. The photoelectric conversion efficiency of 12.1% was 72.1%.

 [607]

 [608] (Example 6)

[609] infrared transmission

[610] Si0 ₂ glass substrate (fused silica) or perovskite compound surface layer formed with perovskite compound surface layer for evaluation of infrared region permeability of substrate / perovskite compound film / substrate sandwich structure

 Bonding was performed using a terephthalate (polyethylene terephthalate, PET) substrate.

A perovskite film was prepared in the same manner as in Example 2 except that a fused silica substrate was used instead of the porous Ti0 ₂ substrate. Both the first and second surface layers were prepared on the fused silica substrate. These two surface layers were laminated so as to be in contact with each other, and hot pressing was performed. Both upper and lower surfaces were heated to 140 ° C. The glass-perovskite compound film-glass specimens were fabricated by applying a pressure of 50 MPa in a hot-press for 10 minutes. In addition, a PET substrate was used instead of the organic substrate. A specimen of 7-perovskite compound film PET was prepared. The results of the measurement of the permeability of the two specimens thus prepared are shown in FIG. 7.

As shown in FIG. 7, the CH ₃ NH ₃ PbI ₃ membrane having a thickness of about 700 nm prepared through the junction was formed.

 It can be seen that 80% of infrared rays of 800 nm or more can be transmitted. This transmittance can be further improved by adjusting the thickness of the perovskite film, and conventional solar cells using an inorganic light absorbing layer absorbing light of 800 nm or more are known. It can be seen that it is very advantageous in tandem with (for example, Si solar cell or metal chalcogenide based solar cell).

 [613]

[614] (Example ⁷ )

 [615] Preparation of surface layers using perovskite compound precursors

[616] CH ₃ NH ₃ I and Pbl ₂ powders were added to a dimethyl sulfoxide (DMSO) solvent at a stoichiometric ratio of 1: 1, and stirred at 60 ° C. for 2 hours to provide 0.8 M CH ₃ NH ₃ I0PbI ₂ -DMSO solution. The precipitate powder formed by dropping the solution into toluene was collected and collected by filter paper and dried at room temperature for 1 hour.

X-ray diffraction analysis of the prepared powder showed that the phases of CH ₃ NH ₃ I and Pbl ₂ materials were not detected and had diffraction peaks different from those of PbI ₂ (DMSO) ₂ (see FIG. 8). ). The prepared powder (shown as PbI ₂ (MAI) (DMSO) in FIG. 8) shows strong diffraction peaks at diffraction angles 2Θ, 6.2 to 6.8 °, 7 to 7.5 ° and 8.9 to 9.5 °. It can be seen that the peaks located at 7 to 7.5 ° have the largest diffraction intensity in the powder range of 2 to 5 °. .

 [618] Fourier transform infrared spectroscopy (FTIR) measurement results of manufactured powder,

It can be seen that there is absorption of S-0 bonds, CH bonds, and NH bonds, which means that the powders produced contain both CH ₃ NH ₃ I and DMSO. It can be seen that it does not, which means that the non-solvent used toluene is not included in the powder. XRD and FTIR results show that the powder produced is a mixed crystal of CH ₃ NH ₃ I-PbI ₂ -DMSO. Elemental analysis was performed for accurate composition analysis. = 1.6%, C = 4.6, N = 2.0%, 0 = 2.2%, S = 3.7%. Based on this, the mass ratio of the remaining elements was estimated to be 85.9%. Assuming that the mixed crystals of CH ₃ NH ₃ I (hereinafter referred to as MAI), Pbl ₂ , and C ₂ H ₆ SO (VISO) were 1: 1 and 1: 1, H = 1.7%, C = 5.2%, N = 2.0%, O = 2.3%, S = 4.6%, Pb = 29.7%, I = 54.5%, which is similar to the result of elemental analysis.

Through this, the prepared powder was formed by reacting MAI-PbI ₂ -DMSO with 1: 1: 1.

The crystal shows that CH ₃ NH ₃ Pb (C ₂ H ₆ SO) I ₃ (= C ₃ H ₁₂ NSOPbI ₃ ). In the AM (GM) _n X ₃ presented, GM is DMSO and n = l.

[620] CH ₃ NH ₃ I and Pbl ₂ powders were combined with dimethyl sulfoxide (DMSO) at a stoichiometric ratio of 1: 1.

A mixed solvent of gamma butyrolactone (GBL) (GBL: DMSO = 7: 3 volume ratio) was added and stirred at 60 ° C. for 2 hours to prepare a 0.8 M CH ₃ NH ₃ I-PM ₂ -complex solvent solution. .

[621] Rotating CH ₃ NH ₃ I-PbI ₂ -complex solvent (1 ml total) prepared on fused silica substrate

After coating (injecting) in the center, spin coating was started at 5000 rpm. After the spin coating time was 50 seconds, injecting non-lumen lml into the substrate and spinning center again, and then spin coating for 5 seconds. After the completion of the spin coatin, it was dried for 1 hour at room temperature. Through this, the same perovskite as CH ₃ NH ₃ Pb (C ₂ H ₆ SO) I ₃ , which was prepared in powder form on the Fused silica substrate. It was confirmed that a layer of the precursor compound precursor was formed.

 Subsequently, the substrate on which the perovskite compound precursor layer was formed was heat-treated at a temperature of 100 ° C. and atmospheric pressure for 30 minutes. After the heat treatment, the X-ray diffraction analysis revealed that the perovskite compound precursor was pure. It was confirmed that the perovskite compound was converted.

 [623]

 [624] (Example 8)

 [625] fabrication of surface layers, using metal halide precursors

[626] Pbl ₂ powder (Lead iodide, 99%) obtained from SIGMA-ALDRICH Co. was stirred in a solvent of dimethyl sulfoxide (hereinafter referred to as DMSO) at 60 ^° C. for 2 hours at 0.8 M PbI ₂ −. A DMSO solution was prepared. The precipitate was formed by drop-wise dilution of the solution into luene. The precipitated powder was separated and recovered with a filter paper and dried for 6 hours in a vacuum chamber at room temperature. FIG. 9 (a) shows the prepared powder X-. The results of ray diffraction analysis indicate that the powder obtained is PbI ₂ (DMSO) ₂ reported by H. Miyamae (Chemistry Lett., 9, 663, 1980).

[627] The PbI ₂ (DMSO) ₂ material was dried for 24 hours in a vacuum oven at 60 ° C.

The X-ray diffraction analysis of this powder is shown in Figure 9 (b). Figure 9 shows PbI ₂ (DMSO) ₂ precursors and different X-ray diffraction patterns. Elemental analysis confirmed that C and H were PW ₂ (DMSO) reduced in half compared to PbI ₂ (DMSO) ₂ .

[62] The prepared PbI ₂ (DMSO) precursor was added to a Ν, Ν-dimethylformamide (DMF) solvent.

The solution was dissolved to prepare an adduct solution of PbI ₂ (DMSO) at a concentration of 1.5 M.

[629] The prepared adduct solution of 1.5 M concentration of PbI ₂ (DMSO) was prepared by FTO substrate

Glass substrates coated with tin oxide, FTO; F-doped Sn0 ₂ , 8 ohms / cm ² , Pilkington) was injected at the center of rotation, and spin-coated at 3000 rpm for 30 seconds. The X-ray diffraction analysis of the thin film thus prepared is shown in Fig. 9 (c). As a result, a diffraction peak was observed near 2Θ = 10 0, indicating that PbI ₂ (DMSO) film was well formed on the substrate. [630] CH (NH ₂ ) ₂ I at a concentration of ² 50 mM on the prepared PbI ₂ (DMSO) membrane

 Isopropanol solution was injected at the center of rotation and spin-coated at 3000 rpm for 30 seconds.

[631] X-ray diffraction analysis of the film formed after the spin coating (FIG. 10 FAPbI ₃ film

Figure 10 (a) is shown in Figure 10 (a), and for comparison, the results of X-ray diffraction analysis of CH (NH ₂ ) ₂ PbI ₃ powder (shown as FAPbl ₃ powder in Figure 10) are shown in Figure 10 (b). In FIG. 10, it can be seen that specific diffraction peaks of the PbI ₂ (DMSO) thin film disappeared, and diffraction peaks corresponding to the CH (NH ₂ ) ₂ PbI ₃ (FAPbI ₃ ) perovskite compound were generated.

 [632] It is applied to the metal halide precursor precursor film at room temperature,

The application simply means that the heterogeneous molecule (GM ') of the precursor material was removed and at the same time CH (N¾) ₂ I reacted with Pbl ₂ to successfully convert to a perovskite compound.

 As described above, the present invention has been described with specific details and limited embodiments and drawings. However, the present invention has been provided only for better understanding of the present invention, and the present invention is not limited to the above embodiments. In the field of the present invention, those with ordinary knowledge can make various modifications and variations from these materials.

 Accordingly, the spirit of the present invention should not be limited to the described embodiments, and all claims having equivalent or equivalent modifications to the scope of the claims as well as the following claims are intended to be included in the scope of the present invention. something to do.

Claims

Claim  [Claim 1] a) i) to v) comprising a first surface layer containing at least one substance  Laminating a second structure comprising a first structure and a second surface layer containing i-v) at least independently of the first surface layer, the second surface layer being in contact with the first surface entanglement layer; and  b) A method of fabricating a device having an inorganic / organic hybrid perovskite compound film, comprising applying thermal and physical forces to a laminate in which the first structure and the second structure are laminated.  i) organic / organic hybrid perovskite compound  ii) organic halides  iii) metal halides  iv) Inorganic / organic hybrid perovskite compound precursor V) Metal halide precursor precursor  2. The method of claim 1,  And b) converting the first surface layer and the second surface layer into a single inorganic / organic hybrid perovskite compound film by applying the thermal and physical forces of step b). [Claim 3] The method of claim 1,  The pair of materials contained in the first surface layer and the materials contained in the second surface layer is one of the following 1) to 5).  1) Inorganic hybrid perovskite compounds-Inorganic hybrid organic perovskite compounds  2) Inorganic / organic hybrid perovskite compound-Inorganic / organic hybrid perovskite compound precursor  3) Inorganic / organic hybrid perovskite compound precursor-Inorganic / organic hybrid perovskite compound precursor  4) Metal Halide Precursor-Organic Halide  5) Metal Halides-Organic Halides 4. The method of claim 1,  The first surface layer and the second surface layer are independent of each other, i to v) at least one of at least one of i) and (v) at least one porous film of at least one material. Manufacturing method consisting of dense membranes or combinations thereof. [Claim 5] In paragraph 1,  The first surface layer and the second surface layer are each independently i-v) a single layer containing at least one material, i-v) a single layer containing at least two materials, or i-v) at least two materials, respectively. Manufacturing method which is two layers and laminated lamination. 6. The method of claim 1, The first surface layer and the second surface layer is a patterned manufacturing method in the shape of each other. [Claim 7] The method according to claim 1,  The first surface layer and the second surface layer are formed independently of each other by printing, coating or deposition. 8. The method of claim 7, wherein  The first surface layer and the second surface layer are formed independently of each other by using a solution in which at least one of i) and at least one of i) and (i) v) a slurry or ink is dispersed. [Claim 9] The method of claim 1,  At least one of the first surface layer and the second surface layer contains i) an organic / organic hybrid perovskite compound and i) a surface layer containing an organic / organic hybrid perovskite compound. A process for producing a layer of an organic hybrid perovskite compound precursor material or iii) a laminate of a metal halide precursor material and iv) an organic halide precursor. 10. The method of claim 1,  Wherein i) the organic / organic hybrid perovskite compound satisfies Formula 1, Formula 2 or Formula 3.  (Formula 1) AMX ₃  (Formula 1, A is a monovalent cation, A is an organic ammonium silver, an amidinium group ion or an organic ammonium ion and an amidinium-based ion, M is a divalent metal ion, X is a halogen Ions)  (Formula 2) A (M _1-a N _a ) X ₃  In Formula 2, A is a monovalent cation, A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group silver, M is a divalent metal ion, and Ν is 1 A doped metal ion selected from at least one of a pseudovalent metal ion and a trivalent metal ion, a being Real number with 0 <a≤0.1, and X is halogen silver)  (Formula 3) A (N ' _1-b N) X ₃ In Formula 3, A is a monovalent cation, A is an organic ammonium silver, an amidinium group ion or an organic ammonium ion and an amidinium-based silver, Ν ¹ is a monovalent metal ion, Ν ² Is a trivalent metal ion, b is a real number with 0.4 ≦ b ≦ 0.6, and X is a halogen ion) 11. The method of claim 10, wherein In Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, A is A _x) A ^b _x , A ^a is an amidinium-based ion, A ^b is an organic ammonium ion, and X is a real number of 0.3 to 0.05. 12. The method of claim 10, wherein  In Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, X includes two different halogen ions. [Claim I ³ ] In paragraph 10 ᅳ, In Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, X is X y) X ^b y, ^a iodine ion, X ^b is bromion, and y is a real number of 0.05 to 0.3. 14. The method of claim 1, wherein  Said iv) organic halide satisfies the following formula (4). (Formula 4)  AX  (In Formula 4, A is a monovalent cation, A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium ion, and X is a halogen ion.) 15. The method of claim 1,  Additive V) The metal halide is a manufacturing method satisfying the following Chemical Formula 5, Chemical Formula 6 or Chemical Formula 7.  (Formula 5) MX ₂  (In Formula 5, Μ is a divalent metal silver and X is a halogen ion.) (Formula 6) _{(M ,. a N a) X} 2  In Formula 6, M is a divalent metal ion, N is a monovalent metal ion and a trivalent metal ion, and is a doped metal ion selected from at least one, a is a real number 0 <a≤0.1, and X is a halogen ion. ) (Formula ⁷ ) (N ' _1-b N ² _b ) X ₂ (Formula 7, N ⁱ is a monovalent metal ion, N ² is a trivalent metal ion, b is 0.4 <b <0.6, X is a halogen ion) [Claim 16] The method according to claim 1,  The physical force includes a compression method [Claim 17] In paragraph 1,  The applying of the heat and physical force of step b) is hot pressing (hot pressing). 18. The method of claim 17, The hot pressing is carried out at a temperature of 50 to 250 ° C and a pressure of 1 to lOOMPa. 19. The method of claim 17, wherein  The hot pressing is a manufacturing method performed in a vacuum in the ground pressure atmosphere. [Claim 20] The method according to claim 1,  The first structure further comprises a first electrode disposed on the first substrate and the first substrate, the second structure further comprises a second substrate and a second electrode located on the second substrate. According to [Claim ^21] of claim 20,  The first structure further comprises an electron transporter located on the first electrode. 22. The method of claim 21,  The electron transporter is an organic or inorganic manufacturing method. [Claim 23] The method according to claim 21,  The electron transporter is a manufacturing method of a dense membrane or a porous membrane structure. [Claim 24] The method according to claim 10,  And the second structure further comprises a hole transporter located on the second electrode. [Claim 25] The method according to claim 24,  The hole carrier is an organic or inorganic manufacturing method. [Claim ² 6] The method of claim 24,  The hole carrier is a dense membrane or a porous membrane structure manufacturing method. According to ^{[27.] 2} 0 wherein  The first substrate and the second substrate is a flexible substrate manufacturing method. 28. The method of claim 20,  Wherein at least one of the first substrate and the second substrate is a transparent substrate, and the first electrode and the second electrode are at least transparent electrodes. [Claim 29] The method according to claim 1,  The first structure further includes a first substrate which is a transparent substrate, a first electrode which is a transparent electrode positioned on the first substrate, and a charge carrier.  The second structure further comprises an inorganic light absorbing layer and a bonding layer positioned on the second electrode and the second electrode and absorbing light of 800 nm or more to generate electrons and holes.  30. The method of claim 29, wherein  The inorganic light absorbing layer is a Group 4 semiconductor, Group 3-5 semiconductor, Group 2-6 semiconductor, Group 4-6 semiconductor or metal chalcogenide compound manufacturing method.  [Claim 31] In paragraph 1, The device may be a light emitting device, a memory device, a light emitting device or a thermoelectric device. Device manufacturing method.  32. A device manufactured by the method of manufacture according to any of paragraphs 1 to 30. 33. A structure comprising a first substrate, a first electrode located on a first substrate, an electron carrier located on the first electrode, and a first surface layer containing at least one of the following materials:  A second structure comprising a second substrate, a second electrode located on the second substrate, and a second surface layer containing at least one of i-v) independent of the first surface layer;  A solar cell manufacturing bulk filler comprising a laminate in which a first surface layer of a first structure and a second surface worm of a second structure are laminated to abut each other.  i) organic / organic hybrid perovskite compound  ii) organic halides  iii) metal halides  iv) organic hybrid organic perovskite compound precursor V) metal halide precursors  [As claimed in claim 33,  The second structure is a solar cell manufacturing laminate further comprises a hole transporter located on the second electrode. [Claim 35] The first substrate, which is a transparent substrate, the first electrode, which is a transparent electrode located on the first substrate,  A first structure comprising a charge carrier positioned on the first electrode and a first surface layer containing at least one of the following materials:  Inorganic light absorbing layer positioned on the second electrode and the second electrode, absorbing 800 nm or more light to generate electrons and holes, bonding layer located on the inorganic light absorbing layer, and independent of the first surface layer i to v) A second structure comprising a bran 12 surface layer containing material,  A tandem structured solar cell manufacturing laminate, in which a laminate is laminated so that a first surface layer of a first structure and a second surface layer of a second structure are in contact with each other.  i) organic / organic hybrid perovskite compound  ii) organic halides  iii) metal halides  iv) Inorganic / organic hybrid perovskite compound precursor V) Metal halide precursor precursor  [Claim 36] In paragraph 35,  The inorganic light absorbing layer of the second structure forms an emitter layer and a back electric field. A semiconductor organ having a back surface field (BSF) layer formed thereon, wherein the second electrode is electrically connected to the BSF layer of the semiconductor substrate, and the bonding layer is positioned on the emitter layer. Tandem structured solar cell further comprising a second charge carrier positioned on the junction layer Production laminates.  [Claim 37] Section 35.  The inorganic light absorbing layer of the second structure includes a metal chalcogenide compound, and the system structure further includes a second substrate, a buffer layer disposed on the inorganic light absorbing layer, and a second charge carrier. ， Tandem-structured solar cell manufacturing laminates in which inorganic light hop insects, buffer layers, junction layers, second charge carriers, and nearly 12 surface layers are sequentially provided.  [Claim 38] Two substrates facing each other, the first substrate and the second substrate, the lower U substrate and the second substrate  A solar cell comprising a first electrode sequentially stacked, a first charge carrier, an organic / organic hybrid perovskite compound layer, a second charge carrier and a second electrode therebetween.  [Claim 39] paragraph 38  At least one of the first charge carrier and the second charge carrier is a porous charge carrier, wherein the inorganic / organic hybrid perovskite compound layer fills the pores of the porous charge carrier and covers the porous charge carrier.  [Claim 40] In paragraph 38,  The first substrate and the second substrate are transparent substrates, and the first and second electrodes are transparent electrodes, respectively.  [Claim 41] The method of claim 38,  The first electrode is in direct contact with and bonded to the first substrate, and the second electrode is in direct contact with and bonded to the second substrate.