TW202006023A - Method and polymer composition for preparing optoelectronic devices - Google Patents

Abstract

The present invention relates to a method for preparing an optoelectronic device comprising a crosslinked polymer material which is prepared from a crosslinkable polymer formulation comprising a polymer with a silazane repeating unit M1 and a metal amide. There is further provided a crosslinkable polymer formulation comprising a silazane and/or siloxazane polymer which is particularly suitable for the preparation of encapsulation materials for optoelectronic devices.

Description

Method for preparing photovoltaic device and polymer composition

The present invention relates to a method for preparing an optoelectronic device containing a cross-linked polymer material prepared from a cross-linkable polymer formulation containing a polymer having a polymer selected from silazane Repeating unit and repeating unit M ^{1 of} metal amide. Metal amide quasi-permitted cross-linked polymer formulations uniformly cure at low temperatures and produce improved mechanical characteristics of cross-linked polymer materials. In particular, metal amides allow rapid and complete cross-linking of polymers with silazane and optionally with siloxane repeating units to prepare cross-linked under mild conditions, such as at temperatures less than 200°C Polymer materials. The obtained cross-linked polymer material has extremely high purity and high hardness and does not show any material deterioration such as cracking or discoloration when exposed to heat and/or radiation. Therefore, it is especially suitable for encapsulating materials of optoelectronic devices, where homogeneous and uniform material texture, optical transparency and/or light resistance are required, such as in light emitting diodes (LED) and organic light emitting diodes (OLED) Encapsulated material.

The invention further relates to optoelectronic devices obtainable by the described method. Optoelectronic devices show improved barrier properties, optical transparency, adjustable refractive index, mechanical stability (non-viscous) and thermal stability and UV stability.

In addition to that, there is provided a specific crosslinkable polymer formulation comprising silazane and optionally a siloxane repeating unit and metal amide. The crosslinkable polymer formulation is particularly suitable for preparing encapsulating materials for optoelectronic devices, where homogeneous and uniform material texture, optical transparency, and/or light resistance are required, such as light emitting diodes (LEDs) and organic light emitting diodes Encapsulation material in polar body (OLED).

Polymers containing repeating units of siloxane are usually called polysiloxanes or silicones and polymers containing repeating units of silazane are usually called polysilazanes or polyepoxysilazanes. Although polysilazane is composed of one or more different silazane repeating units, polyepoxysilazane additionally contains one or more different siloxane repeating units. Polysiloxanes, polysilazanes, and polyepoxysilazanes are generally liquid polymers that become solid at a molecular weight of approximately> 10,000 g/mol. In most applications, liquid polymers of equal molecular weight, usually in the range of 2,000 to 8,000 g/mol, are used. For the preparation of solid coatings from such liquid polymers, a curing step is required, which is usually carried out at a high temperature after the material is applied on the substrate in the form of pure material or formulation.

Polysilazane or polyepoxysilazane is cross-linked by a hydrolysis reaction, in which the moisture from the air reacts according to the mechanism shown in the following equations (I) and (II): Equation (I): Si- Hydrolysis of N bond R ₃ Si-NH-SiR ₃ + H ₂ O → R ₃ Si-O-SiR ₃ + NH ₃ Equation (II): Hydrolysis of Si-H bond R ₃ Si-H + H-SiR ₃ + H ₂ O → R ₃ Si-O-SiR ₃ + 2H ₂ .

During the hydrolysis reaction, the polymer cross-links and the molecular weight increases causing the material to solidify. Therefore, the crosslinking reaction leads to the curing of the polysilazane or polyepoxysilazane material. For this reason, in this application, the terms "curing" and "crosslinking" and the corresponding verbs "curing" and "crosslinking" are used interchangeably as synonyms.

Generally, curing is carried out by hydrolysis under ambient conditions or at high temperatures up to 220°C or higher. However, if possible, the curing time should be as low as possible.

Various additives have been described in the state of the art to accelerate the crosslinking process of polysilazane under thermal conditions:

WO 2007/028511 A2 relates to the use of polysilazane as a permanent coating on metal and polymer surfaces to prevent corrosion, increase scratch resistance, and promote easier cleaning. Additives such as organic amines, organic acids, metals and metal salts can be used to cure polysilazane formulations to obtain permanent coatings. Depending on the polysilazane formulations and additives, curing can even be carried out at room temperature, but can be accelerated by heating.

Similarly, WO 2004/039904 A1 proposes N-heterocyclic compounds, organic or inorganic acids, metal carboxylates, refined metal particles, peroxides, metal chlorides or organometallic compounds for use under thermal conditions Curing polysilazane formulation.

The coating produced by the aforementioned method requires a relatively long curing time. Due to the low film thickness, the void formation is quite high and the barrier properties of the coating are unsatisfactory. Therefore, there is an improvement in the crosslinking of polymers containing silazane repeating units (such as polysilazane and polyepoxysilazane) especially at temperatures up to 200°C, and the improvement of the mechanical properties of the crosslinked polymers Strongly needed.

Depending on the type of application, it is sometimes possible to use higher temperatures for curing, such as 220°C or higher. However, there are applications that do not withstand high temperatures, or it is only impossible to apply heat. Examples of such applications are the coating of rail cars or subway trains or the coating of building walls in order to apply a protective layer against smudges and graffiti. In addition, due to the nature of the substrate to be coated, high temperatures can be excluded. For example, most plastics begin to degrade and decompose at temperatures above 100°C. However, to date, the solidification of pure liquid polysilazane or polyepoxysilazane under ambient conditions is a relatively slow process. Depending on the chemical composition, it may take several days to fully crosslink the coating based on polysilazane or polyepoxysilazane.

Technical problems and the object of the present invention

An object of the present invention is to provide a method for preparing an optoelectronic device having a cross-linked polymer material as an encapsulating material, the cross-linked polymer having no material degradation such as cracking or discoloration when exposed to heat and/or radiation The improved hardness.

This method should overcome the shortcomings in the state of the art and allow rapid and efficient production of photovoltaic devices. Another object of the present invention is to provide an optoelectronic device obtainable by this method. In addition, one of the objectives of the present invention is to find a new crosslinkable polymer formulation that overcomes the shortcomings of the current advanced technology and which allows the rapid and efficient preparation of encapsulation materials for optoelectronic devices, where homogeneous and uniform materials are needed Texture, optical transparency, and/or light resistance, such as encapsulating materials in light emitting diodes (LEDs) and organic light emitting diodes (OLEDs). The cross-linkable polymer formulation should produce a cross-linked polymer material with improved hardness that does not suffer from material degradation, such as cracking or discoloration when exposed to heat and/or radiation, and is therefore particularly suitable for use in optoelectronic devices Encapsulated material.

The inventors have surprisingly discovered that the above objectives can be solved by the embodiments as provided in the following patent application range, alone or in any combination.

The inventors have discovered that certain metal amides permit uniform curing of cross-linkable polymer formulations containing silazane and optionally containing siloxane repeating units at low temperatures, and result in improved cross-linked polymer materials Material properties.

Therefore, a method for preparing an optoelectronic device including a cross-linked polymer material is provided, the cross-linked polymer material is prepared from a cross-linkable polymer formulation, wherein the method includes the following steps: (a) cross-linkable Before applying the polymer formulation to the photovoltaic device; and (b) curing the cross-linkable polymer formulation to obtain a cross-linked polymer material; characterized in that the cross-linkable polymer formulation is obtained from mixing below : Polymer, which contains repeating unit M ¹ , wherein M ¹ is a silazane repeating unit, and metal amide, which is represented by formula (1): M(NR ₂ ) _m L _n (1) wherein M is selected from B , Al, Ga, Ti and Zr; R may be the same or different at each occurrence and independently selected from the group consisting of: hydrogen, linear alkyl having 1 to 20 carbon atoms, having 2 to Linear alkenyl groups of 20 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 20 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 20 carbon atoms, and those having 4 to 18 carbon atoms Aryl or heteroaryl, in which one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -( C=O)-O- substitution; L is a ligand other than NR ₂ , which can be the same or different at each occurrence and is selected from the group consisting of anionic ligand, neutral ligand and free radical ligand Group; m is an integer greater than or equal to 1; and n is an integer greater than or equal to 0; where if M = B, Al or Ga, then m + n = 3; and if M = Ti or Zr, then m + n = 4.

In addition, an optoelectronic device obtainable by the above method is provided.

In addition, a crosslinkable polymer formulation is provided which is obtained from a mixed polymer and metal amide; wherein the polymer contains a repeating unit M ¹ and further contains (i) repeating units M ² or M ³ or (ii) Repeating units M ² and M ³ , wherein repeating unit M ¹ is represented by formula (I), repeating unit M ² is represented by formula (II) and repeating unit M ³ is represented by formula (III): -[-SiR ¹ R ^2- NR ³ -]- (I) -[-SiR ⁴ R ⁵ -NR ⁶ -]- (II) -[-SiR ⁷ R ⁸ -[O-SiR ⁷ R ⁸ -] _a -NR ⁹ -]- (III ) Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups, and a is 1 Integer to 60; and characterized in that the metal amide is represented by the formula (1): M(NR ₂ ) _m L _n (1) where M is selected from the group consisting of B, Al, Ga, Ti and Zr; R in each The second occurrence may be the same or different and independently selected from the group consisting of: hydrogen, linear alkyl having 1 to 20 carbon atoms, linear alkenyl having 2 to 20 carbon atoms, having 3 to 20 Branched alkyl or alkenyl groups of carbon atoms, cyclic alkyl or alkenyl groups with 3 to 20 carbon atoms, and aryl or heteroaryl groups with 4 to 18 carbon atoms, where one or more hydrogen atoms are visible The case is replaced by F, and one or more non-adjacent CH ₂ groups are optionally replaced by -O-, -(C=O)- or -(C=O)-O-; L is other than NR ₂ Ligands, which may be the same or different at each occurrence and are selected from the group consisting of anionic ligands, neutral ligands and free radical ligands; m is an integer greater than or equal to 1; and n is An integer greater than or equal to 0; where if M = B, Al, or Ga, then m + n = 3; and if M = Ti or Zr, then m + n = 4.

The crosslinkable polymer formulations of the present invention are particularly suitable for the preparation of encapsulating materials for optoelectronic devices, where homogeneous and uniform material texture, optical transparency, and/or light resistance are required, such as light emitting diodes (LEDs) and organic Encapsulation material in light emitting diode (OLED). Therefore, the crosslinkable polymer formulation can be used as an encapsulating material for preparing a converter layer of a phosphor-converted LED (pcLED) having a high refractive index. The crosslinkable polymer formulations show higher curing rates when compared to conventional polymer formulations, and thereby allow more efficient processability. In addition, the cross-linked polymer material has an improved hardness and does not show any material degradation, such as cracking or discoloration, when exposed to heat (such as a temperature> 220°C) and/or radiation.

The preferred embodiments of the present invention are described in the scope of the attached patent application.

Definitions The term "crosslinkable polymer formulation" refers to a formulation containing at least one crosslinkable polymer compound. "Crosslinkable polymer compound" is a polymer compound that can be crosslinked thermally by the influence of radiation and/or a catalyst. The cross-linking reaction involves the interaction of sites or groups on the existing polymer or between existing polymers, which leads to the formation of small regions in the polymer where at least three chains are precipitated. The small region may be an atom, a group of atoms, or a plurality of branch points, atoms, or oligomers or polymer chain groups connected by a bond.

The term "polymer" includes but is not limited to homopolymers, copolymers (such as block, random and alternating copolymers), terpolymers, quaternary copolymers, etc. and blends and modifications thereof. In addition, unless otherwise specifically limited, the term "polymer" shall include all possible configuration isomers of the material. These configurations include but are not limited to isotactic, syndiotactic and non-regular symmetry. A polymer is a molecule with a high relative molecular weight, and its structure basically contains a variety of repeating units (ie, repeating units) that are actually or conceptually derived from molecules (ie, monomers) with a low relative mass.

The term "monomer" as used herein refers to a molecule that can undergo polymerization thereby contributing structural units (repeating units) to the basic structure of the polymer.

The term "homopolymer" as used herein represents a polymer derived from a (real, implied or hypothetical) monomer of a species.

The term "copolymer" as used herein generally means any polymer derived from monomers of more than one species, where the polymer contains corresponding repeating units of more than one species. In one embodiment, the copolymer is the reaction product of monomers of two or more species and therefore contains corresponding repeating units of two or more species. Preferably, the copolymer contains two, three, four, five or six species of repeating units. Copolymers obtained by the copolymerization of three monomer species can also be called terpolymers. Copolymers obtained by the copolymerization of four monomer species can also be called tetrapolymers. The copolymer may exist in the form of block, random and/or alternating copolymers.

The term "block copolymer" as used herein refers to a copolymer in which adjacent blocks are structurally different, that is, adjacent blocks include monomers derived from different species or monomers derived from the same species But repeating units with different composition or sequence distribution of repeating units.

In addition, the term "random copolymer" as used herein refers to a polymer formed of macromolecules, where the probability of finding a given repeating unit at any given location in the chain is independent of the nature of the adjacent repeating unit . Generally, in random copolymers, the sequence distribution of repeating units follows Bernoullian statistics.

The term "alternating copolymer" as used herein represents a copolymer consisting of a macromolecule containing repeating units of two species in an alternating sequence.

The term "polysilazane" as used herein refers to a polymer in which silicon and nitrogen atoms alternate to form a basic backbone. Since each silicon atom is bonded to at least one nitrogen atom and each nitrogen atom is bonded to at least one silicon atom, both chains and rings of the general formula [R ¹ R ² Si-NR ³ ] _m appear, where R ¹ to R ³ may be a hydrogen atom or an organic substituent; and m is an integer. If all substituents R ¹ to R ³ are H atoms, the polymer is designated as perhydropolysilazane, polyperhydrosilazane, or inorganic polysilazane ([H ₂ Si-NH] _m ). If at least one substituent R ¹ to R ³ is an organic substituent, the polymer is designated as an organic polysilazane.

The term "polyepoxysilazane" as used herein refers to a polysilazane that additionally contains a segment in which silicon and oxygen atoms alternate. Such a segment may be represented by, for example, [O-SiR ⁴ R ⁵ ] _n , where R ⁴ and R ⁵ may be hydrogen atoms or organic substituents; and n is an integer. If all the substituents of the polymer are H atoms, the polymer is designated as fully hydrogenated polyepoxysilazane. If at least one substituent of the polymer is an organic substituent, the polymer is designated as organic polyepoxysilazane.

The term "photoelectric device" as used herein refers to an electronic device that operates on both photocurrent and current. This includes electrically driven light sources used to convert light into electrical current, such as laser diodes, LEDs, OLEDs, OLET (organic light emitting transistor) components, such as solar and photovoltaic cells and devices that can electronically control the propagation of light.

The term "LED" as used herein refers to a light emitting device including one or more of the following: semiconductor light source (LED chip), lead frame, wiring, solder (flip chip), converter, filling material, encapsulation Materials, primary optics and/or secondary optics. The LED can be prepared from an LED precursor containing a semiconductor light source (LED chip) and/or lead frame and/or gold wire and/or solder (flip chip). In the LED precursor, neither the LED chip nor the converter is enclosed by the encapsulating material. Usually, the encapsulating material and the converter form part of the converter layer. Depending on the type of application, such converter layers can be directly arranged on the LED chip or alternatively away from it.

The term "OLED" as used herein refers to an organic light-emitting device that generally includes electroactive organic light-emitting materials, and includes but is not limited to organic light-emitting diodes. The OLED device includes at least two electrodes, wherein an organic light emitting material is disposed between the two electrodes. Organic light-emitting materials are generally electroluminescent materials that emit light in response to the passage of electric current or a strong electric field.

The term "converter" as used herein means a material that converts light having a first wavelength into light having a second wavelength, where the second wavelength is different from the first wavelength. The converter is an inorganic material, such as phosphor or quantum material.

"Phosphor" is a fluorescent inorganic material that contains one or more light-emitting centers. The luminescent center is formed by activator elements such as atoms or ions of rare earth metal elements, such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and/or atoms or ions of transition metal elements, such as Cr, Mn, Fe, Co, Ni, Cu, Ag, Au, and Zn, and/or atoms or ions of main group metal elements, such as Na, Tl , Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on the following: garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitrilosilicate, Nitrogen-based aluminosilicate, oxo-nitrogen-based silicate, oxo-nitrogen-based aluminosilicate and rare earth-doped silicon aluminum oxynitride Phosphors within the meaning of this application are electromagnetic radiation that absorbs specific wavelength ranges, preferably blue and/or ultraviolet (UV) electromagnetic radiation, and converts the absorbed electromagnetic radiation into electromagnetic radiation with different wavelength ranges. Visible (VIS) light, materials such as violet, blue, green, yellow, orange, or red light.

"Quantum materials" are semiconductor nanocrystals that form a class of nanomaterials with physical properties, which can be widely tunable by controlling the particle size, composition, and shape. One of the most obvious size-dependent properties of such materials is tunable fluorescent emission. Tunability is provided by the quantum confinement effect, where reducing the particle size leads to "particles in the box" behavior, which causes a blue shift of the band gap energy and thus light emission. For example, in this way, the emission of CdSe nanocrystals can be tuned from 660 nm for particles of about 6.5 nm diameter to 500 nm for particles of about 2 nm diameter. Similar behavior can be achieved when other semiconductors are fabricated to allow wide-spectrum coverage of nanocrystals from UV (using for example ZnSe, CdS) through visible (using for example CdSe, InP) to near IR (using for example InAs). Several semiconductor systems have been shown to change the shape of nanocrystals, of which the rod shape is particularly prominent. Nanorods show the nature of modification from spherical particles. For example, it exhibits polarized emission along the long rod axis, while spherical particles exhibit non-polarized emission. In addition, we have shown that nanorods have advantageous properties in terms of optical gain, presenting the possibility of their use as laser materials (Banin et al., Adv. Mater., (2002) 14, 317). A single nanorod is also shown to exhibit a unique behavior under an external electric field, with the emission reversibly turning on and off (Banin et al., Nano Letters., (2005) 5, 1581).

The term "encapsulating material" or "encapsulating body" as used herein means a material that covers or encloses the converter. Preferably, the encapsulating material forms part of a converter layer containing one or more converters. Depending on the type of application, the converter layer can be directly arranged on the semiconductor light source (LED chip) or alternatively away from it. The converter layer may exist in the form of films with different thicknesses or with uniform thickness. The encapsulation material forms a barrier against the external environment of the LED device, thereby protecting the converter and/or the LED chip. The encapsulation material is preferably in direct contact with the converter and/or LED chip. Typically, the encapsulation material forms part of an LED package that includes LED chips and/or lead frames and/or gold wires and/or solder (flip chip), filler materials, converters, and primary and secondary optics. The encapsulation material may cover the LED chip and/or lead frame and/or gold wire and may contain a converter. The encapsulation material has the function of a surface protection material that resists the influence of the external environment, and guarantees the long-term reliability that means aging stability. Preferably, the converter layer containing the encapsulation material has a thickness of 1 µm to 1 cm, more preferably 10 µm to 1 mm.

The encapsulation material needs to resist to protect the external environmental influences of the LED, which may be chemical external environmental influences, such as moisture, acid, alkali, oxygen, etc., or physical external environmental influences, such as temperature, mechanical impact force or stress. The encapsulating material can act as a binder for the converter, such as phosphor powder or quantum materials (eg quantum dots). The encapsulation can also be shaped to provide the main optical function (lens).

It should be noted that the term "layer (layer/layers)" may be used interchangeably throughout this application. Those of ordinary skill in the art will understand that a single "layer" of material may actually contain several individual sub-layers of material. Similarly, several "sub-layers" of a material can be regarded as a single layer in function. In other words, the term "layer" does not indicate a homogeneous layer of material. A single "layer" may contain various material concentrations and compositions located in sublayers. These sub-layers can be formed in a single forming step or in multiple steps. Unless specifically stated otherwise, it is not intended to limit the scope of the invention as embodied in the scope of the patent application by describing the element as "layers/layers" containing materials.

For the purposes of this application, the term "organic group" is used to indicate any organic substituent that has a free valence at a carbon atom regardless of the type of function.

For the purposes of this application, the term "organic heteroatom group" is used to indicate any monovalent group containing carbon, which is therefore organic, but which has a free valence at atoms other than carbon.

As used herein, the term "heteroatom" should be understood to mean an atom that is not an H- or C-atom in an organic compound, and preferably should be understood to mean N, O, S, P, Si, Se , As, Te or Ge.

The organic group or organic heteroatom group containing a chain of 3 or more C atoms may be linear, branched, and/or cyclic, including spiro and/or fused rings.

Preferred organic groups and organic heteroatom groups include alkyl, alkoxy, alkylsilyl, alkylsiloxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, and alkoxycarbonyloxy , Each of which is optionally substituted and has 1 to 40, preferably 1 to 25, more preferably 1 to 18 C atoms, in addition, 6 to 40, preferably 6 to 25 C atoms In case of substituted aryl, aryloxy, arylsilyl or arylsilyloxy, in addition, alkylaryloxy, alkylarylsilyl, alkylarylsilyloxy, arylalkylsilane Group, arylalkyl group, arylcarbonylsilyloxy group, arylcarbonyl group, aryloxycarbonyl group, arylcarbonyloxy group and aryloxycarbonyloxy group, each of which is optionally substituted and has 7 to 40 , Preferably 7 to 20 C atoms, all of which optionally contain one or more heteroatoms selected from N, O, S, P, Si, Se, As, Te, and Ge.

The organic group or organic heteroatom group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups, especially aryl, alkenyl and alkynyl groups (especially ethynyl) are preferred. When the C ₁ -C ₄₀ organic group or organic heteroatom group is acyclic, the group may be linear or branched. The C ₁ -C ₄₀ organic group or organic heteroatom group includes, for example: C ₁ -C ₄₀ alkyl group, C ₁ -C ₄₀ fluoroalkyl group, C ₁ -C ₄₀ alkoxy group or oxaalkyl group, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl, C ₄ -C ₄₀ alkyldienyl, C ₄ -C ₄₀ polyalkenyl, C ₂ -C ₄₀ keto, C ₂ -C ₄₀ ester group, C ₆ -C ₁₈ aryl group, C ₆ -C ₄₀ alkaryl group, C ₆ -C ₄₀ aralkyl group, C ₄ -C ₄₀ cycloalkyl group, C ₄ -C ₄₀ cycloalkenyl group And similar groups. Preferred among the aforementioned groups are C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ fluoroalkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₃ -C ₂₀ allyl , C ₄ -C ₂₀ alkyldienyl, C ₂ -C ₂₀ ketone, C ₂ -C ₂₀ ester, C ₆ -C ₁₂ aryl and C ₄ -C ₂₀ polyalkenyl. Also included are combinations of groups with carbon atoms and groups with heteroatoms, such as alkynyl groups, preferably ethynyl groups, which are substituted with silane groups, preferably trialkylsilyl groups.

The terms "aryl" and "heteroaryl" as used herein preferably mean a monocyclic, bicyclic or tricyclic aromatic or heteroaromatic group having 4 to 18 ring C atoms, which may also include Condensed rings and optionally substituted with one or more groups L, where L is selected from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C(=O)X ⁰ , -C(=O)R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH,- NO ₂ , -CF ₃ , -SF ₅ , optionally substituted silane groups or organic groups or organic heteroatom groups having 1 to 40 C atoms, optionally substituted and optionally containing one or more heteroatoms, And it is preferably a fluorinated alkyl group having 1 to 20 C atoms, an alkoxy group, a thioalkyl group, an alkylcarbonyl group, an alkoxycarbonyl group or an alkoxycarbonyloxy group, and R ⁰ , R ⁰⁰ and X ⁰ have the meanings given below.

An excellent substituent L is selected from halogen, most preferably F, or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl and fluoroalkoxy having 1 to 12 C atoms, or Alkenyl and alkynyl groups with 2 to 12 C atoms.

Particularly preferred aryl and heteroaryl groups are phenyl, pentafluorophenyl, phenyl (where one or more CH groups are replaced by N), naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene , Stilbene and oxazole, the above owners can be unsubstituted, mono- or poly-substituted by L as defined above. Excellent ring is selected from pyrrole (preferably N-pyrrole), furan, pyridine (preferably 2-pyridine or 3-pyridine), pyrimidine, pyrazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isoazole Thiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene (preferably 2-thiophene), selenophene (preferably 2-selenophene), thieno[3,2-b]thiophene, Thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, selenophene[ 2,3-b]Selenophene, thieno[3,2-b]selenophene, thieno[3,2-b]furan, indole, isoindole, benzo[b]furan, benzo[b ]Thiophene, benzo[1,2-b;4,5-b']dithiophene, benzo[2,1-b;3,4-b']dithiophene, quinoline, 2-methylquinoline , Isoquinoline, quinoline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzo Thiadiazole, the above owners can be unsubstituted, mono- or poly-substituted by L as defined above. Other examples of aryl and heteroaryl groups are their groups selected from the groups shown below.

Alkyl or alkoxy, that is, where the terminal CH ₂ group is replaced by -O-, may be linear or branched. It is preferably straight-chain/linear. Suitable examples of such alkyl and alkoxy groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl, tetradecyl, pentadecyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy Group, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy. Preferred alkyl and alkoxy groups have 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. Suitable examples of such preferred alkyl and alkoxy groups can be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy.

Alkenyl, in which one or more CH ₂ groups are replaced by -CH=CH-, may be linear or branched. It is preferably straight-chain, having 2 to 10 C atoms and is therefore preferably vinyl; prop-1-enyl or prop-2-enyl; but-1-enyl, but-2-enyl or But-3-enyl; pent-1-enyl, pent-2-enyl, pent-3-enyl or pent-4-enyl; hex-1-enyl, hex-2-enyl, hex -3-alkenyl, hex-4-enyl or hex-5-enyl; hept-1-enyl, hept-2-enyl, hept-3-enyl, hept-4-enyl, hept- 5-alkenyl or hept-6-alkenyl; oct-1-enyl, oc-2-enyl, oct-3-enyl, oct-4-enyl, oct-5-enyl, oct-6 -Alkenyl or oct-7-alkenyl; non-1-enyl, non-2-enyl, non-3-enyl, non-4-enyl, non-5-enyl, non-6- Alkenyl, non-7-alkenyl or non-8-alkenyl; dec-1-enyl, dec-2-enyl, dec-3-enyl, dec-4-enyl, dec-5-ene Group, dec-6-alkenyl, dec-7-alkenyl, dec-8-alkenyl or dec-9-alkenyl.

Particularly preferred alkenyl groups are C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl, C ₅ -C ₇ -4-alkenyl, C ₆ -C ₇ -5-alkenyl And C ₇ -6-alkenyl, especially C ₂ -C ₇ -1E-alkenyl, C ₄ -C ₇ -3E-alkenyl and C ₅ -C ₇ -4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentyl Alkenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl And similar groups. Alkenyl groups having up to 5 C atoms are generally preferred.

Oxaalkyl, ie one of the CH ₂ groups is replaced by -O-, preferably for example linear 2-oxapropyl (=methoxymethyl), 2-(ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-oxapentyl, 3-oxapentyl or 4-oxapentyl, 2-oxahexyl, 3-oxahexyl, 4-oxahexyl or 5-oxahexyl, 2-oxaheptyl, 3-oxaheptyl, 4-oxaheptyl, 5-oxaheptyl or 6-oxaheptyl, 2-oxa Hetero-octyl, 3-oxa-octyl, 4-oxa-octyl, 5-oxa-octyl, 6-oxa-octyl or 7-oxa-octyl, 2-oxa-nonyl, 3-oxa Nonyl, 4-oxanonyl, 5-oxanonyl, 6-oxanonyl, 7-oxanonyl or 8-oxanonyl or 2-oxadecyl, 3-oxadecyl Group, 4-oxadecyl, 5-oxadecyl, 6-oxadecyl, 7-oxadecyl, 8-oxadecyl or 9-oxadecyl. Oxaalkyl, ie one of the CH ₂ groups is replaced by -O-, preferably for example straight-chain 2-oxapropyl (= methoxymethyl), 2-oxabutyl (= ethoxy Methyl) or 3-oxabutyl (= 2-methoxyethyl), 2-oxapentyl, 3-oxapentyl or 4-oxapentyl, 2-oxahexyl, 3 -Oxahexyl, 4-oxahexyl or 5-oxahexyl, 2-oxaheptyl, 3-oxaheptyl, 4-oxaheptyl, 5-oxaheptyl or 6-oxaheptyl Group, 2-oxactyl, 3-oxactyl, 4-oxactyl, 5-oxactyl, 6-oxactyl or 7-oxactyl, 2-oxanonyl , 3-oxanonyl, 4-oxanonyl, 5-oxanonyl, 6-oxanonyl, 7-oxanonyl or 8-oxanonyl or 2-oxadecyl, 3-oxadecyl, 4-oxadecyl, 5-oxadecyl, 6-oxadecyl, 7-oxadecyl, 8-oxadecyl or 9-oxadecyl.

In a CH ₂ group substituted with -O- and an alkyl group substituted with -C(O)-, such groups are preferably adjacent. Therefore, these groups together form carbonyloxy-C(O)-O- or oxycarbonyl-OC(O)-. Preferably, this group is linear and has 2 to 6 C atoms. Therefore, it is preferably selected from the group consisting of acetyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, acetyloxymethyl, propyloxymethyl , Butyryloxymethyl, pentyloxymethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butyryloxyethyl, 3-ethoxypropyl , 3-Propyloxypropyl, 4-Ethyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl , Ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxy Carbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl and 4-(methoxycarbonyl)-butyl.

The alkyl group in which two or more CH ₂ groups are substituted with -O- and/or -C(O)O- may be a straight chain or a branched chain. It is preferably linear and has 3 to 12 C atoms. Therefore, it is preferably selected from the group consisting of bis-carboxy-methyl, 2,2-biscarboxy-ethyl, 3,3-biscarboxy-propyl, 4,4-biscarboxy-butyl, 5 ,5-Dicarboxy-pentyl, 6,6-dicarboxy-hexyl, 7,7-dicarboxy-heptyl, 8,8-dicarboxy-octyl, 9,9-bis-carboxy-nonyl, 10 ,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl) -Propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl , 7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis -(Ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl and 5,5-bis-( Ethoxycarbonyl)-hexyl.

Thioalkyl, ie one of the CH ₂ groups is replaced by -S-, preferably linear thiomethyl (-SCH ₃ ), 1-thioethyl (-SCH ₂ CH ₃ ), 1- Thiopropyl (= -SCH ₂ CH ₂ CH ₃ ), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), which is preferred The CH ₂ group adjacent to the sp ² mixed with a vinyl carbon atom is replaced.

The fluoroalkyl group is preferably a perfluoroalkyl group C _i F _2i+1 , where i is an integer from 1 to 15, especially CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ or C ₈ F ₁₇ , excellent C ₆ F ₁₃ , or partially fluorinated alkyl, especially 1,1-difluoroalkyl, the above owners are all straight chain or branched chain .

The alkyl group, alkoxy group, alkenyl group, oxaalkyl group, thioalkyl group, carbonyl group, and carbonyloxy group may be a non-parametric or paraparametric group. Particularly preferred para palmyl groups are, for example, 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethyl Hexyl, 2-propylpentyl (especially 2-methylbutyl), 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethyl-hexyloxy , 1-methylhexyloxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methyl-pentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methyl-oxyoctyloxy, 6-methyloctyloxy, 6-methyloctyloxy, 5-Methylheptyloxy-carbonyl, 2-methylbutyryloxy, 3-methylpentyloxy, 4-methylheptyloxy, 2-chloropropionyloxy, 2-chloro-3 -Methylbutyryloxy, 2-chloro-4-methyl-pentyl-oxy, 2-chloro-3-methylpentyloxy, 2-methyl-3-oxapentyl, 2 -Methyl-3-oxa-hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro -2-octyl, 2-fluoromethyloctyloxy. Very good are 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1, 1-trifluoro-2-octyloxy.

Preferred non-para- palm branched chain groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tertiary butyl, isopropoxy, 2 -Methyl-propoxy and 3-methylbutoxy.

其中「ALK」指示具有1至20個、較佳1至12個C原子(在三級基團之情況下極佳1至9個C原子)之視情況經氟化、較佳直鏈烷基或烷氧基，且虛線指示與此等基團所附接至之環的鍵。在此等基團中尤其較佳的為其中所有ALK亞基均相同之彼等基團。In a preferred embodiment, the organic group and the organic heteroatom group are independently selected from the first, second or third alkyl or alkoxy groups having 1 to 30 C atoms, one or more of which are H atoms Aryl, aryloxy, heteroaryl or heteroaryloxy, optionally substituted by F or optionally alkylated or alkoxylated and having 4 to 30 ring atoms. An excellent group of this type is selected from the group consisting of:

Where "ALK" indicates 1 to 20, preferably 1 to 12 C atoms (in the case of tertiary groups, excellent 1 to 9 C atoms) optionally fluorinated, preferably straight-chain alkyl Or alkoxy, and the dotted line indicates the bond to the ring to which these groups are attached. Particularly preferred among these groups are those in which all ALK subunits are the same.

As used herein, "halogen" includes F, Cl, Br, or I, preferably F, Cl, or Br, more preferably F and Cl, and most preferably F.

For the purposes of this application, the term "substituted" is used to indicate the presence of one or more hydrogens replaced by the group R ^S as defined herein.

R ^S at each occurrence is independently selected from the group consisting of any group R ^T as defined herein, an organic group having 1 to 40 carbon atoms or an organic heteroatom group, wherein the organic group or the organic heteroatom group It may be further substituted with one or more groups R ^T and an organic group or organic heteroatom group having 1 to 40 carbon atoms, such carbon atoms including one or more heteroatoms selected from the group consisting of: N, O, S, P, Si, Se, As, Te, Ge, F, and Cl, where N, O, and S are preferred heteroatoms, where the organic group or organic heteroatom group can be further passed through one or more groups R ^T replaced.

Preferred examples of organic groups or organic heteroatom groups suitable for R ^S can be independently selected from phenyl groups, phenyl groups substituted with one or more groups R ^T at each occurrence, alkyl groups and one or more groups Alkyl substituted by R ^T , wherein the alkyl has at least 1, preferably at least 5, more preferably at least 10 and most preferably at least 15 carbon atoms and/or has at most 40, more preferably at most 30 Or even better at most 25 and most preferably at most 20 carbon atoms. It should be noted that, for example, alkyl groups suitable as R ^S also include fluorinated alkyl groups, that is, alkyl groups in which one or more hydrogens are replaced by fluorine, and perfluoroalkyl groups, that is, in which all hydrogens are substituted by Fluorine substituted alkyl.

R ^T is independently selected from the group consisting of F, Br, Cl, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(O)NR ⁰ R ⁰⁰ at each occurrence -C(O)X ⁰ , -C(O)R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH, -OR ⁰ , -NO ₂ , -SF ₅ and -SiR ⁰ R ⁰⁰ R ⁰⁰⁰ . Preferred R ^{T is} selected from the group consisting of: F, Br, Cl, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(O)NR ⁰ R ⁰⁰ , -C(O ) X ⁰ , -C(O)R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -OH, -OR ^0, and -SiR ⁰ R ⁰⁰ R ⁰⁰⁰ .

R ⁰ , R ⁰⁰ and R ⁰⁰⁰ are each independently selected from the group consisting of H, F and an organic group or organic heteroatom group having 1 to 40 carbon atoms at each occurrence. The organic group or organic heteroatom group preferably has at least 5, more preferably at least 10, and most preferably at least 15 carbon atoms. The organic group or organic heteroatom group preferably has at most 30, even more preferably at most 25, and most preferably at most 20 carbon atoms. Preferably, at each occurrence, R ⁰ , R ⁰⁰ and R ⁰⁰⁰ are independently selected from the group consisting of H, F, alkyl, fluorinated alkyl, alkenyl, alkynyl, phenyl and fluorinated Phenyl. More preferably, each time R ⁰ , R ⁰⁰ and R ⁰⁰⁰ are independently selected from the group consisting of H, F, alkyl, fluorinated alkyl (preferably perfluoroalkyl), phenyl and Fluorinated phenyl (preferably perfluorophenyl).

It should be noted that, for example, alkyl groups suitable for R ⁰ , R ⁰⁰ and R ⁰⁰⁰ also include perfluoroalkyl groups, that is, alkyl groups in which all hydrogen is replaced with fluorine. Examples of alkyl groups can be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl (or "third butyl (t-butyl)''), pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Cetyl, heptadecyl, octadecyl, nonadecyl and eicosyl (-C ₂₀ H ₄₁ ).

X ⁰ is halogen. Preferably, X ^{0 is} selected from the group consisting of F, Cl and Br.

Preferred Embodiments The present invention relates to a method for preparing an optoelectronic device including a cross-linked polymer material, which is prepared from a cross-linkable polymer formulation, wherein the method includes the following steps: (a ) Applying the cross-linkable polymer formulation to the precursor of the photovoltaic device; and (b) curing the cross-linkable polymer formulation to obtain a cross-linked polymer material; characterized by the cross-linkable polymer formulation It is obtained by mixing a polymer containing a repeating unit M ¹ , where M ¹ is a silazane repeating unit, and a metal amide, which is represented by formula (1): M(NR ₂ ) _m L _n (1) where M is selected Free group consisting of B, Al, Ga, Ti, and Zr; R may be the same or different at each occurrence and is independently selected from the group consisting of: hydrogen, linear alkyl having 1 to 20 carbon atoms, having Linear alkenyl groups of 2 to 20 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 20 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 20 carbon atoms, and 4 to 18 carbon atoms Atom aryl or heteroaryl, where one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -(C=O)-O- substitution; L is a ligand other than NR ₂ , which may be the same or different at each occurrence and is selected from anionic ligand, neutral ligand and free radical coordination Group consisting of volumes; m is an integer greater than or equal to 1; and n is an integer greater than or equal to 0; where if M = B, Al or Ga, then m + n = 3; and if M = Ti or Zr, then m + n = 4.

Preferably, m is an integer selected from 1, 2, 3, and 4.

Preferably, n is an integer selected from 0, 1, 2 and 3. More preferably, n is 0.

Preferably, if M = B, Al, or Ga, M is trivalent. Preferably, if M = Ti or Zr, M is tetravalent.

Preferably, the polymer contains a repeating unit M ¹ and another repeating unit M ² , where M ¹ and M ² are silazane units different from each other. Preferably, the polymer contains a repeating unit M ¹ and another repeating unit M ³ , where M ¹ is a silazane unit and M ³ is an epoxysilazane unit. More preferably, the polymer contains a repeating unit M ¹ , another repeating unit M ² and another repeating unit M ³ , where M ¹ is a silazane unit, M ² is a silazane unit different from M ¹ , and M ³ is epoxy silazane unit.

In a preferred embodiment, the polymer is polysilazane which may be perhydropolysilazane or organic polysilazane. Preferably, the polysilazane contains a repeating unit M ¹ and optionally another repeating unit M ² , where M ¹ and M ² are different silazane units from each other.

In another alternative preferred embodiment, the polymer is polyepoxysilazane which may be perhydropolyepoxysilazane or organic polyepoxysilazane. Preferably, the polyepoxysilazane contains a repeating unit M ¹ and another repeating unit M ³ , where M ¹ is a silazane unit and M ³ is an epoxy silazane unit. More preferably, the polyepoxysilazane contains a repeating unit M ¹ , another repeating unit M ² and another repeating unit M ³ , where M ¹ and M ² are different silazane units from each other and M ³ is an epoxy Silazane unit.

In a particularly preferred embodiment, the polymer is polysilazane which can be perhydropolysilazane or organic polysilazane and can be perhydropolyepoxysilazane or organic polyepoxysilazane Of polyepoxysilazane.

As mentioned above, one component of the crosslinkable polymer composition used in the method according to the invention is a polymer containing repeating units M ¹ . Preferably, the repeating unit M ^{1 is a} silazane repeating unit represented by formula (I): -[-SiR ¹ R ² -NR ³ -]- (I) wherein R ¹ , R ² and R ³ are independent of each other It is selected from the group consisting of hydrogen, organic groups and organic heteroatom groups.

Preferably, R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl having 1 to 40 carbon atoms, alkenyl having 2 to 40 carbon atoms and having 6 to 30 Aryl groups of one carbon atom. More preferably, R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, and phenyl. Optimally, R ¹ , R ² and R ³ are independently hydrogen, methyl or vinyl.

In a preferred embodiment, the polymer also contains another repeating unit M ^{2 in} addition to the repeating unit M ¹ , which is a silazane repeating unit represented by formula (II): -[-SiR ⁴ R ^5- NR ⁶ -]- (II) where R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups; and wherein M ^{2 is} different from M ¹ .

Preferably, R ⁴ , R ⁵ and R ⁶ in formula (II) are independently selected from the group consisting of hydrogen, alkyl groups having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms Groups and aryl groups having 6 to 30 carbon atoms. More preferably, R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, and phenyl. Most preferably, R ⁴ , R ⁵ and R ⁶ are independently hydrogen, methyl or vinyl.

In another preferred embodiment, the polymer containing other repeating units other than repeating units of M ¹ M ³ alkoxy polyalkylene oxide silicone of nitrogen, the other repeating unit represented by the formula M ³ (III): - [-SiR ⁷ R ⁸ -[O-SiR ⁷ R ⁸ -] _a -NR ⁹ -]- (III) where R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups Group, and a is an integer of 1 to 60, preferably 1 to 50. More preferably, a may be an integer of 5 to 50 (long-chain monomer M ³ ); or a may be an integer of 1 to 4 (short-chain monomer M ³ ).

Preferably, R ⁷ , R ⁸ and R ⁹ in formula (III) are independently selected from the group consisting of hydrogen, alkyl groups having 1 to 40 carbon atoms, alkenes having 2 to 40 carbon atoms Groups and aryl groups having 6 to 30 carbon atoms. More preferably, R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, and phenyl. Optimally, R ⁷ , R ⁸ and R ⁹ are independently hydrogen, methyl or vinyl.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred organic groups can be independently selected from the group consisting of: alkyl, substituted Alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkadienyl, substituted alkadienyl, alkynyl, substituted alkynyl, aryl and substituted aryl.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, better organic groups can be independently selected from the group consisting of: alkyl, substituted Alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, substituted alkenyl, alkadienyl, and substituted alkadienyl.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , even better organic groups can be independently selected from the group consisting of: alkyl, Substituted alkyl, alkenyl, substituted alkenyl, alkadienyl and substituted alkadienyl.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, even better organic groups can be independently selected from alkyl and substituted alkyl Form a group.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, the optimal organic group may be independently selected from alkyl groups.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , preferred alkyl groups may be selected from having at least 1 carbon atom and at most 40 carbon atoms , Preferably an alkyl group of at most 30 or 20 carbon atoms, more preferably at most 15 carbon atoms, even more preferably at most 10 carbon atoms and most preferably at most 5 carbon atoms.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , alkyl groups having at least 1 carbon atom and up to 5 carbon atoms can be independently selected from Group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl (2,2-methyl-butyl) And neopentyl (2,2-dimethyl-propyl); preferably selected from the group consisting of methyl, ethyl, n-propyl and isopropyl; more preferably selected from methyl or ethyl; And best selected from methyl.

With respect to R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , preferred cycloalkyl groups may be selected from having at least 3, preferably at least 4 and Cycloalkyl having at least 5 carbon atoms is preferred. Preferred cycloalkyl groups may be selected from cycloalkyl groups having at most 30, preferably at most 25, more preferably at most 20, even more preferably at most 15 and most preferably at most 10 carbon atoms.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred examples of cycloalkyl can be selected from the group consisting of: cyclopentyl, ring Hexyl, cycloheptyl and cyclooctyl.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred alkenyl groups may be selected from having at least 2 carbon atoms and up to 20, more It is preferably an alkenyl group of up to 15, even more preferably up to 10 and most preferably up to 6 carbon atoms. The alkenyl group may contain a C=C double bond at any position within the molecule; for example, the C=C double bond may be terminal or non-terminal.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , the alkenyl group having at least 2 and at most 10 carbon atoms may be vinyl or allyl The base is preferably vinyl.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred alkadienyl groups may be selected from having at least 4 and at most 20, more It is preferably at most 15, even more preferably at most 10, and most preferably at most 6 carbon atoms. The alkenyl group can contain two C=C double bonds at any position in the molecule, with the restriction that the two C=C double bonds are not adjacent to each other; for example, the C=C double bond can be terminal or non- At the end.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , the alkadienyl group having at least 4 and at most 6 carbon atoms may be, for example, butadiene Ene or hexadiene.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred aryl groups may be selected from having at least 6 carbon atoms and up to 30, more It is preferably an aryl group having up to 24 carbon atoms.

For R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , preferred examples of aryl groups can be selected from the group consisting of: phenyl, naphthyl, Phenanthrenyl, anthracenyl, fused tetraphenylyl, tetracyclo[a]anthracene, fused pentaphenyl, quinyl, benzo[a]pyrene, azulenyl, perylene, indenyl, stilbyl and In any of these, one or more (eg 2, 3, or 4) CH groups are replaced by N. In any of these phenyl, naphthyl and any of these, one or more (eg 2, 3 or 4) CH groups are replaced by N. Phenyl is the best.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, preferred organic heteroatom groups may be independently selected from the group consisting of: alkoxy , Alkylsilyl, alkylsiloxy, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 20, more preferably 1 to 18 C atoms; optionally substituted aryloxy, arylsilyl, and arylsilyloxy groups, each of which has 6 to 40, preferably 6 to 20 C atoms; and alkane Aryloxy, alkylarylsilyl, alkylarylsiloxy, arylalkylsilyl, arylalkylsiloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and Aryloxycarbonyloxy, each of which is optionally substituted and has 7 to 40, preferably 7 to 20 C atoms, wherein all such groups optionally contain N, O, One or more heteroatoms of S, P, Si, Se, As, Te, Ge, F and Cl. The organic heteroatom group may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. Unsaturated acyclic or cyclic groups are preferred. In the case where the organic heteroatom group is acyclic, the group may be linear or branched.

As far as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are concerned, better organic heteroatom groups may be selected from organic heteroatom groups as defined in the above definition .

It should be understood that those skilled in the art can freely combine the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the polymer in any desired manner. The preferred and better embodiments mentioned above.

Preferably, the polymer is a copolymer, such as a random copolymer or a block copolymer or a copolymer containing at least one random sequence segment and at least one block sequence segment. More preferably, the polymer is a random copolymer or a block copolymer.

Preferably, the polymer used in the present invention has a molecular weight _Mw of at least 1,000 g/mol, more preferably at least 2,000 g/mol, even more preferably at least 3,000 g/mol as determined by GPC. Preferably, the molecular weight _{Mw of the} polymer is less than 100,000 g/mol. More preferably, the molecular weight _{Mw of the} polymer is in the range of 3,000 to 50,000 g/mol.

Preferably, the total content of the polymer in the crosslinkable polymer formulation is in the range of 0.1 to 99.9% by weight, preferably 0.5 to 99.8% by weight.

In a preferred embodiment of the present invention, the substituent R in the metal amide at each occurrence is independently selected from the group consisting of: hydrogen, linear alkyl having 1 to 12 carbon atoms, having 2 Linear alkenyl groups up to 12 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 12 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 12 carbon atoms and 4 to 10 carbon atoms Aryl or heteroaryl, where one or more hydrogen atoms are optionally replaced by F and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -( C=O)-O- replacement.

In a more preferred embodiment, the substituent R in the metal amide at each occurrence is independently selected from the group consisting of: hydrogen, straight-chain alkyl having 1 to 10 carbon atoms, having 3 to 10 Branched-chain alkyl groups of carbon atoms, cyclic alkyl groups with 3 to 10 carbon atoms, and aryl or heteroaryl groups with 4 to 10 carbon atoms, in which one or more hydrogen atoms are optionally replaced by F and One or more non-adjacent CH ₂ groups may optionally be replaced by -O-, -(C=O)-, or -(C=O)-O-.

In a preferred embodiment, each occurrence of the substituent R is selected from the group consisting of hydrogen, methyl, ethyl and propyl.

As mentioned above, L at each occurrence is independently selected from anionic ligands, neutral ligands or free radical ligands. The anionic ligand and the neutral ligand can be single, double or triple. The free radical ligand can be monovalent, divalent or trivalent.

Preferred anionic ligands and neutral ligands are halide or organic ligands that coordinate M via one, two, or more than two heteroatoms (such as N, O, P, and S).

Preferred anionic ligands are selected from the group consisting of halides, cyanides, alcoholates, carboxylates, deprotonated keto acids, deprotonated ketoesters, and deprotonated diketones.

Preferred halides include fluoride, chloride, bromide and iodide. Preferred alcoholates include methylates, ethanolates, propanolates, butanolates, pentanolates, hexanolates, heptanolates, octanolates, 1,2-diolates (such as vinyl glycolate) ), 1,3-diolate (such as propylene glycolate), 1,4-diolate (such as butylene glycolate), 1,5-diolate (such as pentenyl glycolate), and glycerin Acid esters and their isomers. Preferred carboxylates include formate, acetate, propionate, butyrate, valerate, hexanoate, enanthate, octanoate, oxalate, malonate, succinate , Glutarate, adipate, oxylate, citrate and its isomers. Preferred deprotonated keto acids include those derived from α-keto acid (such as pyruvic acid, oxaloacetic acid and α-ketoglutaric acid), β-keto acid (such as acetoacetic acid and β-ketoglutaric acid) and Deprotonated species of gamma-keto acid (such as acetopropionic acid). Preferred deprotonated ketone esters include deprotonation derived from keto acid esters, such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate and butyl acetoacetate Chemical species. Preferred deprotonated diketones include deprotonated species derived from 1,3-diketones, such as acetylacetone.

Particularly preferred anionic ligands are selected from the group consisting of acetate, propionate, acetopyruvate, cyanide and ethylacetate.

The preferred neutral ligand is selected from the group consisting of alcohol and carbon monoxide.

Preferred alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butanediol, pentanediol, glycerin, and isomers thereof.

A particularly preferred neutral coordination system is selected from the group consisting of carbon monoxide.

Free radical ligands are organic ligands that coordinate M via one, two, or more than two group carbon atoms. Preferred free radical ligands are selected from the group consisting of hydrogen, linear alkyl groups having 1 to 20 carbon atoms, linear alkenyl groups having 2 to 20 carbon atoms, and 3 to 20 carbon atoms Branched alkyl or alkenyl groups, cyclic alkyl or alkenyl groups with 3 to 20 carbon atoms and aryl or heteroaryl groups with 4 to 18 carbon atoms, one or more hydrogen atoms of which may be F is substituted and one or more non-adjacent CH ₂ groups are optionally substituted with -O-, -(C=O)-, or -(C=O)-O-.

More preferably, the free radical ligand is selected from the group consisting of hydrogen, a linear alkyl group having 1 to 12 carbon atoms, a linear alkenyl group having 2 to 12 carbon atoms, and 3 to 12 carbons Atom branched alkyl or alkenyl groups, cyclic alkyl or alkenyl groups with 3 to 12 carbon atoms and aryl or heteroaryl groups with 4 to 10 carbon atoms, where one or more hydrogen atoms are optional Replaced by F and one or more non-adjacent CH ₂ groups are optionally replaced by -O-, -(C=O)- or -(C=O)-O-.

Optimally, the free radical ligand is selected from the group consisting of: hydrogen, a linear alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, having 3 to 10 carbons Atomic cyclic alkyl groups and aryl or heteroaryl groups with 4 to 10 carbon atoms, where one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally available Replaced by -O-, -(C=O)- or -(C=O)-O-.

Particularly preferably, the free radical ligand is selected from the group consisting of hydrogen, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclobutyl, cyclo Amyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, phenyl and naphthyl, which may be partially or fully fluorinated as appropriate.

Optimally, the free radical ligand is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, N-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2, 2-dimethylpropyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylpent-2-yl, 3-methylpent-2-yl, 2-methylpent-3-yl, 3-methylpent-3-yl, 2-ethylbutyl, 3-ethylbutyl, 2,3-dimethyl Butylbutyl, 2,3-dimethylbut-2-yl, 2,2-dimethylbutyl, n-heptyl, n-octyl, n-nonyl, n-decyl, phenyl and naphthyl, which Depending on the situation, it may be partially or completely fluorinated.

In one particularly preferred embodiment of the present invention, the metal amide in the crosslinkable polymer formulation is selected from the group consisting of: Ti(NMe ₂ ) ₄ , Zr(NMe ₂ ) ₄ , Al(NMe ₂ ) ₃ and B(NMe ₂ ) ₃ .

Depending on the metal amide used, the presence of moisture or oxygen can play a role in curing. Those skilled in the art are familiar with these effects and should properly adjust the atmospheric conditions by means of suitable optimization methods.

In a preferred embodiment of the present invention, based on the total weight of the cross-linkable polymer formulation, the content of metal amide in the cross-linkable polymer formulation is 0.001 to 10.00% by weight, preferably 0.005 to 5.00% by weight %, more preferably 0.01 to 3.00% by weight, most preferably 0.02 to 2.00% by weight.

Solvents suitable for crosslinkable polymer formulations are especially organic solvents which are free of water and also free of reactive groups such as hydroxyl groups. Such solvents are, for example, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, esters (such as ethyl acetate or butyl acetate), ketones (such as acetone or methyl ethyl ketone), ethers (such as tetrahydrofuran or dibutyl ether), and mono Alkylene glycol dialkyl ether and polyalkylene glycol dialkyl ether (ethylene glycol dimethyl ether) or a mixture of these solvents.

In a preferred embodiment, the cross-linkable polymer formulation contains the solvent in an amount of ≤ 5% by weight based on the total weight of the cross-linkable polymer formulation.

In an alternative preferred embodiment, the cross-linkable polymer formulation contains the solvent in an amount> 5 wt% based on the total weight of the cross-linkable polymer formulation.

Preferably, the formulation may include one or more additives selected from the group consisting of nanoparticles, conversion agents, viscosity modifiers, surfactants, additives that affect film formation, additives that affect evaporation behavior, and crosslinking Agent. Optimally, the formulation further contains a conversion agent. Nanoparticles can be selected from nitrides, titanates, diamonds, oxides, sulfides, sulfites, sulfates, silicates, and carbides that are optionally modified by the surface of the blocking agent. Preferably, the nanoparticles are materials with a particle size of <100 nm, more preferably <80 nm, even better <60 nm, even better <40 nm and most preferably <20 nm. The particle size can be determined by any standard method known to those skilled in the art, such as dynamic light scattering (DLS), microscopy (SEM or TEM), or calculating the average particle size from BET surface area measurement results.

Preferably, in step (a) of the method for preparing a photovoltaic device, a coating method for coating a liquid formulation is used to provide the crosslinkable polymer formulation on the surface of the precursor of the photovoltaic device. Such coating methods include, for example, a method of wiping with a fabric, a method of wiping with a sponge, spray coating, flow coating, roll coating, dip coating, slit coating, dispensing, screen printing, stencil printing, or inkjet printing. Other methods include, for example, knife coating, spraying, gravure printing, dipping, hot melting, roller, slot die, spinning, or any other method.

More preferably, the crosslinkable polymer formulation is applied as a layer in step (a) at a thickness of 1 µm to 1 cm, more preferably 10 µm to 1 mm. In a preferred embodiment, the formulation is applied as a layer having a thickness of 1 to 800 µm and more preferably 10 to 500 µm. In an alternative preferred embodiment, the formulation is coated as a layer with a thickness of 200 µm to 1 cm, more preferably 200 µm to 5 mm, and most preferably 200 µm to 1 mm.

Preferably, in step (b) of the method for manufacturing a photovoltaic device, the curing is preferably in the range of 140°C to 200°C, more preferably in the range of 150°C to 190°C, and most preferably at 160°C to Carried out at a high temperature in the range of 185°C.

Preferably, the curing in step (b) is performed on a hot plate, in an oven, or in a climatic chamber.

In a preferred embodiment, the curing in step (b) is performed on a hot plate or in an oven at a temperature selected from 140°C to 200°C, more preferably 150°C to 190°C, and most preferably 160°C to 185°C Proceed.

In an alternative preferred embodiment, the curing in step (b) is at a temperature selected from 10°C to 95°C, more preferably 15°C to 85°C, and most preferably 20°C to 85°C at 50% to 99%, more preferably 60 to 95% and optimally 80 to 90% relative humidity in a climatic chamber.

The optoelectronic device obtainable by the method as described above may be an electronic device that operates on both photocurrent and current. Preferably, the optoelectronic device obtainable by this method is a laser diode, LED, OLED, OLET (organic light emitting transistor), solar cell or photovoltaic cell.

Particularly preferred here are LEDs comprising semiconductor light sources (LED chips) and at least one converter, preferably phosphors or quantum materials. The LED preferably emits white light or emits light with a specific color point (according to the principle of color requirements). The concept of color requirements means that the use of pc-LEDs (=phosphor-converted LEDs) uses one or more phosphors to generate light with a specific color point. The encapsulation material forms a barrier against the external environment of the LED device, thereby protecting the converter and/or the LED chip. The encapsulation material is preferably in direct contact with the converter and/or LED chip.

In a preferred embodiment, the semiconductor light source (LED chip) contains light-emitting indium aluminum gallium nitride, which preferably has the formula In _i Ga _j Al _k N, where 0 ≤ i, 0 ≤ j, 0 ≤ k, and I ＋ j ＋ k =1.

In another preferred embodiment, the LED is a light emitting configuration based on ZnO, TCO (transparent conductive oxide), ZnSe or SiC. In another preferred embodiment, the LED is a light source that exhibits electroluminescence and/or photoluminescence.

Preferably, the cross-linked polymer material is included in the converter layer of the LED. Preferably, the converter layer contains a cross-linked polymer material and one or more converters, which are preferably selected from phosphors and/or quantum materials.

Depending on the type of application, the converter layer is placed directly on the semiconductor light source (LED chip) or away from it (the latter configuration also includes "remote phosphor technology"). The advantages of remote phosphor technology are known to those skilled in the art and can be found in, for example, the following publication: Japanese J. of Appl. Phys. Vol. 44, No. 21 (2005), L649-L651.

The optical coupling between the semiconductor light source (LED chip) and the converter layer can also be achieved by the configuration of the light guide. This makes it possible for the semiconductor to be installed at a central location and optically coupled to the converter layer by means of a light guide such as, for example, an optical fiber. In this way, it is possible to achieve a lamp suitable for lighting desired, which consists only of one or various phosphors that can be configured to form an optical screen and a waveguide that can be coupled to the light source. In this way, it is possible to place the strong light source in a position favorable for electrical installation, and to install the lamp containing the phosphor coupled to the optical waveguide at any desired position without additional electrical cables, but instead only By arranging optical waveguides.

Preferably, the converter is a phosphor, that is, a substance with luminescent properties. The term "luminescence" is intended to include both phosphorescence and fluorescence.

For the purposes of this application, the type of phosphor is not particularly limited. Suitable phosphors are well known to those skilled in the art and can be easily obtained from commercial sources. For the purposes of this application, the term "phosphor" is intended to include materials that absorb in one wavelength of the electromagnetic spectrum and emit at different wavelengths.

Examples of suitable phosphors are inorganic fluorescent materials in the form of particles containing one or more emission centers. The emission centers can be formed, for example, by using so-called activators, which are preferably atoms or ions selected from the group consisting of rare earth elements, transition metal elements, main group elements, and any of these elements Any combination of one. Examples of suitable rare earth elements can be selected from the group consisting of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Examples of suitable transition metal elements can be selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Ag, Au, and Zn. Examples of suitable main group elements can be selected from the group consisting of Na, Tl, Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on the following: garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitrilosilicate, Nitrogen-based aluminosilicate, oxo-nitrogen-based silicate, oxo-nitrogen-based aluminosilicate and rare earth-doped silicon aluminum oxynitride

Phosphors that can be used as converters in the crosslinkable polymer formulations of the present invention are, for example: Ba ₂ SiO ₄ :Eu ²⁺ , Ba ₃ SiO ₅ :Eu ²⁺ ,(Ba,Ca) ₃ SiO ₅ : Eu ²⁺ , BaSi ₂ N ₂ O ₂ : Eu, BaSi ₂ O ₅ : Pb ²⁺ , Ba ₃ Si ₆ O ₁₂ N ₂ : Eu, Ba _x Sr _1-x F ₂ : Eu ²⁺ (0 ≤ x ≤ 1), BaSrMgSi ₂ O ₇ :Eu ²⁺ ,BaTiP ₂ O ₇ ,(Ba,Ti) ₂ P ₂ O ₇ :Ti, BaY ₂ F ₈ :Er ³⁺ ,Yb ⁺ ,Be ₂ SiO ₄ :Mn ²⁺ , Bi ₄ Ge ₃ O ₁₂ , CaAl ₂ O ₄ : Ce ³⁺ , CaLa ₄ O ₇ : Ce ³⁺ , CaAl ₂ O ₄ : Eu ²⁺ , CaAl ₂ O ₄ : Mn ²⁺ , CaAl ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , CaAl ₂ O ₄ : Tb ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ : Ce ³⁺ , Ca ₃ Al ₂ Si ₃ O ₁₂ :Eu ²⁺ , Ca ₂ B ₅ O ₉ Br:Eu ²⁺ ,Ca ₂ B ₅ O ₉ Cl:Eu ²⁺ ,Ca ₂ B ₅ O ₉ Cl:Pb ²⁺ ,CaB ₂ O ₄ :Mn ²⁺ , Ca ₂ B ₂ O ₅ : Mn ²⁺ , CaB ₂ O ₄ : Pb ²⁺ , CaB ₂ P ₂ O ₉ : Eu ²⁺ , Ca ₅ B ₂ SiO ₁₀ : Eu ³⁺ , Ca _0.5 Ba _0.5 Al ₁₂ O ₁₉ ^{: Ce 3+, Mn 2+, Ca} 2 Ba 3 (PO 4) 3 Cl: Eu 2+, in SiO ₂ in the CaBr _2: Eu ^2+, in SiO ₂ in the CaCl _2: Eu ^2+, on SiO the _{2 ^{CaCl 2: Eu 2+, Mn 2+}} , CaF 2: Ce 3+, CaF 2: Ce 3+, Mn 2+, CaF 2: Ce 3+, Tb 3+, CaF 2: Eu 2+, CaF ₂ : Mn ²⁺ , CaGa ₂ O ₄ : Mn ²⁺ , CaGa ₄ O ₇ : Mn ²⁺ , CaGa ₂ S ₄ : Ce ³⁺ , CaGa ₂ S ₄ : Eu ²⁺ , CaGa ₂ S ₄ : M ^{_{n 2+, CaGa 2 S 4:}} Pb 2+, CaGeO 3: Mn 2+, in SiO ₂ in the CaI _2: Eu ^2+, in SiO ₂ in the ^{_{CaI 2: Eu 2+, Mn 2+}} , CaLaBO 4 :Eu ³⁺ ,CaLaB ₃ O ₇ :Ce ³⁺ ,Mn ²⁺ ,Ca ₂ La ₂ BO _{6 .5} :Pb ²⁺ ,Ca ₂ MgSi ₂ O ₇ ,Ca ₂ MgSi ₂ O ₇ :Ce ³⁺ ,CaMgSi ₂ O ₆ : Eu ²⁺ , Ca ₃ MgSi ₂ O ₈ : Eu ²⁺ , Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , CaMgSi ₂ O ₆ : Eu ²⁺ , Mn ²⁺ , Ca ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , CaMoO ₄ , CaMoO ₄ : Eu ³⁺ , CaO: Bi ³⁺ , CaO: Cd ²⁺ , CaO: Cu ⁺ , CaO: Eu ³⁺ , CaO: Eu ³⁺ , Na ⁺ , CaO: Mn ²⁺ , CaO: Pb ²⁺ , CaO: Sb ³⁺ , CaO: Sm ³⁺ , CaO: Tb ³⁺ , CaO: Tl, CaO: Zn ²⁺ , Ca ₂ P ₂ O ₇ : Ce ³⁺ , Α-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , β-Ca ₃ (PO ₄ ) ₂ : Ce ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl : Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ Cl: Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Eu ²⁺ , Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F: Mn ²⁺ , Ca ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Ca ₅ (PO ₄ ) ₃ F: Sn ²⁺ , α-Ca ₃ (PO ₄ ) ₂ : Eu ^{2 +} , Β-Ca ₃ (PO ₄ ) ₂ : Eu ²⁺ , Ca ₂ P ₂ O ₇ : Eu ²⁺ , Ca ₂ P ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , CaP ₂ O ₆ : Mn ²⁺ , Α-Ca ₃ (PO ₄ ) ₂ : Pb ²⁺ , α-Ca ₃ (PO ₄ ) ₂ : Sn ²⁺ , β-Ca ₃ (PO ₄ ) ₂ : Sn ²⁺ , β-Ca ₂ P ₂ O ₇ : Sn, Mn, α-Ca ₃ (PO ₄ ) ₂ : Tr, CaS: Bi ³⁺ , CaS: Bi ³⁺ , Na, CaS: Ce ³⁺ , CaS: Eu ²⁺ , CaS: Cu ⁺ , Na ⁺ , CaS: La ³⁺ , CaS: Mn ²⁺ , CaSO ₄ : Bi , CaSO ₄ : Ce ³⁺ , CaSO ₄ : Ce ³⁺ , Mn ²⁺ , CaSO ₄ : Eu ²⁺ , CaSO ₄ : Eu ²⁺ , Mn ²⁺ , CaSO ₄ : Pb ²⁺ , CaS: Pb ²⁺ , CaS: Pb ²⁺ , Cl, CaS: Pb ²⁺ , Mn ²⁺ , CaS: Pr ³⁺ , Pb ²⁺ , Cl, CaS: Sb ³⁺ , CaS: Sb ³⁺ , Na, CaS: Sm ³⁺ , CaS: Sn ²⁺ , CaS: Sn ²⁺ , F, CaS: Tb ³⁺ , CaS: Tb ³⁺ , Cl, CaS: Y ³⁺ , CaS: Yb ²⁺ , CaS: Yb ²⁺ , Cl, CaSc ₂ O ₄ : Ce, Ca ₃ (Sc, Mg) ₂ Si ₃ O ₁₂ : Ce, CaSiO ₃ : Ce ³⁺ , Ca ₃ SiO ₄ Cl ₂ : Eu ²⁺ , Ca ₃ SiO ₄ Cl ₂ : Pb ²⁺ , CaSiO ₃ : Eu ²⁺ , Ca ₃ SiO ₅ : Eu ²⁺ , (Ca, Sr) ₃ SiO ₅ : Eu ²⁺ , (Ca, Sr) ₃ MgSi ₂ O ₈ : Eu ²⁺ , (Ca, Sr) ₃ MgSi ₂ O ₈ :Eu ²⁺ ,Mn ²⁺ ,CaSiO ₃ :Mn ²⁺ ,Pb,CaSiO ₃ :Pb ²⁺ ,CaSiO ₃ :Pb ²⁺ ,Mn ²⁺ ,CaSiO ₃ :Ti ⁴⁺ ,CaSr ₂ (PO ₄ ) ₂ : Bi ³⁺ , β-(Ca, Sr) ₃ (PO ₄ ) ₂ : Sn ²⁺ Mn ²⁺ , CaTi _0.9 Al _0.1 O ₃ : Bi ³⁺ , CaTiO ₃ : Eu ³⁺ , CaTiO ₃ : Pr ³⁺ , Ca ₅ (VO ₄ ) ₃ Cl, CaWO ₄ , CaWO ₄ : Pb ²⁺ , CaWO ₄ : W, Ca ₃ WO ₆ : U, CaYAlO ₄ : Eu ³⁺ , CaYBO ₄ : Bi ³⁺ , CaYBO ₄ : Eu ³⁺ , CaYB _0.8 O _3.7 : Eu ³⁺ , CaY ₂ ZrO ₆ : Eu ³⁺ , (Ca, Zn, Mg) ₃ (PO ₄ ) ₂ : Sn, (Ce, Mg) BaAl ₁₁ O ₁₈ : Ce, (Ce, Mg) SrAl ₁₁ O ₁₈ : Ce, CeMgAl ₁₁ O ₁₉ : Ce: Tb, Cd ₂ B ₆ O ₁₁ : Mn ²⁺ , CdS: Ag ⁺ , Cr, CdS: In, CdS: In, CdS : In, Te, CdS: Te, CdWO ₄ , CsF, Csl, CsI: Na ⁺ , CsI: Tl, (ErCl ₃ ) _0.25 (BaCl ₂ ) _0.75 , GaN: Zn, Gd ₃ Ga ₅ O ₁₂ : Cr ³⁺ , Gd ₃ Ga ₅ O ₁₂ : Cr, Ce, GdNbO ₄ : Bi ³⁺ , Gd ₂ O ₂ S: Eu ³⁺ , Gd ₂ O ₂ Pr ³⁺ , Gd ₂ O ₂ S: Pr, Ce, F, Gd ₂ O ₂ S: Tb ³⁺ , Gd ₂ SiO ₅ : Ce ³⁺ , KAI ₁₁ O ₁₇ : Tl ⁺ , KGa ₁₁ O ₁₇ : Mn ²⁺ , K ₂ La ₂ Ti ₃ O ₁₀ : Eu, KMgF ₃ : Eu ²⁺ , KMgF ₃ : Mn ²⁺ , K ₂ SiF ₆ : Mn ⁴⁺ , LaAl ₃ B ₄ O ₁₂ : Eu ³⁺ , LaAlB ₂ O ₆ : Eu ³⁺ , LaAlO ₃ : Eu ³⁺ , LaAlO ₃ : Sm ³⁺ , LaAsO ₄ : Eu ³⁺ , LaBr ₃ : Ce ³⁺ , LaBO ₃ : Eu ³⁺ , LaCl ₃ : Ce ³⁺ , La ₂ O ₃ : Bi ³⁺ , LaOBr: Tb ³⁺ , LaOBr: Tm ^{3 +, LaOCl: Bi 3+, LaOCl} : Eu 3+, LaOF: Eu 3+, La 2 O 3: Eu 3+, La 2 O 3: Pr 3+, La 2 O 2 S: Tb 3+, LaPO 4 : Ce ³⁺ , LaPO ₄ : Eu ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , LaSiO ₃ Cl: Ce ³⁺ , Tb ³⁺ , LaVO ₄ : Eu ³⁺ , La ₂ W ₃ O ₁₂ : Eu ³⁺ , LiAlF ₄ : Mn ²⁺ , LiAl ₅ O ₈ : Fe ³⁺ , LiAlO ₂ : Fe ³⁺ , LiAlO ₂ : Mn ²⁺ , LiAl ₅ O ₈ : Mn ²⁺ , Li ₂ CaP ₂ O ₇ : Ce ³⁺ , Mn ²⁺ , LiCeBa ₄ Si ₄ O ₁₄ : Mn ²⁺ , LiCeSrBa ₃ Si ₄ O ₁₄ : Mn ²⁺ , L iInO ₂ :Eu ³⁺ , LiInO ₂ :Sm ³⁺ , LiLaO ₂ :Eu ³⁺ ,LuAlO ₃ :Ce ³⁺ , (Lu,Gd) ₂ SiO ₅ :Ce ³⁺ ,Lu ₂ SiO ₅ :Ce ³⁺ , Lu ₂ Si ₂ O ₇ : Ce ³⁺ , LuTaO ₄ : Nb ⁵⁺ , Lu _1-x Y _x AlO ₃ : Ce ³⁺ (0 ≤ x ≤ 1), (Lu,Y) ₃ (Al,Ga,Sc ) ₅ O ₁₂ : Ce, MgAl ₂ O ₄ : Mn ²⁺ , MgSrAl ₁₀ O ₁₇ : Ce, MgB ₂ O ₄ : Mn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : Sn ²⁺ , MgBa ₂ (PO ₄ ) ₂ : U, MgBaP ₂ O ₇ : Eu ²⁺ , MgBaP ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , MgBa ₃ Si ₂ O ₈ : Eu ²⁺ , MgBa(SO ₄ ) ₂ : Eu ²⁺ , Mg ₃ Ca ₃ (PO ₄ ) ₄ : Eu ²⁺ , MgCaP ₂ O ₇ : Mn ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ Ca(SO ₄ ) ₃ : Eu ²⁺ , Mn ² , MgCeAl _n O ₁₉ : Tb ³⁺ , Mg ₄ (F) GeO ₆ : Mn ²⁺ , Mg ₄ (F) (Ge, Sn) O ₆ : Mn ²⁺ , MgF ₂ : Mn ²⁺ , MgGa ₂ O ₄ : Mn ²⁺ , Mg ₈ Ge ₂ O ₁₁ F ₂ : Mn ⁴⁺ , MgS: Eu ²⁺ , MgSiO ₃ : Mn ²⁺ , Mg ₂ SiO ₄ : Mn ²⁺ , Mg ₃ SiO ₃ F ₄ : Ti ⁴⁺ , , MgSO ₄ : Eu ²⁺ , MgSO ₄ : Pb ²⁺ , MgSrBa ₂ Si ₂ O ₇ : Eu ²⁺ , MgSrP ₂ O ₇ : Eu ²⁺ , MgSr ₅ (PO ₄ ) ₄ : Sn ²⁺ , MgSr ₃ Si ₂ O ₈ : Eu ²⁺ , Mn ²⁺ , Mg ₂ Sr(SO ₄ ) ₃ : Eu ²⁺ , Mg ₂ TiO ₄ : Mn ⁴⁺ , MgWO ₄ , MgYBO ₄ : Eu ³⁺ , M ₂ MgSi ₂ O ₇ : Eu ²⁺ (M = Ca, Sr and/or Ba), M ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ (M = Ca, Sr and/or Ba), M ₂ M gSi ₂ O ₇ : Eu ²⁺ , Zr ⁴⁺ (M = Ca, Sr and/or Ba), M ₂ MgSi ₂ O ₇ : Eu ²⁺ , Mn ²⁺ , Zr ⁴⁺ (M = Ca, Sr and/ Or Ba), Na ₃ Ce(PO ₄ ) ₂ : Tb ³⁺ , Na _1.23 K _0.42 Eu _0.12 TiSi ₄ O ₁₁ : Eu ³⁺ , Na _1.23 K _0.42 Eu _0.12 TiSi ₅ O ₁₃ xH ₂ O: Eu ³⁺ , Na _1.29 K _0.46 Er _0.08 TiSi ₄ O ₁₁ : Eu ³⁺ , Na ₂ Mg ₃ Al ₂ Si ₂ O ₁₀ : Tb, Na(Mg _2-x Mn _x ) LiSi ₄ O ₁₀ F ₂ : Mn (0 ≤ x ≤ 2), NaYF ₄ : Er ³⁺ , Yb ³⁺ , NaYO ₂ : Eu ³⁺ , P46 (70%) + P47 (30%), β-SiAlON: Eu, SrAl ₁₂ O ₁₉ : Ce ³⁺ , Mn ²⁺ , SrAl ₂ O ₄ : Eu ²⁺ , SrAl ₄ O ₇ : Eu ³⁺ , SrAl ₁₂ O ₁₉ : Eu ²⁺ , SrAl ₂ S ₄ : Eu ²⁺ , Sr ₂ B ₅ O ₉ Cl: Eu ²⁺ , SrB ₄ O ₇ : Eu ²⁺ (F, Cl, Br), SrB ₄ O ₇ : Pb ²⁺ , SrB ₄ O ₇ : Pb ²⁺ , Mn ²⁺ , SrB ₈ O ₁₃ : Sm ²⁺ , Sr _x Ba _y Cl _z Al ₂ O _4-z/2 : Mn ²⁺ , Ce ³⁺ , SrBaSiO ₄ : Eu ²⁺ , (Sr, Ba) ₃ SiO ₅ : Eu, (Sr, Ca) Si ₂ N ₂ O ₂ : Eu, in SiO ₂ in the Sr (Cl, Br, I) 2: Eu 2+, in the SiO ₂ in ^{_{SrCl 2: Eu 2+, Sr 5}} Cl (PO 4) 3: Eu, Sr w F x B ₄ O _6.5 : Eu ²⁺ , Sr _w F _x B _y O _z : Eu ²⁺ , Sm ²⁺ , SrF ₂ : Eu ²⁺ , SrGa ₁₂ O ₁₉ : Mn ²⁺ , SrGa ₂ S ₄ : Ce ³⁺ , SrGa ₂ S ₄ :Eu ²⁺ , Sr _2-y Ba _y SiO ₄ :Eu (0 ≤ y ≤ 2), SrSi ₂ O ₂ N ₂ :Eu, SrGa ₂ S ₄ :Pb ²⁺ , SrIn ₂ O ₄ : Pr ³⁺ , Al ³⁺ , (Sr, Mg) ₃ (PO ₄ ) ₂ : Sn, SrMgSi ₂ O ₆ : Eu ²⁺ , Sr ₂ MgSi ₂ O ₇ : Eu ²⁺ , Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ , SrMoO ₄ : U, SrO·3B ₂ O ₃ : Eu ²⁺ , Cl, β-SrO·3B ₂ O ₃ : Pb ²⁺ , β-SrO·3B ₂ O ₃ :Pb ²⁺ ,Mn ²⁺ ,α-SrO·3B ₂ O ₃ :Sm ²⁺ ,Sr ₆ P ₅ BO ₂₀ :Eu,Sr ₅ (PO ₄ ) ₃ Cl:Eu ²⁺ ,Sr ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ , Pr ^{3 +} , Sr ₅ (PO ₄ ) ₃ Cl: Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ Cl: Sb ³⁺ , Sr ₂ P ₂ O ₇ : Eu ²⁺ , β- Sr ₃ (PO ₄ ) ₂ : Eu ²⁺ , Sr ₅ (PO ₄ ) ₃ F: Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Sr ₅ (PO ₄ ) ₃ F: Sb ³⁺ , Mn ²⁺ , Sr ₅ (PO ₄ ) ₃ F: Sn ^{2 +} , Sr ₂ P ₂ O ₇ : Sn ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Sn ²⁺ , β-Sr ₃ (PO ₄ ) ₂ : Sn ²⁺ , Mn ²⁺ (Al), SrS: Ce ³⁺ , SrS: Eu ²⁺ , SrS: Mn ²⁺ , SrS: Cu ⁺ , Na, SrSO ₄ : Bi, SrSO ₄ : Ce ³⁺ , SrSO ₄ : Eu ²⁺ , SrSO ₄ : Eu ²⁺ , Mn ²⁺ , Sr ₅ Si ₄ O ₁₀ Cl ₆ : Eu ²⁺ , Sr ₂ SiO ₄ : Eu ²⁺ , Sr ₃ SiO ₅ : Eu ²⁺ , (Sr,Ba) ₃ SiO ₅ :Eu ²⁺ , SrTiO ₃ :Pr ³⁺ ,SrTiO ₃ :Pr ³⁺ ,Al ³⁺ ,SrY ₂ O ₃ :Eu ³⁺ ,, ThO ₂ :Eu ³⁺ ,ThO ₂ : Pr ³⁺ , ThO ₂ : Tb ³⁺ , YAl ₃ B ₄ O ₁₂ : Bi ³⁺ , YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , Mn, YAl ₃ B ₄ O ₁₂ : Ce ³⁺ , Tb ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ , YAl ₃ B ₄ O ₁₂ : Eu ³⁺ , Cr ³⁺ , YAl ₃ B ₄ O ₁₂ : Th ⁴⁺ , Ce ³⁺ , Mn ²⁺ , YAlO ₃ : Ce ³⁺ , Y ₃ Al ₅ O ₁₂ : Ce ³⁺ , Y ₃ Al ₅ O ₁₂ : Cr ³⁺ , YAlO ₃ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Eu ^3r , Y ₄ Al ₂ O ₉ : Eu ³⁺ , Y ₃ Al ₅ O ₁₂ : Mn ⁴⁺ , YAlO ₃ : Sm ³⁺ , YAlO ₃ : Tb ³⁺ , Y ₃ Al ₅ O ₁₂ : Tb ³⁺ , YAsO ₄ : Eu ³⁺ , YBO ₃ : Ce ³⁺ , YBO ₃ : Eu ³⁺ , YF ₃ : Er ³⁺ , Yb ³⁺ , YF ₃ : Mn ²⁺ , YF ₃ : Mn ²⁺ , Th ⁴⁺ , YF ₃ : Tm ³⁺ , Yb ³⁺ , (Y, Gd)BO ₃ :Eu, (Y,Gd)BO ₃ :Tb, (Y,Gd) ₂ O ₃ :Eu ³⁺ ,Y _1.34 Gd _0.60 O ₃ :(Eu,Pr),Y ₂ O ₃ :Bi ^{3 +} , YOBr: Eu ³⁺ , Y ₂ O ₃ : Ce, Y ₂ O ₃ : Er ³⁺ , Y ₂ O ₃ : Eu ³⁺ , Y ₂ O ₃ : Ce ³⁺ , Tb ³⁺ , YOCl: Ce ^{3 +} , YOCl: Eu ³⁺ , YOF: Eu ³⁺ , YOF: Tb ³⁺ , Y ₂ O ₃ : Ho ³⁺ , Y ₂ O ₂ S: Eu ³⁺ , Y ₂ O ₂ S: Pr ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ O ₃ : Tb ³⁺ , YPO ₄ : Ce ³⁺ , YPO ₄ : Ce ³⁺ , Tb ³⁺ , YPO ₄ : Eu ³⁺ , YPO ₄ : Mn ²⁺ , Th ⁴⁺ , YPO ₄ : V ⁵⁺ , Y(P, V) O ₄ : Eu, Y ₂ SiO ₅ : Ce ³⁺ , YTaO ₄ , YTaO ₄ : Nb ⁵⁺ , YVO ₄ : Dy ³⁺ , YVO ₄ : Eu ³⁺ , ZnAl ₂ O ₄ : Mn ²⁺ , ZnB ₂ O ₄ : Mn ²⁺ , ZnBa ₂ S ₃ : Mn ²⁺ , (Zn,Be) ₂ SiO ₄ : Mn ²⁺ , Zn _0.4 Cd _0.6 S : Ag, Zn _0.6 Cd _0.4 S: Ag, (Zn, Cd) S: Ag, Cl, (Zn, Cd) S: Cu, ZnF ₂ : Mn ²⁺ , ZnGa ₂ O ₄ , ZnGa ₂ O ₄ : Mn ²⁺ , ZnGa ₂ S ₄ : Mn ²⁺ , Zn ₂ GeO ₄ : Mn ²⁺ , (Zn, Mg)F ₂ : Mn ²⁺ , ZnMg ₂ (PO ₄ ) ₂ : Mn ²⁺ , (Zn, Mg) ₃ (PO ₄ ) ₂ : Mn ²⁺ , ZnO: Al ³⁺ , Ga ³⁺ , ZnO: Bi ³⁺ , ZnO ^{: Ga 3+, ZnO: Ga,} ZnO-CdO: Ga, ZnO: S, ZnO: Se, ZnO: Zn, ZnS: Ag +, Cl -, ZnS: Ag, Cu, Cl, ZnS: Ag, Ni, ZnS : Au, In, ZnS-CdS (25-75), ZnS-CdS (50-50), ZnS-CdS (75-25), ZnS-CdS: Ag, Br, Ni, ZnS-CdS: Ag ⁺ , Cl , ZnS-CdS: Cu, Br , ZnS-CdS: Cu, I, ZnS: Cl -, ZnS: Eu 2+, ZnS: Cu, ZnS: Cu +, Al 3+, ZnS: Cu +, Cl -, ZnS : Cu, Sn, ZnS: Eu 2+, ZnS: Mn 2+, ZnS: Mn, Cu, ZnS: Mn 2+, Te 2+, ZnS: P, ZnS: P 3-, Cl -, ZnS: Pb 2 ⁺ , ZnS: Pb ²⁺ , Cl ^- , ZnS: Pb, Cu, Zn ₃ (PO ₄ ) ₂ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , Zn ₂ SiO ₄ : Mn ²⁺ , As ⁵⁺ , Zn ₂ SiO ₄ : Mn, Sb ₂ O ₂ , Zn ₂ SiO ₄ : Mn ²⁺ , P, Zn ₂ SiO ₄ : Ti ⁴⁺ , ZnS: Sn ²⁺ , ZnS: Sn, Ag, ZnS: Sn ²⁺ , Li ⁺ , ZnS: Te, Mn, ZnS-ZnTe: Mn ²⁺ , ZnSe: Cu ⁺ , Cl and ZnWO ₄ .

Preferably, the LED precursor contains a semiconductor light source (LED chip) and/or lead frame and/or gold wire and/or solder (flip chip). The LED precursor may further include a converter and/or primary optics and/or secondary optics as the case may be. Depending on the type of application, the converter layer can be directly arranged on the semiconductor light source (LED chip) or alternatively away from it. The encapsulation material forms a barrier against the external environment of the LED device, thereby protecting the converter and/or the LED chip. The encapsulation material is preferably in direct contact with the converter and/or LED chip.

Preferably, the crosslinkable polymer formulation applied to the LED precursor forms part of the converter layer. More preferably, the converter layer is in direct contact with or away from the LED chip.

Preferably, the converter layer further comprises one or more converters, such as phosphors and/or quantum materials as defined above.

LEDs prepared according to the method of the present invention can be used, for example, in backlights of liquid crystal (LC) displays, traffic lights, outdoor displays, billboards, general-purpose lighting (to name a few non-limiting examples).

Typical LEDs can be prepared similar to the LEDs described in US 6,274,924 B1 and US 6,204,523 B1. In addition, LED filaments as described in US 2014/0369036 A1 can be prepared using the crosslinkable polymer formulation of the present invention as an encapsulation adhesive layer. Such an LED filament includes a substrate, a light-emitting unit fastened to at least one side surface of the substrate, and a packaging adhesive layer surrounding the periphery of the light-emitting unit. The base plate is configured to have an elongated rod structure. The emitting unit includes a plurality of blue light chips and red light chips regularly distributed on the substrate and connected in series with each other in sequence. The encapsulating adhesive layer is made of a crosslinkable polymer formulation according to the invention containing a converter.

The invention further relates to a crosslinkable polymer formulation obtained from a mixed polymer and metal amide; wherein the polymer contains a repeating unit M ¹ and further contains (i) repeating units M ² or M ³ or ( ii) Repeating units M ² and M ³ , wherein repeating unit M ¹ is represented by formula (I), repeating unit M ² is represented by formula (II) and repeating unit M ³ is represented by formula (III): -[-SiR ¹ R ² -NR ³ -]- (I) -[-SiR ⁴ R ⁵ -NR ⁶ -]- (II) -[-SiR ⁷ R ⁸ -[O-SiR ⁷ R ⁸ -] _a -NR ⁹ -]- (III) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups, and a Is an integer from 1 to 60; and is characterized in that the metal amide is represented by the formula (1): M(NR ₂ ) _m L _n (1) wherein M is selected from the group consisting of B, Al, Ga, Ti and Zr; R Each occurrence may be the same or different and independently selected from the group consisting of: hydrogen, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, having 3 to Branched chain alkyl or alkenyl group of 20 carbon atoms, cyclic alkyl or alkenyl group having 3 to 20 carbon atoms, and aryl or heteroaryl group having 4 to 18 carbon atoms, one or more of which are hydrogen Atoms may be replaced by F, and one or more non-adjacent CH ₂ groups may be replaced by -O-, -(C=O)- or -(C=O)-O-; L is divided by NR Ligands other than ₂ which may be the same or different at each occurrence and are selected from the group consisting of anionic ligands, neutral ligands and free radical ligands; m is an integer greater than or equal to 1; and n is an integer greater than or equal to 0; where if M = B, Al or Ga, then m + n = 3; and if M = Ti or Zr, then m + n = 4.

Preferably, m is an integer selected from 1, 2, 3, and 4.

Preferably, n is an integer selected from 0, 1, 2 and 3. More preferably, n is 0.

Preferably, if M = B, Al, or Ga, M is trivalent. Preferably, if M = Ti or Zr, M is tetravalent.

Preferably, a is an integer from 1 to 50. More preferably, a may be an integer of 5 to 50 (long-chain monomer M ³ ); or a may be an integer of 1 to 4 (short-chain monomer M ³ ).

In a preferred embodiment, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of: hydrogen, having 1 to 40 Alkyl groups with 2 carbon atoms, alkenyl groups with 2 to 40 carbon atoms and aryl groups with 6 to 30 carbon atoms. More preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of: hydrogen, having 1 to 20 carbon atoms Alkyl, alkenyl having 2 to 20 carbon atoms and phenyl. Optimally, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, methyl or vinyl.

Further preferred substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} combined with the above cross-linkable polymers in the method for preparing photovoltaic devices The formulation is the same as described.

For the substituent R in the metal amide, the preferred, better, and preferred embodiments as described above in combination with the crosslinkable polymer formulation used in the method of preparing the photovoltaic device are applicable.

The preferred ligand L of the metal amide in the formulation of the present invention is the same as described above in connection with the crosslinkable polymer formulation in the method for preparing the photovoltaic device.

In a particularly preferred embodiment, the metal amide in the crosslinkable polymer formulation according to the invention is selected from the group consisting of: Ti(NMe ₂ ) ₄ , Zr(NMe ₂ ) ₄ , Al(NMe ₂ ) ₃ and B(NMe ₂ ) ₃ .

Depending on the metal amide used, the presence of moisture or oxygen can play a role in curing. Those skilled in the art are familiar with these effects and should properly adjust the atmospheric conditions by means of suitable optimization methods.

In a preferred embodiment of the present invention, based on the total weight of the cross-linkable polymer formulation, the content of metal amide in the cross-linkable polymer formulation is 0.001 to 10.00% by weight, preferably 0.005 to 5.00% by weight %, more preferably 0.01 to 3.00% by weight, most preferably 0.02 to 2.00% by weight.

Suitable solvents for the crosslinkable polymer formulation of the present invention are the same as described above in connection with the crosslinkable polymer formulation in the method for preparing the photovoltaic device.

Preferably, the formulation of the present invention may contain one or more additives selected from the group consisting of nanoparticles, converters, viscosity modifiers, surfactants, additives that affect film formation, additives that affect evaporation behavior And crosslinking agent. Optimally, the formulation further includes a converter. Nanoparticles can be selected from nitrides, titanates, diamonds, oxides, sulfides, sulfites, sulfates, silicates, and carbides that are optionally modified by the surface of the blocking agent. Preferably, the nanoparticles are materials with a particle size of <100 nm, more preferably <80 nm, even better <60 nm, even better <40 nm and most preferably <20 nm. The particle size can be determined by any standard method known to those skilled in the art.

The crosslinkable polymer formulation of the present invention is prepared by mixing the polymer with metal amide. The above situation also applies to crosslinkable polymer formulations, which are used in the method of preparing the photovoltaic device of the present invention. In a preferred embodiment, the metal amide is added to the polymer and then mixed. In an alternative preferred embodiment, the polymer is added to the metal amide and then mixed. The polymer and/or metal amide may be present in the solution. After mixing, the polymer and metal amide can form a polymer-metal amide adduct as shown generally in FIG.

Preferably, the formulation is prepared at ambient temperature. The ambient temperature refers to a temperature selected from the range of 20°C to 25°C. However, the formulation can also be prepared at a temperature> 25°C, preferably at a temperature> 25°C to 150°C.

Preferably, the formulation is prepared under an inert gas atmosphere, such as under argon or nitrogen.

The crosslinkable polymer formulations of the present invention can be used in the inventive method for preparing photovoltaic devices as described above.

The invention is further illustrated by the following examples which should in no way be considered limiting. Those skilled in the art will recognize that various modifications, additions and changes can be made to the present invention without departing from the spirit and scope of the invention as defined in the scope of the accompanying patent application.

EXAMPLES Example 1 ( reference substance , epoxysilazane 2020) was charged with 1,500 g of liquid ammonia in a 4 l pressure vessel at 0°C and a pressure between 3 and 5 bar. A mixture of 442 g of dichloromethylsilane and 384 g of 1,3-dichlorotetramethyldisilazane was slowly added over a period of 3 h. After stirring the resulting reaction mixture for an additional 3 h, the stirrer was stopped and the lower phase was separated and evaporated to remove the dissolved ammonia. After filtration, 429 g of colorless viscous oil remained. Dissolve 100 g of this oil in 100 g 1,4-dioxane and cool to 0°C. 100 mg KH was added and the reaction solution was stirred for 4 h until gas formation ceased. 300 mg of chlorotrimethylsilane and 250 g of xylene were added and the temperature was raised to room temperature. The turbid liquid was filtered and the resulting clear solution was reduced to dryness under a vacuum of 20 mbar or less at a temperature of 50°C. The remaining 95 g of epoxysilazane 2020 is a colorless, highly viscous oil.

Example 2 ( Reference material , epoxysilazane 2020 containing triphenylaluminum catalyst ) 10% by weight of 20 g of epoxysilazane 2020 and 2 g of triphenylaluminum solution in THF under nitrogen atmosphere The solution was placed in a 50 ml flask and stirred at 25°C for 4 h until the mixture was completely homogeneous. The flask was connected to a rotary evaporator and the THF was completely removed at a temperature of 50°C and a pressure of 20 mbar. The residue is a clear viscous liquid.

Example 3 Under nitrogen atmosphere, 20 g of epoxysilazane 2020 and 0.2 g of ginseng-(dimethylamino)-aluminum were placed in a 50 ml flask and stirred at 25°C for 4 h until the mixture was completely homogeneous until. The product is a clear viscous liquid.

Example 4 Under a nitrogen atmosphere, 20 g of epoxysilazane 2020 and 0.2 g of ginseng-(dimethylamino)-aluminum were placed in a 50 ml flask and stirred at a temperature of 100° C. for 6 h. Allow the mixture to cool to room temperature. The product is a clear liquid with a slightly increased viscosity compared to the raw material epoxysilazane 2020.

Example 5 In a nitrogen atmosphere, 20 g of epoxysilazane 2020 and 0.2 g of (dimethylamino)-zirconium were placed in a 50 ml flask and stirred at 25°C for 4 h until the mixture was completely homogeneous until. The product is a clear viscous liquid.

Example 6 Under nitrogen atmosphere, 20 g of epoxysilazane 2020 and 0.2 g of (dimethylamino)-titanium were placed in a 50 ml flask and stirred at 25°C for 4 h until the mixture was completely homogeneous . The product is a clear color viscous liquid.

Curing conditions Condition I: 150 ℃ in the heating box for 2 h, 4 h and 6 h. Condition II: 180 ℃ in the heating box for 2 h, 4 h and 6 h.

表1： 在150℃下固化2 h、4 h及6 h之後的肖氏A硬度(固化條件I)

表2： 在180℃下固化2 h、4 h及6 h之後的肖氏A硬度(固化條件II) Application test procedure : Shore A hardness of cured film The materials prepared according to Example 1 and Examples 3 to 6 were coated with a doctor blade with a film thickness of 90 µm-100 µm on a glass plate. Next, the glass plate was exposed to 150°C and 180°C for different times of 2 h, 4 h and 6 h (as described under curing conditions I and II) and after cooling to room temperature, using a product from q-tec GmbH "Shore A Nano Typ SHAN.01" type of Shore-A hardness testing equipment to measure.

Table 1: Shore A hardness after curing at 150°C for 2 h, 4 h and 6 h (curing condition I)

Table 2: Shore A hardness after curing at 180°C for 2 h, 4 h and 6 h (curing condition II)

These results show the effect of the presence of metal amide on the curing rate of organopolyepoxysilazane. Compared with the pure epoxy silazane of Example 1, the curing rate expressed as a change (increase) in Shore A hardness over time is significantly increased. In addition, a comparison between the material of Example 3 and the material of Example 4 shows that there is no significant difference between the two preparation methods for room temperature and high temperature reactions.

表3： 在180℃下4 h且在220℃下4 h之後的不同膜厚度下之裂紋形成。「否」指示無裂紋形成，「是」指示裂紋形成。 Application test procedure : Crack formation of cured film The materials prepared according to Examples 1 to 6 were coated with a doctor blade with a film thickness of 50 µm up to 300 µm on a glass plate in a step of 50 µm. The glass plate was then exposed to 180° C. for 4 h and then 220° C. for 4 h. Remove the sample from the heating box, cool to room temperature and optically inspect to detect cracks in the film.

Table 3: Crack formation at different film thicknesses at 180°C for 4 h and after 220°C for 4 h. "No" indicates no crack formation, and "Yes" indicates crack formation.

In contrast to the reference material of Example 1 which showed cracks at 200 µm, the metal amide-containing materials of Examples 3 to 6 did not form cracks up to a film thickness of 300 µm. The addition of other metal additives as shown in Example 2 also has a small positive effect on higher film thicknesses without cracks, however, film thicknesses of more than 200 µm cannot be achieved here.

表4： 1000 h之後之色點偏差⁽¹⁾ 量測誤差= +/- 0.001 Application test procedure : LED reliability test In order to show its usefulness for LED devices, the materials prepared according to Example 1, Example 3, Example 4 and Example 5 were tested on Excelitas LED packages. Each material was mixed by using a planetary centrifugal mixer and phosphor (isiphor® YYG 545 200, available from MERCK KGaA) in a weight ratio of 4:1 (material mass and phosphor mass). The resulting slurry is then distributed on LED packages (available from Excelitas) by means of automatic dispensing equipment. The target color point is selected to be at a correlated color temperature (CCT) of 5500 K ± 200 K. The LED-package was cured on a hot plate at 180°C for 6 h under an air atmosphere. Then operate the LED at 1000 mA current under ambient conditions for 1000 h, and measure the change in color coordinates (Δx and Δy in the CIE 1931 chromaticity coordinate system). The goal is that the color coordinates do not change or at least the color coordinates change very little (less change is better).

Table 4: Color point deviation after 1000 h ⁽¹⁾ Measurement error = +/- 0.001

Comparison of item 1 with items 2, 3, and 4 shows improved color stability of materials containing metal amides (reduced color point shifts Δx and Δy).

Figure 1 : Schematic representation of the formation of polymer-metal amide adducts after mixing polysilazane polymer with metal amide species Zr(NMe ₂ ) ₄ . The metal amide and HNMe _{2 are} cleaved to coordinate the nitrogen atom of the polysilazane chain. Multiple coordination with the same or another polysilazane chain is possible.

Claims (17)

A method for preparing an optoelectronic device containing a cross-linked polymer material, the cross-linked polymer material is prepared from a cross-linkable polymer formulation, wherein the method includes the following steps: (a) The cross-linkable polymer is formulated Before applying to the photovoltaic device; and (b) curing the cross-linkable polymer formulation to obtain a cross-linked polymer material; characterized in that the cross-linkable polymer formulation is obtained by mixing the following components A polymer containing a repeating unit M ¹ , wherein M ¹ is a silazane repeating unit, and the metal amide represented by formula (1): M(NR ₂ ) _m L _n (1) wherein M is selected from the group consisting of B, Al, The group consisting of Ga, Ti, and Zr; R may be the same or different at each occurrence and is independently selected from the group consisting of: hydrogen, a linear alkyl group having 1 to 20 carbon atoms, and having 2 to 20 carbons Straight-chain alkenyl groups of atoms, branched chain alkyl or alkenyl groups having 3 to 20 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 20 carbon atoms, and aryl groups having 4 to 18 carbon atoms or Heteroaryl, where one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -(C=O )-O- substitution; L is a ligand other than NR ₂ which may be the same or different at each occurrence and is selected from the group consisting of anionic ligands, neutral ligands and free radical ligands; m is an integer greater than or equal to 1; and n is an integer greater than or equal to 0; where M + n = 3 if M = B, Al, or Ga; and m + n = 4 if M = Ti or Zr . The method for preparing a photovoltaic device according to claim 1, wherein the repeating unit M ^{1 is a} silazane repeating unit represented by formula (I): -[-SiR ¹ R ² -NR ³ -]- (I) where R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups. The method for producing a photovoltaic device according to claim 2, wherein R ¹ , R ² and R ³ are independently selected from the group consisting of hydrogen, alkyl having 1 to 40 carbon atoms, having 2 to 40 carbon atoms Alkenyl and aryl groups with 6 to 30 carbon atoms. The method for preparing a photovoltaic device according to any one of claims 1 to 3, wherein the polymer contains another repeating unit M ² , wherein M ^{2 is a} silazane repeating unit represented by formula (II): -[-SiR ⁴ R ⁵ -NR ⁶ -]- (II) wherein R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups; and wherein M ^{2 is} different from M ¹ . The method for producing a photovoltaic device according to claim 4, wherein R ⁴ , R ⁵ and R ⁶ are independently selected from the group consisting of hydrogen, alkyl having 1 to 40 carbon atoms, having 2 to 40 carbon atoms Alkenyl and aryl groups with 6 to 30 carbon atoms. The method for preparing a photovoltaic device according to any one of claims 1 to 5, wherein the polymer contains another repeating unit M ³ , where M ³ is represented by formula (III): -[-SiR ⁷ R ⁸ -[O- SiR ⁷ R ⁸ -] _a -NR ⁹ -]- (III) wherein R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, organic groups and organic heteroatom groups; and a is from 1 to 60 Integer. The method for preparing a photovoltaic device according to claim 6, wherein R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of hydrogen, alkyl having 1 to 40 carbon atoms, having 2 to 40 carbon atoms Alkenyl and aryl groups with 6 to 30 carbon atoms. As claimed in any one of the items 1 to 7, the method of preparing a photovoltaic device, Based on the total weight of the cross-linkable polymer formulation, the content of the metal amide in the cross-linkable polymer formulation is 0.001% by weight to 10.00% by weight, preferably 0.005% by weight to 5.00% by weight, more Preferably 0.01 wt% to 3.00 wt%, most preferably 0.02 wt% to 2.00 wt%. The method for preparing a photovoltaic device according to any one of claims 1 to 8, wherein each occurrence of R is independently selected from the group consisting of: hydrogen, linear alkyl having 1 to 12 carbon atoms, having 2 Linear alkenyl groups up to 12 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 12 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 12 carbon atoms and 4 to 10 carbon atoms Aryl or heteroaryl, where one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or- (C=O)-O- replacement. The method for preparing a photovoltaic device according to any one of claims 1 to 9, wherein the anionic ligands are selected from halide, cyanide, alcoholate, carboxylate, deprotonated keto acid, deprotonated ketoester And deprotonated diketones; the neutral ligands are selected from alcohols and carbon monoxide; and the free radical ligands are selected from the group consisting of hydrogen, linear alkyl groups having 1 to 20 carbon atoms, Linear alkenyl groups having 2 to 20 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 20 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 20 carbon atoms and having 4 to 18 carbon atoms Carbon atom aryl or heteroaryl, where one or more hydrogen atoms are optionally replaced by F and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -(C=O)-O- replacement. As claimed in any one of the items 1 to 10, a method for preparing a photovoltaic device, Wherein the curing in step (b) is preferably in the range of 140°C to 200°C, more preferably in the range of 150°C to 190°C, and most preferably in the range of 160°C to 185°C Carry out at high temperature. An optoelectronic device, It can be obtained by a method as in any one of request items 1 to 11. A crosslinkable polymer formulation obtained by mixing the following components: a polymer, and a metal amide; characterized in that the polymer contains a repeating unit M ¹ and further contains (i) a repeating unit M ² or M ³ or (ii) repeating units M ² and M ³ , wherein the repeating unit M ¹ is represented by formula (I), the repeating unit M ² is represented by formula (II) and the repeating unit M ³ is represented by formula (III) ： -[-SiR ¹ R ² -NR ³ -]- (I) -[-SiR ⁴ R ⁵ -NR ⁶ -]- (II) -[-SiR ⁷ R ⁸ -[O-SiR ⁷ R ⁸ -] _a -NR ⁹ -]- (III) where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from hydrogen, organic groups and organic heteroatoms Group consisting of groups, and a is an integer from 1 to 60; and is characterized in that the metal amide is represented by formula (1): M(NR ₂ ) _m L _n (1) where M is selected from the group consisting of B, Al, Ga, The group consisting of Ti and Zr; R may be the same or different at each occurrence and is independently selected from the group consisting of: hydrogen, a linear alkyl group having 1 to 20 carbon atoms, and a group having 2 to 20 carbon atoms Linear alkenyl, branched alkyl or alkenyl having 3 to 20 carbon atoms, cyclic alkyl or alkenyl having 3 to 20 carbon atoms, and aryl or heteroaromatic having 4 to 18 carbon atoms Radical, in which one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- or -(C=O)- O-displacement; L is a ligand other than NR ₂ which may be the same or different at each occurrence and is selected from the group consisting of anionic ligands, neutral ligands and free radical ligands; m is An integer greater than or equal to 1; and n is an integer greater than or equal to 0; where M + n = 3 if M = B, Al, or Ga; and m + n = 4 if M = Ti or Zr. The crosslinkable polymer formulation according to claim 13, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently selected from the group consisting of: Hydrogen, alkyl groups having 1 to 40 carbon atoms, alkenyl groups having 2 to 40 carbon atoms, and aryl groups having 6 to 30 carbon atoms. If the crosslinkable polymer formulation of claim 13 or 14, Based on the total weight of the cross-linkable polymer formulation, the content of the metal amide in the cross-linkable polymer formulation is 0.001% by weight to 10.00% by weight, preferably 0.005% by weight to 5.00% by weight, more Preferably 0.01 wt% to 3.00 wt%, most preferably 0.02 wt% to 2.00 wt%. The crosslinkable polymer formulation according to any one of claims 13 to 15, wherein each occurrence of R is independently selected from the group consisting of hydrogen, linear alkyl having 1 to 12 carbon atoms, Linear alkenyl groups having 2 to 12 carbon atoms, branched chain alkyl or alkenyl groups having 3 to 12 carbon atoms, cyclic alkyl or alkenyl groups having 3 to 12 carbon atoms and having 4 to 10 carbon atoms An aryl or heteroaryl group of a carbon atom in which one or more hydrogen atoms are optionally replaced by F, and one or more non-adjacent CH ₂ groups are optionally substituted by -O-, -(C=O)- Or -(C=O)-O- replacement. If the crosslinkable polymer formulation of any one of claims 13 to 16, Where L is selected from the list consisting of anionic ligands, neutral ligands and free radical ligands.

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