WO2019164054A1 - Novel compound, method for manufacturing same, and organic electronic element using same - Google Patents

Abstract

The present invention provides a novel organic semiconductor compound, a method for manufacturing same, and an organic electronic element using same. The novel organic semiconductor compound of the present invention has a halo-substituted indane functional group introduced to a particular central frame, and thus can significantly improve optical characteristics of the organic electronic element comprising same.

Description

Novel compound, preparation method thereof and organic electronic device using same

The present invention relates to a novel organic semiconductor compound, a preparation method thereof and an organic electronic device using the same.

Organic semiconductor compounds are applied to a wide range of devices or devices, including, for example, organic solar cells (OPVs), organic field effect transistors (OFETs), organic light emitting diodes (OLEDs), photodetectors, sensors, memory devices, logic circuits, and the like. have.

The organic solar cell is a device that uses a donor material (electron donor) and an acceptor material (electron acceptor) together as a photoactive layer. The organic solar cell is not difficult to form a film compared to a conventional inorganic semiconductor compound, and has a thin thickness of several hundred nm or less. It is possible to construct the photoactive layer at a relatively low cost. In particular, in the case of using the organic semiconductor compound, a lot of research has recently been progressed due to the advantage that the flexible device can be bent at will.

On the other hand, the efficiency of the organic solar cell is determined by the open circuit voltage (Voc), the short-circuit current (Jsc), and the fill factor (FF). The open voltage is determined by the energy levels of the donor and acceptor materials, and the short-circuit current is closely related to the absorption spectra of the donor and acceptor materials that absorb light. The fill factor is also determined by the morphology of the mixed film of the donor material and the acceptor material. Accordingly, research on optical characteristics and electro-optical characteristics of a photovoltaic device is required according to the change of the structure of the donor material to increase the efficiency of the organic solar cell.

In general, donor materials used in organic solar cells can be classified into polymer materials and monomolecular materials. When using monomolecular materials, purity can be improved compared to polymer materials, and compared to polymer materials in reproducing synthesis and mass production. It is characterized by ease, but due to the problem of falling compared to the polymer material in film film formation, the disadvantage of the fill factor is worse than the polymer material.

Therefore, in order to secure a highly efficient monomolecular donor material for commercialization of organic solar cells, it is necessary to develop a monomolecular material with a new structure with high charge mobility to improve the fill factor, and to ensure long-term stability. There is a need for development of new monomolecular materials that can be produced.

It is an object of the present invention to provide a novel compound and a method for producing the same, which realize high efficiency with improved charge mobility and thus an improvement in the fill factor.

Still another object of the present invention is to provide an organic photoelectric conversion material and an organic electronic device including the compound, specifically, the compound as an electron donor and having a high energy conversion efficiency.

In order to realize the above object of the present invention, a compound represented by the following formula (1) is provided.

[Formula 1]

[In Formula 1,

Z ¹ and Z ² are each independently O, S or Se;

R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, said aryl or Heteroaryls may each be further substituted with one or more substituents independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio;

A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano;

Y ¹ and Y ² are each independently O or S;

Each R ³ is independently halogen;

n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other;

m is an integer from 1 to 5;

The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P.]

In order to achieve the above object of the present invention, there is provided a method for preparing a compound represented by the following formula (1) comprising the step of reacting a dicarbaldehyde compound of formula (A) and a phosphorus compound of formula (B).

[Formula 1]

[Formula A]

[Formula B]

[In Formula 1, A and B,

Z ¹ and Z ² are each independently O, S or Se;

R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, said aryl or Heteroaryls may each be further substituted with one or more substituents independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio;

A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, halo C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano;

Y ¹ and Y ² are each independently O or S;

Each R ³ is independently halogen;

n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other;

m is an integer from 1 to 5;

The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P.]

In order to realize the above object of the present invention, an organic photoelectric conversion material including the compound of Formula 1 is provided.

In order to realize the above object of the present invention, an organic electronic device comprising the compound of the formula (1) is provided.

The compound of the present invention has a high light absorption and has an absorption spectrum of almost all wavelengths (gray color) in the visible light region and can be used in various organic semiconductor compounds, and is very useful as a photoelectric conversion material.

In addition, the compound of the present invention has a high crystallinity, improves the pi-pi stacking in the solid phase to increase the charge mobility. Thus, the organic electronic device including the compound of the present invention can realize a high fill factor even though the monomolecular compound is used as the electron donor. That is, the organic electronic device containing the compound of the present invention has high efficiency.

In addition, the compound of the present invention is a monomolecular compound having excellent chemical stability, and can be manufactured in high purity and high yield by a simple process, and thus has high industrial applicability, and can be easily applied to a solution process.

Hereinafter, the present invention will be described in detail. At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning that is commonly understood by those of ordinary skill in the art to which the present invention belongs, and the gist of the present invention is unnecessary in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may be blurred are omitted.

As used herein, substituents including alkyl other than "alkyl", "alkoxy" and "alkylthio" refer to organic radicals derived from straight chain or pulverized hydrocarbons. In addition, the alkyl and the substituent including the alkyl according to the present invention is preferably a long chain having 6 or more carbon atoms, but is not limited thereto. In addition, said alkoxy means * -O-alkyl, and alkylthio means * -S-alkyl.

In addition, the term "aryl" as used herein means an organic radical derived from an aromatic hydrocarbon ring by one hydrogen removal, each ring containing 4 to 7, preferably 5 or 6 ring atoms, as appropriate. It includes a single or fused ring system, and includes a form in which a plurality of aryl is connected by a single bond. Examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. It is not limited to this.

In addition, the term "arylene" in the present specification may be applied to the description of the aryl except that it is a divalent organic radical.

In addition, the term "heteroaryl" as used herein refers to an organic radical derived from an aromatic ring by one hydrogen removal, B, N, O, S, Se, -P (= O)-, -C (= O)-, may be an organic radical derived from a monocyclic or polycyclic aromatic ring containing 3 to 9 ring atoms containing at least one heteroatom selected from Si, P and the like, suitably 4 to each ring It includes single or fused ring systems containing seven, preferably five or six ring atoms, up to the form in which a plurality of heteroaryls are linked by a single bond. Examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, tria Monocyclic aromatic rings such as zolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; And benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindoleyl, indolyl, indazolyl, benzothiadia Polycyclic aromatic rings such as zolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolinzinyl, quinoxalinyl, carbazolyl, phenanthridinyl, and benzodioxolyl; And the like, but are not limited thereto.

In addition, the term "heteroarylene" may be applied to the description of the heteroaryl, except that the term "heteroarylene" is a divalent organic radical, and the connection direction of the heteroarylene is not specified to the right or left direction.

In addition, the term "alkoxycarbonyl" as used herein means * -C (= O) alkoxy, which alkoxy follows the above definition.

The term "halogen" herein also means fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atoms.

The compound according to the present invention introduces a halo-substituted indane functional group into the central skeleton represented by benzodithiophene, benzodiselenophene, benzodifuran, etc., thereby improving the planarity of the molecule to minimize phase transition and at the same time, high crystallinity and improved pi Promote pi stacking. In other words, the compounds according to the invention impart high fill factor values with the implementation of significantly improved charge mobility.

In addition, the compound according to the present invention has a structure in which at least one halogen is substituted in the indan functional group introduced at the terminal, thereby having excellent charge mobility as well as excellent light stability. Therefore, the organic electronic device including the compound according to the present invention has high life conversion efficiency as well as high energy conversion efficiency.

Specifically, the present invention provides organic semiconductor compounds useful as various photoelectric conversion materials.

Compound according to an embodiment of the present invention may be represented by the following formula (1).

[Formula 1]

[In Formula 1,

Z ¹ and Z ² are each independently O, S or Se;

R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, said aryl or Heteroaryls may each be further substituted with one or more substituents independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio;

A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano;

Y ¹ and Y ² are each independently O or S;

Each R ³ is independently halogen;

n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other;

m is an integer from 1 to 5;

The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P.]

The compound of Formula 1 has a broad absorption spectrum of the monochromatic region by introducing a halo-substituted indan functional group in the central skeleton represented by benzodithiophene, benzodiselenophene, etc., and has excellent light absorption and excellent light stability. .

Furthermore, the compound of formula 1 has significantly improved charge mobility due to high crystallinity and improved pi-pie stacking. That is, the compound of Formula 1 may be usefully used as an organic photoelectric conversion material of the organic electronic device. Specifically, the compound of Formula 1 may be usefully used as an organic photoelectric conversion material using the photoelectric conversion properties as an electron donor.

Compound according to an embodiment of the present invention is a compound of Formula 1, wherein Z ¹ and Z ² are each independently O, S or Se; R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, wherein the aryl and heteroaryl radicals can be further substituted with one or more substituents each independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and selected from C ₁ -C ₃₀ alkylthio; Each A is independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C May be further substituted with one or more substituents selected from ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen, cyano and the like; Y ¹ and Y ² are each independently O or S; Each R ³ is independently halogen; N is each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other; M may be a compound of an integer of 1 to 5.

Compound according to an embodiment of the present invention may be a compound represented by the following formula (2).

[Formula 2]

[In Formula 2,

Z ¹ and Z ² are each independently O or S;

R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylC ₆ -C ₃₀ aryl or C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl ;

Each A is independently C ₃ -C ₃₀ heteroarylene, wherein the heteroarylene is C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, May be further substituted with one or more substituents selected from C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano;

Each R ³ is independently halogen;

n are each independently an integer from 1 to 4;

m is an integer of 1 to 5.]

Compound according to an embodiment of the present invention is in formula 1 or formula 2, preferably wherein R ¹ and R ² are each independently C ₁ -C ₃₀ alkoxy or C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl Compound.

Compound according to an embodiment of the present invention may be one of Formula 1 or Formula 2, preferably m is an integer of 1 to 3.

The compound according to an embodiment of the present invention may be one of Formula 1 or Formula 2, preferably A is heteroarylene substituted with at least one substituent. Specific examples of the substituents include C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyan It may be a furnace.

Compound according to an embodiment of the present invention in Formula 1 or Formula 2, A may be selected from heteroarylene having the following structure.

[In the above structure,

L ¹ and L ² are each independently O, S or Se;

R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, Halogen or cyano;

R ¹³ is C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen or cyano;

p is an integer of 1 to 4, q is an integer of 0 to 4, and when p or q is an integer of 2 or more, the R ¹¹ and R ¹² and L ^{2 which} are substituents of repeating units may be the same or different from each other. ]

Specifically, the compound according to an embodiment of the present invention is to form a more improved conjugated structure, to increase the plan view to minimize the phase transition and at the same time improve the pi-pie stacking, the number of the center skeleton and the center skeleton and halo-substituted The form of the linking group (substituent A of Formula 1) between indan functional groups can be controlled. That is, the improved solubility and charge mobility can be realized by controlling the substituents mentioned.

For example, the compound of Formula 1 may be a repeating unit of the central skeleton is an integer of at least two or more.

For example, the compound of Formula 1 may include a linking group having at least two monocyclic aromatic rings (substituent A of Formula 1) or a linking group including a polycyclic aromatic ring.

For example, when the compound of Formula 1 includes a linking group having at least two monocyclic aromatic rings, the repeating aromatic rings may have different or different substituents from each other.

In addition, the compound according to an embodiment of the present invention, when the repeating unit of the central skeleton is 1, it exhibits excellent light stability and long-term stability with high compatibility with the electron acceptor, giving excellent life characteristics.

The compound according to an embodiment of the present invention, in Formula 1 or Formula 2, A is selected from the above structure, and preferably may include S as a heteroatom.

The compound according to an embodiment of the present invention may be specifically selected from the following structures, but is not limited thereto.

Hereinafter, a method for preparing a compound according to an embodiment of the present invention will be described, but it is not limited if the preparation method is possible within a range that can be recognized by those skilled in the art.

Specifically, the compound of Formula 1 may be prepared by reacting a dicarbaldehyde compound of Formula A and an indane compound of Formula B.

[Formula 1]

[Formula A]

[Formula B]

[In Formula 1, A and B,

Z ¹ and Z ² are each independently O, S or Se;

R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, wherein the aryl or heteroaryl are each independently C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio;

A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano;

Y ¹ and Y ² are each independently O or S;

Each R ³ is independently halogen;

n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other;

m is an integer from 1 to 5;

The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P.]

The compounds of the present invention are easy to manufacture in high yield and high purity by the simple process described above, and thus are highly industrially available.

In the production method according to an embodiment of the present invention, any solvent used may be a conventional organic solvent. For example, dichloromethane (DCM), dichloroethane (DCE), toluene, toluene, acetonitrile (MeCN), nitromethan, tetrahydrofuran (THF), N, N -dimethyl form One or two or more mixed solvents selected from amide (DMF) and N, N -dimethylacetamide (DMA) and the like can be used.

The reaction temperature may be used at a temperature used in a conventional organic synthesis, but may vary depending on the reaction time and the amount of the starting material, and complete the reaction after confirming that the starting material is completely consumed through TLC. After the reaction is completed, the solvent may be distilled off under reduced pressure after the extraction process, and the desired product may be separated and purified through conventional methods such as column chromatography.

The present invention provides an organic photoelectric conversion material comprising the compound of formula (1).

The compound of formula 1 has a maximum absorption wavelength in the 400 to 700 nm range showing the highest energy intensity in the solar spectrum.

As such, the organic photoelectric conversion material according to the exemplary embodiment of the present invention may be applied to a photovoltaic device, an organic light emitting diode, an organic thin film transistor, or the like.

In another aspect, the present invention provides an organic electronic device comprising a compound of formula (1).

The organic electronic device according to an embodiment of the present invention may be an organic solar cell.

Specifically, the organic solar cell according to the present invention may include a substrate, a first electrode, a buffer layer, a photoactive layer and a second electrode.

The substrate is preferably a transparent material, for example, glass; Or plastics such as polyethylene terephthalate (PET), polyethylene naphthelate (PEN), polypropylene (PP), polyamide (PI), and triacetyl cellulose (TAC).

The first electrode is formed on one surface of the substrate by applying a transparent material or coating in the form of a film using a method such as sputtering or spin coating. The first electrode functions as an anode, and a material having transparency and conductivity is used as a material having a lower work function than the second electrode described later. For example, indium-tin oxide (ITO), fluorine doped tin oxide (FTO), ZnO- (Ga ₂ O ₃ or Al ₂ O ₃ ), SnO ₂ -Sb ₂ O ₃ , or the like may be used.

The buffer layer formed on the first electrode may include PEDOT: PSS (poly (3,4-ethylenedioxythiophene) doped with polystyrenesulfonate) to improve charge mobility. In this case, the buffer layer may be introduced through a method such as spin coating, but is not limited thereto.

The photoactive layer is formed on the buffer layer. The photoactive layer may be formed of a compound using the compound of the present invention as an electron donor and using a single molecule selected from C 60 fullerene, C 70 fullerene derivative and a non fullerene derivative as an electron acceptor. In addition, when the compound of the present invention and a C 60 fullerene derivative or a C 70 fullerene derivative are combined, they are prepared by dissolving them in a single organic solvent or two or more organic solvents having different boiling points, wherein the organic solvent is chlorobenzene, 1,2-dichloro. Benzene, chloroform and the like may be used, and the organic solvent may be prepared so as to contain a solid content of 1.0 to 5.0% by weight. In addition, when the electron donor (compound of the present invention) and the electron acceptor are blended, the ratio may be specifically blended in a weight ratio of 1: 0.5 to 1: 4, and more specifically in a weight ratio of 1: 1 to 1: 2. It is good to be combined. When the above-described compounding ratio is satisfied, not only efficient absorption of light but also pi-pie stacking on the crystallized solid phase may be improved to realize high charge mobility. In addition, the solution in which the electron donor (compound of the present invention) and the electron acceptor are dissolved is applied or coated by a method such as an inkjet printing method, a spin coating method, a screen printing method, a doctor blade method, or the like, and about 70 nm or more, preferably 80 to 80 nm. A 300 nm thick photoactive layer is formed.

The second electrode acts as a cathode, and gold, aluminum, copper, silver or alloys thereof (calcium / aluminum alloy, magnesium / silver alloy, aluminum / lithium alloy, etc.) may be used.

In addition, the organic solar cell according to the exemplary embodiment of the present invention may be a stacked organic solar cell including two or more photoactive layers having different absorptions. This absorbs the necessary area for each layer, thereby achieving higher efficiency than a single layer organic solar cell.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples. At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. In addition, repeated description of the same technical configuration and operation as in the prior art will be omitted.

Example 1 Preparation of Compound 1

Step 1.

Benzodithiophene (1) (5 g, 6.82 mmol) was dissolved in 60 mL of THF and the temperature was lowered to -78 ° C and n-butyllithium (3.8 ml, 6.14 mmol, 1.6 M solution in Hexane) was slowly added. After stirring at −78 ° C. for 1 hour, 1,2-dioodoethane (1.92 g, 6.82 mmol) was added while maintaining −78 ° C. After further stirring at room temperature (23 ° C.) for 15 hours, methanol was added to the reaction solution to terminate the reaction. The solvent was distilled under reduced pressure and the residue was separated by column chromatography to obtain the title compound (2) (4.7 g, 80%). Got it.

¹ H-NMR (400 MHz, CHCl 3): δ 7.84 (s, 1H), 7.65 (d, J = 5.6 Hz, 1H), 7.48 (d, J = 5.7 Hz, 1H), 7.17 (s, 2H), 2.74 (m, 4H), 2.59 (dd, J = 11.2, 7.8 Hz, 4H), 1.65 (m, 6H), 1.52-1.32 (m, 24H), 1.03-0.79 (m, 18H).

Step 2.

Toluene / dimethylformamide (1/1 (v / v), 100 mL) solution of (2) with (5.0 g, 5.73 mmol), Cs2CO3 (1.96 g, 6.01 mmol) and hydroquinone (0.38 g, 3.44 mmol) Pd ₂ (dba) ₃ (0.26 g, 0.29 mmol) and tri (ortho-tolyl) phosphine (0.26 g, 0.86 mmol) were added to an argon atmosphere, and the mixture was stirred at 90 ° C. for 12 hours. The catalysts were removed using a celite filter, the solvent was distilled off under reduced pressure, and then separated by column chromatography to obtain the title compound (3) (2.8 g, 65%).

¹ H-NMR (400 MHz, CHCl 3): δ 7.82 (s, 2H), 7.62 (d, J = 5.7 Hz, 2H), 7.44 (d, J = 5.7 Hz, 2H), 7.23 (s, 2H), 7.20 (s, 2H), 2.76 (dd, J = 6.9, 4.6 Hz, 8H), 2.61 (td, J = 8.0, 4.4 Hz, 8H), 1.65 (dd, J = 17.3, 11.3 Hz, 12H), 2.04 -1.20 (m, 56H), 2.04-0.70 (m, 36H).

Step 3.

Compound (3) (1.0 g, 0.67 mmol) was dissolved in 50 mL of tetrahydrofuran (THF) and the temperature was lowered to -78 ° C, and n-butyllithium (1.0 ml, 1.68 mmol, 1.6 M solution in Hexane) was slowly added. . After stirring at −78 ° C. for 1 hour, trimethyltinchloride (1.7 ml, 1.68 mmol) was added. After further stirring at room temperature for 15 hours, the reaction was terminated with cold water, extracted with ethyl acetate, water was removed with magnesium sulfate (MgSO ₄ ), and the solvent was distilled off under reduced pressure to obtain the title compound (4) (0.8 g). , 78%) used directly for next step reaction without further purification.

Step 4.

A solution of compound (4) (1.15 g, 0.63 mmol) and compound (5) (0.83 g, 1.58 mmol) in toluene / dimethylformamide (20 mL, 4: 1, v / v) was dissolved in Pd ( PPh3) 4 (0.040 g, 0.035 mmol) was added thereto and stirred at 110 ° C. for 16 hours. The solvent was distilled under reduced pressure and then separated by column chromatography to obtain the title compound (6) (0.75 g, 50%).

¹ H-NMR (400 MHz, CHCl 3): δ 9.89 (s, 2H), 7.78 (d, J = 2.0 Hz, 2H), 7.71-7.70 (m, 2H), 7.66 (s, 2H), 7.24 (dd , J = 8.4, 5.4 Hz, 6H), 7.12 (s, 2H), 7.01 (s, 2H), 2.84-2.75 (m, 16H), 2.64 (t, J = 6.9 Hz, 8H), 1.88-1.67 ( m, 20H), 1.52-1.30 (m, 80H), 1.07-0.74 (m, 48H).

Step 5.

Triethylamine (0.1 mL) was added to a dichloroethane (10 mL) solution in which compound (6) (0.267 g, 0.11 mmol) and 3-chloroindandione (0.1 g, 0.56 mmol) were dissolved, followed by argon atmosphere. Stir at room temperature for 13 hours. Dropping the reaction solution in methanol (20 mL) to form a precipitate, and the resulting precipitate was filtered and dissolved again with a minimum amount of chloroform and again precipitated with hexane to give Compound 1 (0.25 g, 81%).

¹ H-NMR (400 MHz, CHCl 3): δ 8.08-8.04 (m, 2H), 7.90 (s, 1H), 7.86-7.80 (m, 2H), 7.73 (s, 2H), 7.68-7.60 (m, 6H ), 7.29-7.24 (m, 6H), 7.09 (s, 2H), 7.02 (s, 2H), 2.94-2.87 (m, 4H), 2.81-2.79 (m, 8H), 2.68-2.63 (m, 8H ), 1.72-1.68 (m, 20H), 1.51-1.19 (m, 80H), 1.13-0.69 (m, 48H).

Example 2 Preparation of Compound 2

Step 1.

Compound (7) (2.0 g, 2.72 mmol) was dissolved in 100 mL of tetrahydrofuran and the temperature was lowered to −78 ° C. and n-butyllithium (4.26 ml, 6.82 mmol, 1.6 M solution in Hexane) was slowly added. After stirring at −78 ° C. for 1 h, trimethyltin chloride (6.8 ml, 6.82 mmol) was added. After further stirring at room temperature for 15 hours, the reaction was terminated with cold water, extracted with ethyl acetate, water was removed with magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain the title compound (8) (2.85 g, 97%). Used directly in the next step reaction without further purification.

Step 2.

A solution of compound (8) (1.11 g, 1.03 mmol) and compound (9) (1.50 g, 2.58 mmol) in toluene / dimethylformamide (20 mL, 4: 1, v / v) was dissolved in Pd (argon). PPh ₃ ) ₄ (0.067 g, 0.058 mmol) was added thereto and stirred at 110 ° C. for 16 hours. The solvent was distilled under reduced pressure and then separated by column chromatography to obtain the title compound (10) (1.03 g, 57%).

¹ H-NMR (400 MHz, CHCl 3): δ 9.83 (s, 2H), 7.68 (s, 2H), 7.60 (s, 2H), 7.23-7.26 (m, 4) 7.12 (s, 4H), 2.85- 2.77 (m, 14H), 2.67-2.63 (m, 4H), 1.75-1.60 (m, 16H), 1.50-1.28 (m, 76H), 0.98-0.85 (m, 34H).

Step 3.

Triethylamine (0.1 mL) in dichloroethane (5 mL) solution of compound 10 (0.108 g, 0.062 mmol) and 3-fluoroindandione (compound (11), 0.81 g, 0.49 mmol). ) Was added and stirred at room temperature for 13 hours under an argon atmosphere. Dropping the reaction solution in methanol (20 mL) gave a precipitate, and the resulting precipitate was filtered and dissolved again with a minimum amount of chloroform and again precipitated with hexane to give the title compound 2 (63 mg, 50%).

¹ H-NMR (400 MHz, CHCl 3): δ 7.90 (m, 1H), 7.89 (s, 1H), 7.76 (m, 2H), 7.69 (s, 1H), 7.41 (m, 2H), 7.25 (m, 1H), 7.17 (d, 1H), 7.14 (s, 1H), 2.87 (m, 6H), 2.66 (t, 2H), 1.71 (m, 8H), 1.43-1.36 (m, 25H), 0.97-0.88 (m, 15 H)

(Examples 3 to 34)

Compounds 3 to 34 were prepared by a method similar to the preparation method of Example 1 or 2, and the structures and the ¹ H NMR of the prepared compounds are shown in Table 1 below.

Example 35-68 Fabrication of Organic Solar Cell Containing Compound of the Invention

An organic substrate coated with ITO (Indium Tin Oxide) coated with a transparent transparent electrode (first electrode) is immersed in deionized water containing a washing solution, and then washed in an ultrasonic cleaner for 15 minutes, and then deionized water, acetone, and isopropyl alcohol (IPA). ) Three times each, and dried in an oven at 130 ° C. for 5 hours. The ITO glass substrate washed as described above was subjected to UV / ozone treatment for 15 minutes and then spin-coated ZnO.NPs having a thickness of 30 nm on the ITO substrate. The substrate coated with ZnO.NPs was heat-treated at 100 ° C. for 10 minutes on a hot plate. Next, a PEDOT / PSS buffer layer for hole-migration was formed to a thickness of 20 nm. The device was then transferred to a glove box filled with argon to apply a photoactive layer. The photoactive layer was prepared by dissolving the compound of the present invention and PC71BM described in Table 1 in a chloroform solvent in a ratio of 1: 1 by weight, and spin-coating the solution with a solution filtered through a 0.45 μm (PTFE) syringe filter. It was prepared by coating over a buffer layer to a thickness of 100 nm. An organic solar cell was completed by depositing a 100 nm thick Ag electrode as a 10 nm thick MoO ₃ , top electrode on the photoactive layer under 3 × 10 ⁻⁶ torr vacuum in a thermal evaporator.

The open circuit voltage (Voc), short circuit current (Jsc), fill factor (FF) and power conversion efficiency (PCE), which are electrical characteristics of the fabricated organic solar cell, are shown in Table 2 below.

Comparative Example 1 Fabrication of Organic Solar Cell

An organic solar cell was manufactured in the same manner as in Example 35, using a compound having the following structure instead of a compound of the present invention. The results are shown in Table 2 below.

As shown in Table 2, the organic solar cell employing the compound according to the present invention has a high efficiency by affecting the rise of all factors such as the open voltage, current, fill factor affecting the energy conversion efficiency (photoelectric conversion efficiency) It can be seen that the result of.

Specifically, the organic solar cell employing the compound according to the present invention implements an energy conversion efficiency of up to 10.25%. In particular, the organic solar cell has a fill factor value of 70% or more. These results (fill factor value) is up to a level of 127% or more compared to the comparative example, and is expected to be a synergistic effect by introducing a halo-substituted indan functional group in the central skeleton.

Therefore, the compound according to the present invention can be usefully used as an organic photoelectric conversion material that can implement a high efficiency with an excellently improved charge mobility. In addition, the compound according to the present invention is expected to be highly commercially available, as it is confirmed that the structure is easy for the solution process.

Although described in detail with respect to embodiments of the present invention as described above, those of ordinary skill in the art, within the scope not departing from the spirit of the invention defined in the appended claims Various modifications may be made to the invention. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.

Claims (10)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, Z ¹ and Z ² are each independently O, S or Se; R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, said aryl or Heteroaryls may each be further substituted with one or more substituents independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio; A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano; Y ¹ and Y ² are each independently O or S; Each R ³ is independently halogen; n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other; m is an integer from 1 to 5; The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P. The method of claim 1, Z ¹ and Z ² are each independently O, S, or Se; R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, wherein the aryl Or heteroaryl may each be further substituted with one or more substituents independently selected from C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio; Each A is independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C May be further substituted with one or more substituents selected from ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano; Y ¹ and Y ² are each independently O or S; Each R ³ is independently halogen; N is each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other; M is an integer from 1 to 5, a compound. The method of claim 1, The compound is represented by the following formula (3), a compound: [Formula 2]

In Chemical Formula 2, Z ¹ and Z ² are each independently O or S; R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylC ₆ -C ₃₀ aryl or C ₁ -C ₃₀ alkylC ₃ -C ₃₀ heteroaryl ; Each A is independently C ₃ -C ₃₀ heteroarylene, wherein the heteroarylene is C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, May be further substituted with one or more substituents selected from C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano; Each R ³ is independently halogen; n are each independently an integer from 1 to 4; m is an integer of 1-5. The method of claim 1, A is selected from heteroarylene having the structure:

In the above structure, L ¹ and L ² are each independently O, S or Se; R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, Halogen or cyano; R ¹³ is C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen or cyano; p is an integer of 1 to 4, q is an integer of 0 to 4, and when p or q is an integer of 2 or more, the R ¹¹ and R ¹² and L ^{2 which} are substituents of repeating units may be the same or different from each other. The method of claim 1, The compound is selected from the following structures.

A method for preparing a compound represented by the following Chemical Formula 1, comprising: reacting a dicarbaldehyde compound of the Chemical Formula A and a phosphorus compound of the Chemical Formula B; [Formula 1]

[Formula A]

[Formula B]

In Formula 1, A and B, Z ¹ and Z ² are each independently O, S or Se; R ¹ and R ² are each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl, wherein the aryl or heteroaryl are each independently C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy and C ₁ -C ₃₀ alkylthio; A is each independently C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene, and the arylene or heteroarylene is each independently C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₁ May be further substituted with one or more substituents selected from -C ₃₀ alkylthio, haloC ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxycarbonyl, halogen and cyano; Y ¹ and Y ² are each independently O or S; Each R ³ is independently halogen; n are each independently an integer of 1 to 4, and when n is an integer of 2 or more, the R ³ may be the same or different from each other; m is an integer from 1 to 5; The heteroaryl and heteroarylene each independently include at least one selected from B, N, O, S, Se, -P (= 0)-, -C (= 0)-, Si and P. An organic photoelectric conversion material comprising the compound according to any one of claims 1 to 5. An organic electronic device comprising the compound according to any one of claims 1 to 5. The method of claim 8, The organic electronic device is an organic solar cell. The method of claim 9, The compound is an organic electronic device that is included in the photoactive layer of the organic solar cell.