KR102319359B1 - Inorganic-organic hybrid solar cell - Google Patents

Abstract

The present specification is a cathode; an anode provided to face the cathode; a photoactive layer comprising a compound having a perovskite structure provided between the cathode and the anode; And it relates to an organic-inorganic hybrid solar cell comprising a hole transport layer comprising the polymer represented by Formula 1 provided between the anode and the photoactive layer.

Description

Organic-inorganic hybrid solar cell {INORGANIC-ORGANIC HYBRID SOLAR CELL}

The present specification relates to an organic-inorganic hybrid solar cell.

In order to solve the global environmental problems caused by the depletion of fossil energy and its use, research on renewable and clean alternative energy sources such as solar energy, wind power, and hydroelectric power is being actively conducted. Among them, interest in solar cells that directly change electrical energy from sunlight is increasing significantly. Here, the solar cell refers to a cell that generates current-voltage using the photovoltaic effect of absorbing light energy from sunlight to generate electrons and holes. Currently, it is possible to manufacture np diode-type silicon (Si) single-crystal-based solar cells with a light energy conversion efficiency of more than 20%, which is used in actual photovoltaic power generation. Compound semiconductors such as gallium arsenide (GaAs) with better conversion efficiency There are also solar cells using However, since such inorganic semiconductor-based solar cells require very high-purity purified materials for high efficiency, a lot of energy is consumed for refining raw materials, and expensive process equipment is required for single crystal or thin film using raw materials. As a result, there is a limit to lowering the manufacturing cost of solar cells, which has become an obstacle to large-scale utilization.

Accordingly, in order to manufacture a solar cell at a low cost, it is necessary to significantly reduce the cost of the material or manufacturing process used as the core of the solar cell. As an alternative to the inorganic semiconductor-based solar cell, dye sensitization that can be manufactured with low-cost materials and processes Solar cells and organic solar cells are being actively studied.

The dye-sensitized solar cell (DSSC) was first successfully developed by Professor Michael Gratzel of Lausanne Institute of Technology (EPFL) in Switzerland in 1991, and was introduced in the journal Nature. The initial structure of the dye-sensitized solar cell was a simple structure in which a light-absorbing dye was adsorbed to a porous photoanode on a transparent electrode film that conducts light and electricity, another conductive glass substrate was placed on top, and a liquid electrolyte was filled. is made of The principle of operation of the dye-sensitized solar cell is that when dye molecules chemically adsorbed on the porous photocathode surface absorb sunlight, the dye molecules generate electron-hole pairs, and electrons are injected into the conduction band of the semiconductor oxide used as the porous photocathode. It is transferred to the transparent conductive film to generate an electric current. The holes remaining in the dye molecules are transferred to the photocathode by hole-conducting or hole-conducting polymers by oxidation-reduction reactions of liquid or solid electrolytes to form a complete solar cell circuit and work to the outside. will do

Fluorine doped tin oxide (FTO) or indium dopted tin oxide (ITO) is mainly used for the transparent conductive film in the configuration of the dye-sensitized solar cell, and nanoparticles with a wide bandgap are used as the porous photocathode. As a dye, light absorption is particularly good and the LUMO (lowest unoccupied molecular orbital) energy level of the dye is higher than that of the conduction band of the photocathode material. Various substances are chemically synthesized and used. The highest efficiency reported so far for liquid-type dye-sensitized solar cells has remained at 11-12% for about 20 years. Although the liquid-type dye-sensitized solar cell has a relatively high efficiency, it has potential for commercialization, but there are also problems with stability over time due to the volatile liquid electrolyte and cost reduction due to the use of expensive ruthenium (Ru)-based dyes. In order to solve this problem, the use of non-volatile electrolytes using ionic solvents instead of volatile liquid electrolytes, the use of polymer gel electrolytes, and the use of inexpensive pure organic dyes are being studied. There is a problem in that the efficiency is lower than that of the battery.

On the other hand, organic photovoltaic (OPV), which has been studied in earnest since the mid-1990s, is made of organic materials with electron donor (electron donor, D, or sometimes called hole acceptor) characteristics and electron acceptor (A) characteristics. is composed When a solar cell made of organic molecules absorbs light, electrons and holes are formed, which are called excitons. Excitons move to the D-A interface to separate charges, and electrons move to an electron acceptor and holes move to an electron donor to generate a photocurrent. The distance that excitons generated from the electron donor can travel is usually very short, around 10 nm, so photoactive organic materials cannot be stacked thickly, so the efficiency is low due to low light absorption. An organic solar cell with an efficiency of over 8% has been reported (Advanced Materials, 23 (2011)) ) 4636). The organic solar cell has a simple manufacturing process compared to the conventional solar cell due to the easy processability, diversity, and low cost of organic materials. However, organic solar cells have a major problem in the stability of the solar cell, in that the structure of the BHJ is deteriorated by moisture or oxygen in the air, and thus the efficiency is rapidly reduced. However, there is a problem that the price increases.

As a method to solve the problem of dye-sensitized solar cells caused by liquid electrolytes, Michael Gratzel, the inventor of the dye-sensitized solar cell (DSSC), Department of Chemistry at the Lausanne Institute of Technology (EPFL) in Switzerland, published a liquid electrolyte in Nature in 1998. Instead, a solid hole-conducting organic material, Spiro-OMeTAD[2,2',7,7'-tetrkis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene], was used to achieve an efficiency of 0.74%. An all-solid-state dye-sensitized solar cell has been reported. Afterwards, the efficiency was increased up to about 6% by optimizing the structure, improving the interfacial properties, and improving hole conductivity. In addition, solar cells using ruthenium-based dyes, such as inexpensive pure organic dyes and P3HT and PEDOT as hole conductors, have been manufactured, but the efficiency is still low at 2-7%.

In addition, studies using quantum dot nanoparticles as light absorbers instead of dyes and using hole-conducting inorganic or organic materials instead of liquid electrolytes have been reported. A number of solar cells using CdSe, PbS, etc. as quantum dots and conductive polymers such as spiro-OMeTAD or P3HT as hole conductive organic materials have been reported, but their efficiency is still very low, less than 5%. _{In addition, the solar cell using Sb 2} S ₃ as the light-absorbing inorganic material and PCPDTBT as the hole-conducting organic material reports an efficiency of about 6% [Nano Letters, 11 (2011) 4789], but no further improvement in efficiency has been reported. .

In addition, among the solar cells that can be manufactured by the solution method, promising solar cells are CZTS/Se (Copper Zinc TinChalcogenides) or CIGS/Se (Copper Indium Gallium Chalcogenides), but their efficiency is staying in the 11% range, There are limitations in resources such as indium, the use of very toxic substances such as hydrazine, or the need for secondary heat treatment at high temperatures. The stability and reproducibility are poor, and as it is difficult to heat treatment for a long time at high temperature due to the chalcogen element, there is a limit to manufacturing coarse grains by the solution method.

As described above, various solar cells such as organic solar cells, dye-sensitized solar cells, inorganic quantum dot-sensitized solar cells, and organic/inorganic hybrid solar cells have been proposed to replace semiconductor-based solar cells, but their efficiency In this case, there is a limit to replacing the semiconductor-based solar cell.

Republic of Korea Patent No. 1172534

Advanced Materials, 23 (2011) 4636 Nano Letters, 11 (2011) 4789 J. Am. Chem. Soc., 131 (2009) 6050

The present specification provides an organic-inorganic hybrid solar cell.

The present specification is a cathode; an anode provided to face the cathode; a photoactive layer comprising a compound having a perovskite structure provided between the cathode and the anode; And it provides an organic-inorganic hybrid solar cell comprising a hole transport layer comprising a polymer represented by the following formula (1) provided between the anode and the photoactive layer.

[Formula 1]

In Formula 1,

l is the mole fraction, a real number with 0≤l < 1,

m is the mole fraction, a real number with 0≤m < 1,

o is the mole fraction, a real number with 0 ≤ o < 1,

p is the mole fraction, a real number with 0≤p < 1,

l+m+o+p = 1,

n is the number of repetitions of the unit, and is an integer from 1 to 10,000,

A to D are the same as or different from each other, and are each independently any one selected from units represented by the following Chemical Formulas 2 to 5,

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,

X1 to X19 are the same as or different from each other, and are each independently S, Se, O, CRR' or NR;

Y1 to Y4 are the same as or different from each other, and are each independently N or CR",

Ar1 to Ar4, R1 to R24, R, R' and R" are the same as or different from each other, and each independently represents hydrogen; deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group ; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group;

L1 to L4 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

a1, a2, a3, a5, a7 and a8 are each 0 or 1,

a4 is an integer from 1 to 3,

a6 is 1 or 2,

When a4 is 2 or more, the structures in a plurality of parentheses are the same as or different from each other,

When a6 is 2, structures within a plurality of parentheses are the same as or different from each other.

The present specification provides an organic-inorganic hybrid solar cell including the compound of the perovskite structure as a material for the photoactive layer and the polymer represented by Formula 1 as a material for the hole transport layer.

According to an exemplary embodiment of the present specification, when the compound of the perovskite structure is used as a material for the photoactive layer and the polymer represented by Formula 1 is used as a hole transport material, open circuit voltage, short circuit current and fill factor and excellent properties such as efficiency.

The polymer according to an exemplary embodiment of the present specification has high solubility and/or charge mobility, so it is economical in terms of time and cost of the manufacturing process of an organic-inorganic hybrid solar cell, and may exhibit excellent properties in terms of efficiency.

1 is a diagram illustrating an organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification.
2 is a view showing UV data of Polymer 1.
3 is a diagram showing CV data of Polymer 1.
4 is a view showing UV data of Polymer 2.
5 is a diagram showing CV data of Polymer 2.
6 is a view showing UV data of Polymer 3.
7 is a diagram showing CV data of Polymer 3.
8 is a view showing UV data of Polymer 4.
9 is a diagram showing CV data of Polymer 4.
10 is a view showing UV data of polymer 5.
11 is a diagram showing CV data of Polymer 5.
12 is a view showing UV data of Polymer 6.
13 is a diagram showing CV data of Polymer 6.
14 is a view showing UV data of polymer 7.
15 is a diagram showing CV data of Polymer 7.

Hereinafter, the present specification will be described in more detail.

As used herein, a 'unit' is a repeating structure included in a monomer of a polymer, and refers to a structure in which the monomer is bonded to the polymer by polymerization.

In the present specification, the meaning of 'including a unit' means included in the main chain in the polymer.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

According to an exemplary embodiment of the present specification, the present specification is a cathode; an anode provided to face the cathode; a photoactive layer comprising a compound having a perovskite structure provided between the cathode and the anode; And it provides an organic-inorganic hybrid solar cell comprising a hole transport layer comprising the polymer represented by Formula 1 provided between the anode and the photoactive layer.

In the present specification, the compound of the perovskite structure may be a compound of the perovskite structure in which an inorganic material and an organic material are mixed and bonded. Specifically, according to an exemplary embodiment of the present specification, the compound of the perovskite structure is an organo-metal halide compound of the perovskite structure.

According to another exemplary embodiment of the present specification, in order to obtain the compound of the perovskite structure, the constituent ions of three ions may satisfy Equation 1 below.

[Equation 1]

In the above formula 1,

R _A , R _B , R _O means the radius of each ion,

t is a tolerance factor indicating the contact state of ions. When t is 1, it is an ideal perovskite compound, meaning that each ion is in contact with an adjacent ion.

According to an exemplary embodiment of the present specification, the compound of the perovskite structure is represented by the following formula (6).

In Formula 6,

Q is C _n H _2n+1 NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,

M is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Bi ²⁺ , Pb ²⁺ and It is a divalent metal ion selected from ^{Yb 2+,}

X is a halogen ion,

n is an integer from 1 to 9;

In the temporary state of the present specification, the compound of the perovskite structure, the compound satisfying Formula 6, has a perovskite structure, and M is the center of the unit cell in the perovskite structure. , X is located at the center of each side of the unit cell to form an octahedron structure with M as the center, and Q may be located at each corner of the unit cell.

According to an exemplary embodiment of the present specification, X is one or more halogen ions selected from the group consisting ^{of F -} , Cl ^- , Br ^- and I ^-.

According to an exemplary embodiment of the present specification, the compound of the perovskite structure may include three halogen ions, X, and the three halogen ions may be the same or different from each other.

In the present specification, the compound of the perovskite structure may include a single cation. In this specification, a single cation means that one type of monovalent cation is used. That is, in Formula 6, it means that only one type of monovalent cation is selected as Q. For example, Q in Formula 6 may be C _n H _2n+1 NH ₃ ⁺ , and n may be an integer of 1 to 9.

According to an exemplary embodiment of the present specification, M is Pd ²⁺ .

According to another exemplary embodiment, the organo-metal halogen compound is CH ₃ NH ₃ PbI _x Cl _y , CH ₃ NH ₃ PbI _x Br _y , CH ₃ NH ₃ PbCl _x Br _y and CH ₃ NH ₃ PbI _x F _{1 or 2 or more selected from y} , x is a real number of 0 or more and 3 or less, y is a real number of 0 or more and 3 or less, and x+y=3.

According to another exemplary embodiment, the organo-metal halogen compound is CH ₃ NH ₃ PbI ₃ (MAPbI ₃ ).

According to an exemplary embodiment of the present specification, the photoactive layer includes only a compound having a perovskite structure.

According to an exemplary embodiment of the present specification, the photoactive layer is made of a compound having a perovskite structure.

According to an exemplary embodiment of the present specification, the compound of the perovskite structure has a high extinction coefficient, and thus has an excellent light collecting effect even in a thin film. Therefore, the organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification can be expected to have excellent energy conversion efficiency.

According to another exemplary embodiment of the present specification, the thickness of the photoactive layer including the compound of the perovskite structure is 10 nm to 2,000 nm. According to another exemplary embodiment, the thickness of the photoactive layer including the compound of the perovskite structure is 10 nm to 1,500 nm. According to another exemplary embodiment, the thickness of the photoactive layer including the compound of the perovskite structure is 10 nm to 1,000 nm.

As used herein, the term “thickness” means a width between one surface facing the cathode or the anode of the photoactive layer and one surface facing the surface.

Examples of the substituents are described below, but are not limited thereto.

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; imid; amide group; hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be 1 or 2 substituted with a nitrogen of the amide group with hydrogen, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto. does not

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.

In the present specification, when the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-C24. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

,

,

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

,

and

etc. can be However, the present invention is not limited thereto.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Si, Se, and S. have. Although the number of carbon atoms of the heteroaryl group is not particularly limited, it is preferably from 2 to 60 carbon atoms, specifically, 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. The amine group may be substituted with an N atom, an aryl group, an alkyl group, an arylalkyl group, a heterocyclic group, and the like, and specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, and a phenylamine group. group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group and the like, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, and the arylsulfoxy group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, and the like. There is a thioxy group, and the arylsulfoxy group includes, but is not limited to, a benzenesulfoxy group, a p-toluenesulfoxy group, and the like.

In the present specification, the alkyl group in the alkylthioxy group and the alkylsulfoxy group is the same as the example of the alkyl group described above. Specifically, the alkyl thiooxy group includes a methyl thioxy group, ethyl thiooxy group, tert-butyl thioxy group, hexyl thioxy group, octyl thiooxy group, etc., and the alkyl sulfoxy group includes mesyl, ethyl sulfoxy group, propyl sulfoxy group, butyl sulfoxy group and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, the polymer is a random polymer.

According to an exemplary embodiment of the present specification, the Chemical Formula 2 is represented by any one of the following Chemical Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

The definitions of X1 to X7, Y1, Y2, R1 to R6, L1, L2, Ar1 and Ar2 are the same as those defined in Formula 2 above.

According to an exemplary embodiment of the present specification, Chemical Formula 3 is represented by the following Chemical Formula 3-1 or 3-2.

[Formula 3-1]

[Formula 3-2]

In Formulas 3-1 and 3-2,

The definitions of X8 to X10, R7 and R8 are the same as those defined in Formula 3 above,

X81 and X82 are the same as or different from each other and are each independently S, Se, O, CRR' or NR;

R71, R72, R81, R82, R and R' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Chemical Formula 4 is represented by the following Chemical Formula 4-1 or 4-2.

[Formula 4-1]

[Formula 4-2]

In Formulas 4-1 and 4-2,

The definitions of X11 to X16, R9 to R14, L3, L4, Ar3 and Ar4 are the same as defined in Formula 4 above,

X131 is S, Se, O, CRR' or NR;

R111. R121, R and R' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, Chemical Formula 5 is represented by the following Chemical Formula 5-1 or 5-2.

[Formula 5-1]

[Formula 5-2]

In Formulas 5-1 and 5-2,

The definitions of X17 to X19, Y3, Y4, and R15 to R24 are the same as those defined in Formula 5 above.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,

The definitions of l, m, n, o and p are the same as defined in Formula 1 above,

The definitions of X1 to X7, Y1, Y2, R1 to R6, L1, L2, Ar1 and Ar2 are the same as defined in Formula 2 above,

The definitions of X8 to X10, R7 and R8 are the same as those defined in Formula 3 above,

The definitions of X11 to X16, R9 to R14, L3, L4, Ar3 and Ar4 are the same as defined in Formula 4 above,

The definitions of X17 to X19, Y3, Y4 and R15 to R24 are the same as defined in Formula 5 above,

X61, X71, X81, X82, X111, X211, X131, X132, X141, X151, X161 are the same as or different from each other and are each independently S, Se, O, CRR' or NR;

Ar11, Ar12, R51, R61, R71, R72, R81, R82, R111, R112, R121, R122, R131, R141, R211, R and R' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

L11 and L12 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, X1 to X19 are the same as or different from each other, and are each independently S or NR.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a 2-ethylhexyl group; or a 2-hexyldecyl group; or an n-dodecyl group.

According to an exemplary embodiment of the present specification, Y1 to Y4 are N.

According to an exemplary embodiment of the present specification, R1 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, R1 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; Or a substituted or unsubstituted C1-C30 linear or branched alkoxy group.

According to an exemplary embodiment of the present specification, R1 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; or a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R1 to R24 are the same as or different from each other, and each independently hydrogen; fluorine; n-octyl group; n-dodecyl group; or an n-dodecyloxy group.

According to an exemplary embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted C1-C30 linear or branched alkoxy group.

According to an exemplary embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 30 carbon atoms; or a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 to Ar4 are the same as or different from each other, and each independently a 2-ethylhexyl group; or a 2-ethylhexyloxy group.

According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently a monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, L1 to L4 are the same as or different from each other, and each independently a phenylene group; or a divalent thiophene group.

According to an exemplary embodiment of the present specification, in Formula 2, a1, a2, and a3 are each 0 or 1, and a1 + a2 + a3 = 1.

According to an exemplary embodiment of the present specification, in Formula 3, a4 is 1 or 3.

According to an exemplary embodiment of the present specification, in Formula 4, a5 is 0 or 1.

According to an exemplary embodiment of the present specification, in Formula 4, a6 is 1 or 2.

According to an exemplary embodiment of the present specification, in Formula 5, a7 is 0 or 1.

According to an exemplary embodiment of the present specification, in Formula 5, a8 is 0 or 1.

According to an exemplary embodiment of the present specification, in Formula 2, X1 to X3 and X5 to X7 are S.

According to an exemplary embodiment of the present specification, in Formula 2, X4 is NR.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a 2-ethylhexyl group; or a 2-hexyldecyl group; or an n-dodecyl group.

According to an exemplary embodiment of the present specification, in Formula 2, Y1 and Y2 are N.

According to an exemplary embodiment of the present specification, in Formula 2, R1, R2, R5 and R6 are hydrogen.

According to an exemplary embodiment of the present specification, in Formula 2, R3 and R4 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 2, R3 and R4 are the same as or different from each other, and each independently represent a substituted or unsubstituted straight-chain or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, R3 and R4 are the same as or different from each other, and each independently represent a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, R3 and R4 are the same as or different from each other, and each independently represents an n-dodecyloxy group.

According to an exemplary embodiment of the present specification, in Formula 2, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 2, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted C1-C30 linear or branched alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 2, Ar1 and Ar2 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 30 carbon atoms; or a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, Ar1 and Ar2 are the same as or different from each other, and each independently a 2-ethylhexyl group; or a 2-ethylhexyloxy group.

According to an exemplary embodiment of the present specification, in Formula 2, L1 and L2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, L1 and L2 are the same as or different from each other, and each independently a monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 2, L1 and L2 are the same as or different from each other, and each independently a phenylene group; or a divalent thiophene group.

According to an exemplary embodiment of the present specification, in Formula 3, X8 and X9 are S.

According to an exemplary embodiment of the present specification, in Formula 3, X10 is NR.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a 2-ethylhexyl group; or a 2-hexyldecyl group; or an n-dodecyl group.

According to an exemplary embodiment of the present specification, in Formula 3, R7 and R8 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, in Formula 3, R7 and R8 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted C1-C30 linear or branched alkyl group.

According to an exemplary embodiment of the present specification, in Formula 3, R7 and R8 are the same as or different from each other, and each independently hydrogen; or a linear or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 3, R7 and R8 are the same as or different from each other, and each independently hydrogen; n-octyl group; or an n-dodecyl group.

According to an exemplary embodiment of the present specification, in Formula 4, X11, X12, X13 and X16 are S.

According to an exemplary embodiment of the present specification, in Formula 4, X14 and X15 are NR.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, R is a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a straight-chain or branched alkyl group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R is a 2-ethylhexyl group; or a 2-hexyldecyl group; or an n-dodecyl group.

According to an exemplary embodiment of the present specification, in Formula 4, Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 4, Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted C1-C30 linear or branched alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 4, Ar3 and Ar4 are the same as or different from each other, and each independently a linear or branched alkyl group having 1 to 30 carbon atoms; or a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 4, Ar3 and Ar4 are the same as or different from each other, and each independently a 2-ethylhexyl group; or a 2-ethylhexyloxy group.

According to an exemplary embodiment of the present specification, in Formula 4, L3 and L4 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a substituted or unsubstituted monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 4, L3 and L4 are the same as or different from each other, and each independently a monocyclic or polycyclic arylene group having 6 to 25 carbon atoms; or a monocyclic or polycyclic heteroarylene group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 4, L3 and L4 are the same as or different from each other, and each independently a phenylene group; or a divalent thiophene group.

According to an exemplary embodiment of the present specification, in Formula 4, R9 to R14 are hydrogen.

According to an exemplary embodiment of the present specification, in Formula 5, X17 to X19 are S.

According to an exemplary embodiment of the present specification, in Formula 5, R15 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 5, R15 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a substituted or unsubstituted C1-C30 linear or branched alkyl group; Or a substituted or unsubstituted C1-C30 linear or branched alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 5, R15 to R24 are the same as or different from each other, and each independently hydrogen; halogen group; a linear or branched alkyl group having 1 to 30 carbon atoms; or a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 5, R15 to R24 are the same as or different from each other, and each independently hydrogen; fluorine; n-octyl group; n-dodecyl group; or an n-dodecyloxy group.

According to an exemplary embodiment of the present specification, in Formula 5, R15, R16, R18, R19, R21 and R22 are hydrogen.

According to an exemplary embodiment of the present specification, in Formula 5, R17 and R20 are halogen groups.

According to an exemplary embodiment of the present specification, in Formula 5, R17 and R20 are fluorine.

According to an exemplary embodiment of the present specification, in Formula 5, R23 and R24 are the same as or different from each other, and each independently represent a substituted or unsubstituted alkoxy group.

According to an exemplary embodiment of the present specification, in Formula 5, R23 and R24 are the same as or different from each other, and each independently represents a substituted or unsubstituted straight-chain or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 5, R23 and R24 are the same as or different from each other, and each independently represent a linear or branched alkoxy group having 1 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, in Formula 5, R23 and R24 are the same as or different from each other, and each independently represents an n-dodecyloxy group.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following compounds 1-1 to 1-7.

[Compound 1-1]

[Compound 1-2]

[Compound 1-3]

[Compound 1-4]

[Compound 1-5]

[Compound 1-6]

[화합물 1-7]

[Compound 1-7]

In the compounds 1-1 to 1-7,

The definitions of l, m, n, o and p are the same as those defined in Formula 1 above.

According to another exemplary embodiment of the present specification, the thickness of the hole transport layer including the polymer represented by Formula 1 is 10 nm to 2,000 nm. According to another exemplary embodiment, the thickness of the hole transport layer including the polymer represented by Formula 1 is 10 nm to 1,500 nm. According to another exemplary embodiment, the thickness of the hole transport layer including the polymer represented by Formula 1 is 10 nm to 1,000 nm.

According to an exemplary embodiment of the present specification, when the polymer is included in the hole transport layer of the organic-inorganic hybrid solar cell, solubility is high, and the manufacturing process of a device and/or module including the polymer is easy.

In addition, by controlling the ratio of units constituting the polymer, it is easy to control the HOMO energy level, so it is easy to provide a HOMO energy level suitable for the organic-inorganic hybrid solar cell, so that a high-efficiency organic-inorganic hybrid solar cell can be manufactured. can

According to one embodiment of the present specification, the end group of the polymer uses a trifluoro-benzene group and/or 4-Bromodiphenyl ether, but a generally known end group may be used according to the needs of those skilled in the art. It can be changed and used, but it is not limited thereto.

In the present specification, the trialkyl may be trimethyl or tributyl.

According to an exemplary embodiment of the present specification, the number average molecular weight of the copolymer is preferably 500 g/mol to 1,000,000 g/mol. According to another exemplary embodiment, the number average molecular weight of the copolymer is 3,000 g/mol to 1,000,000 g/mol. Preferably, the number average molecular weight of the copolymer is preferably 10,000 g/mol to 100,000 g/mol. According to an exemplary embodiment of the present specification, the number average molecular weight of the copolymer is 10,000 g/mol to 100,000 g/mol.

According to an exemplary embodiment of the present specification, the polymer may have a molecular weight distribution of 1 to 10. Preferably the polymer has a molecular weight distribution of 1 to 3.

The lower the molecular weight distribution and the larger the number average molecular weight, the better the electrical and mechanical properties.

In addition, it is preferable that the number average molecular weight is 100,000 or less in order to have solubility above a certain level so that the application of the solution application method is advantageous.

The copolymer may be prepared based on Preparation Examples to be described later.

The polymer according to the present specification can be prepared by a multi-step chemical reaction. After preparing monomers through an alkylation reaction, a Grignard reaction, a Suzuki coupling reaction, and a Stille coupling reaction, the final polymer is subjected to a carbon-carbon coupling reaction such as a Stille coupling reaction. can be manufactured. When the substituent to be introduced is a boronic acid or boronic ester compound, it may be prepared through a Suzuki coupling reaction, but is not limited thereto.

According to an exemplary embodiment of the present specification, the organic-inorganic hybrid solar cell further includes a substrate, and the cathode is provided on the substrate. Specifically, the organic-inorganic hybrid solar cell may be an organic-inorganic hybrid solar cell having an inverted structure.

According to an exemplary embodiment of the present specification, the organic-inorganic hybrid solar cell has an inverted structure, the cathode is a transparent electrode, and an anode is provided opposite the cathode, and a hole transport layer is formed between the anode and the photoactive layer. provided, and the hole transport layer includes the polymer. The organic-inorganic solar cell may absorb light via the cathode. According to an exemplary embodiment of the present specification, the cathode may be provided on a transparent substrate.

According to an exemplary embodiment of the present specification, between the anode and the cathode, one or more layers selected from the group consisting of an electron blocking layer, a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer and an electron injection layer may be further included. can

According to an exemplary embodiment of the present specification, the organic-inorganic hybrid solar cell may include an electron transport layer between the cathode and the photoactive layer.

According to an exemplary embodiment of the present specification, the hole transport layer is provided in contact with the photoactive layer.

1 shows a schematic diagram of an organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification. Specifically, in FIG. 1 , a cathode 102 is provided on a substrate 101 , and a photoactive layer 103 is provided on the cathode. It shows that the hole transport layer 104 is provided on the photoactive layer 103, and the anode 105 is provided on the hole transport layer. According to an exemplary embodiment of the present specification, the photoactive layer 103 includes the compound of the perovskite structure, and the hole transport layer 104 includes the polymer.

According to an exemplary embodiment of the present specification, the structure of FIG. 1 is not limited, and an organic-inorganic hybrid solar cell further including an additional member may be configured.

According to an exemplary embodiment of the present specification, a substrate having excellent transparency, surface smoothness, handling easiness and waterproofness may be used as the substrate. As the substrate in the present specification, an organic material such as plastic having flexibility, glass, or metal may be used. At this time, as organic materials, polyimide (PI), polycarbonate (PC), polyethersulfone (PES), polyetheretherketone (PEEK), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE), ethylene copolymer, polypropylene (PP), propylene copolymer, poly (4-methyl-1-pentene) (TPX), polyarylate (PAR), polyacetal (POM), Polyphenylene oxide (PPO), polysulfone (PSF), polyphenylene sulfide (PPS), polyvinylidene chloride (PVDC), polyvinyl acetate (PVAC), polyvinyl alcohol (PVAL), polyvinyl acetal, polystyrene ( PS), AS resin, ABS resin, polymethyl methacrylate (PMMA), fluororesin, phenol resin (PF), melamine resin (MF), urea resin (UF), unsaturated polyester (UP), epoxy resin (EP) ), diallyl phthalate resin (DAP), polyurethane (PUR), polyamide (PA), silicone resin (SI), or mixtures and compounds thereof.

According to an exemplary embodiment of the present specification, the cathode may be a transparent electrode.

When the cathode is a transparent electrode, the cathode may be a conductive oxide such as indium tin oxide (ITO), tin oxide doped with fluorine (FTO), or indium zinc oxide (IZO). Furthermore, the cathode may be a translucent electrode. When the cathode is a translucent electrode, it may be made of a translucent metal such as Ag, Au, Mg, Ca, or an alloy thereof. When a translucent metal is used as the cathode, the solar cell may have a microcavity structure.

When the cathode of the present specification is a transparent conductive oxide layer, the electrode is PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS ( polystylene), POM (polyoxyethlene), AS resin (acrylonitrile styrene copolymer), ABS resin (acrylonitrile butadiene styrene copolymer), TAC (Triacetyl cellulose), PAR (polyarylate), etc. A material doped may be used. Specifically, indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zink oxide (AZO), indium zink oxide (IZO), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O _{3 ,} and antimony tin oxide (ATO) may be used, and more specifically, FTO.

According to an exemplary embodiment of the present specification, the step of forming the transparent electrode is sequentially cleaning the patterned cathode substrate with a cleaning agent, acetone, and isopropanol (IPA), and then from 1 to 100 ° C. to 250 ° C. on a heating plate for moisture removal. After drying for 30 minutes, specifically, at 250° C. for 10 minutes, and the substrate is completely cleaned, the surface of the substrate can be modified to be hydrophilic. As a pretreatment technique for this, a) a surface oxidation method using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet rays in a vacuum state, and c) using oxygen radicals generated by plasma oxidizing method and the like can be used. Through the surface modification as described above, the junction surface potential can be maintained at a level suitable for the cathode buffer layer surface potential, the thin film on the cathode can be easily formed, and a thin film of improved quality can be provided. One of the above methods is selected depending on the condition of the substrate. In any method, the practical effect of the pretreatment can be expected only when the oxygen escape from the surface of the substrate is commonly prevented and the residual moisture and organic matter is suppressed as much as possible.

In the examples described below in the present specification, a method of oxidizing the surface through ozone generated using UV was used, and after ultrasonic cleaning, the patterned cathode substrate was baked on a hot plate and dried well. Then, it is put into the chamber and a UV lamp is applied to clean the patterned cathode substrate by ozone generated by the reaction of oxygen gas with UV light. However, the method for modifying the surface of the patterned cathode substrate in the present invention does not need to be particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

According to an exemplary embodiment of the present specification, the anode may be a metal electrode. Specifically, the metal electrode is silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium ( Pd) may include one or two or more selected from the group consisting of.

According to an exemplary embodiment of the present specification, the organic-inorganic hybrid solar cell may have an inverted structure. When the organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification has an inverted structure, the anode may be (Ag), MoO ₃ /Al, MoO ₃ /Ag, MoO ₃ /Au, or Au.

The organic-inorganic hybrid solar cell of the inverted structure of the present specification may mean that an anode and a cathode of a solar cell having a general structure are configured in reverse directions. The Al layer used in a solar cell having a general structure is very vulnerable to oxidation in air, and it is difficult to ink it, so there is a limitation in commercializing it through a printing process. Since the solar cell of the inverted structure according to the exemplary embodiment of the present specification can use Ag instead of Al, it is stable to oxidation reaction compared to the solar cell of a general structure, and since Ag ink is easy to manufacture, it is suitable for commercialization through the printing process. There are advantageous advantages.

In the present specification, the organic-inorganic hybrid solar cell may have a nip structure. When the organic-inorganic hybrid solar cell according to the present specification has a nip structure, the anode may be a metal electrode, an oxide/metal composite electrode, or a carbon electrode. Specifically, the second metal is gold (Au), silver (Ag), aluminum (Al), MoO ₃ /Au, MoO ₃ /Ag MoO ₃ /Al, V ₂ O ₅ /Au, V ₂ O ₅ /Ag, V ₂ O ₅ /Al, WO ₃ /Au, WO ₃ /Ag or WO ₃ /Al.

In the present specification, the n-i-p structure means a structure in which a cathode, an electron transport layer, a photoactive layer, a hole transport layer, and an anode are sequentially stacked.

The hole transport layer and/or the electron transport layer material of the present specification may be a material that increases the probability that the generated charge is transferred to the electrode by efficiently transferring electrons and holes to the photoactive layer, but is not particularly limited.

According to an exemplary embodiment of the present specification, the hole transport layer refers to a layer that allows the holes generated in the photoactive layer to be easily transferred to the anode.

According to an exemplary embodiment of the present specification, the hole transport layer includes the polymer.

According to another embodiment, the polymer and additional other hole transport materials may be included. The hole transporting material is polythiophene, polystyrene, polypyrrole, polyaniline, polydiphenylacetylene, and their derivatives PEDOT (poly(3,4-ethylenedioxythiophene):PSS (polystyrene sulfonate) mixture, etc. or TDATA, m-MTDATA, 2-TNATA , TPTE, NPB, TPD, etc. may be used, but is not limited thereto.

According to an exemplary embodiment of the present specification, the organic-inorganic hybrid solar cell may include an electron transport layer between the cathode and the photoactive layer.

According to an exemplary embodiment of the present specification, the electron transport layer may include a metal oxide. Metal oxides are specifically Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, One or more selected from Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, and composites thereof may be used, but the present invention is not limited thereto.

According to one embodiment, the electron transport layer is Al ₂ O ₃ , ZnO, TiO ₂ , SnO ₂ , WO ₃ , TiSrO ₃ 1 or 2 or more selected from the group consisting of.

Specifically, according to an exemplary embodiment of the present specification, the electron transport layer includes Al ₂ O ₃ or TiO ₂ .

According to an exemplary embodiment of the present specification, the electron transport layer may be selected from the group consisting of fullerene, fullerene derivatives, vasocuproin, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, fullerene, fullerene derivatives (PCBM ((6,6)-phenyl-C61-butyric acid-methylester) or PCBCR ((6,6)-phenyl-C61-butyric acid-cholesteryl ester), perylene ( perylene) may include one or two or more selected from the group consisting of polybenzimidazole (PBI), and PTCBI (3,4,9,10-perylene-tetracarboxylic bis-benzimidazole), but is not limited thereto.

According to one embodiment, the electron transport layer is a fullerene derivative (PCBM ((6,6)-phenyl-C61-butyric acid-methylester).

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

Preparation Example 1. Preparation of Polymer 1

In a microwave reactor vial, 5 ml of chlorobenzene (CB), compound (4,8-bis(3-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4,5 -b']dithiophene-2,6-diyl)bis(trimethylstannane) 0.7 mmol, compound 2,6-dibromo-4H-cyclopenta[2,1-b:3,4-b']dithiophen-4-one 0.35 mmol , compound thienopyrroledione (TPD) 0.35 mmol, Tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ 12.8 mg, tri-(o-tolyl) phosphine, 17 mg ( After Soxhlet extraction, the chloroform portion was again precipitated in methanol to filter out the solid to obtain Polymer 1.

2 is a view showing UV data of Polymer 1.

Specifically, the UV data in the film state in FIG. 2 is the UV data measured after dissolving polymer 1 in chlorobenzene and manufacturing the film (a) through the spin coating method, and the UV data in the solution state (b) is the polymer 1 UV data measured after dissolving in chlorobenzene. FIG. 3 is a diagram showing CV data of Polymer 1. FIG.

In the present specification, cyclic voltammetry is composed of a working electrode that is a carbon electrode, a reference electrode, and a counter electrode that is a platinum plate. A method of measuring the current flowing through the

Table 1 shows the physical properties of the polymer 1.

Mn Mw PDI Band gap(s) 58640 69049 1.17 1.54 Band gap(f) HOMO (eV) LUMO (eV) 1.517 5.43 3.89

Preparation Example 2. Preparation of Polymer 2

In a microwave reactor vial, 5 ml of chlorobenzene (CB), compound (4,8-bis(3-((2-ethylhexyl)oxy)phenyl)benzo[1,2-b:4,5 -b']dithiophene-2,6-diyl)bis(trimethylstannane) 0.7 mmol, compound 2,6-dibromo-4H-cyclopenta[2,1-b:3,4-b']dithiophen-4-one 0.35 mmol , compound benzothiadiazole (BT) 0.35 mmol, Tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) 12.8 mg, tri-(o-tolyl)phosphine, 17mg) and reacted under the conditions of 120°C for 10 minutes, 150°C for 20 minutes, 170°C for 30 minutes, and 180°C for 10 minutes. After the mixture was cooled to room temperature and poured into methanol, the solid was filtered and Soxhlet extraction was performed with methanol, hexane, dichloromethane, and chloroform, and the chloroform portion was again precipitated in methanol to filter the solid to obtain Polymer 2.

4 is a view showing UV data of Polymer 2.

Specifically, the UV data of the film state (a) in FIG. 4 is the UV data measured after dissolving Polymer 2 in chlorobenzene and preparing a film through the spin coating method, and the UV data of the solution state (b) is the polymer 2 These are UV data measured after dissolving in chlorobenzene.

5 is a diagram showing CV data of Polymer 2.

Table 2 shows the physical properties of the polymer 2.

Mn Mw PDI Band gap(s) 13396 26149 1.95 1.67 Band gap(f) HOMO (eV) LUMO (eV) 1.52 5.46 3.94

Preparation Example 3. Preparation of Polymer 3

The polymer 3 may be prepared by the method described in Korean Patent Publication No. 2016-0075370.

6 is a view showing UV data of Polymer 3.

Specifically, the UV data in the film state in FIG. 6 is the UV data measured after dissolving polymer 3 in chlorobenzene and manufacturing a film through the spin coating method, and the UV data in the solution state is measured after dissolving polymer 3 in chlorobenzene. One UV data.

7 is a diagram showing CV data of Polymer 3.

Table 3 shows the physical properties of the polymer 3 above.

Mn Mw PDI UV _edge (nm) 67800 101400 1.5 673 Band gap(s) Band gap(f) HOMO (eV) LUMO (eV) 1.84 1.83 5.48 3.65

Preparation Example 4. Preparation of Polymer 4

The polymer 4 may be prepared by the method described in Korean Patent Laid-Open No. 2017-0067028.

8 is a view showing UV data of Polymer 4.

Specifically, the UV data in the film state in FIG. 8 is the UV data measured after dissolving polymer 4 in chlorobenzene and manufacturing it into a film through the spin coating method, and the UV data in the solution state is measured after dissolving polymer 4 in chlorobenzene. One UV data.

9 is a diagram showing CV data of Polymer 4.

Table 4 shows the physical properties of the Polymer 4.

Mn Mw PDI UV _edge (nm) 21315 24970 1.17 685.12 Band gap(s) Band gap(f) HOMO (eV) LUMO (eV) 1.82 1.81 5.53 3.72

Preparation Example 5. Preparation of Polymer 5

In a microwave reactor vial, 5 ml of chlorobenzene (CB), 0.35 mmol of compound A, 0.7 mmol of compound B, 0.35 mmol of compound C, Pd ₂ (dba) ₃ (Tris(dibenzylideneacetone)dipalladium(0)) 12.8 mg, tri-(o-tolyl) phosphine (tri-(o-tolyl) phosphine, 17 mg) was added and reacted for 1 hour at 150°C. After the mixture was cooled to room temperature and poured into methanol, the solid was filtered, Soxhlet extraction was performed with methanol, acetone, hexane, and chloroform, and the chloroform portion was again precipitated in methanol to filter out the solid.

10 is a view showing UV data of polymer 5.

In FIG. 10, (a) is UV data of polymer 5 in a film state, and (b) is UV data of polymer 5 measured in solution state.

In this case, (a) is UV data measured after dissolving polymer 5 in chlorobenzene and preparing a film through the spin coating method, and (b) is UV data measured after dissolving polymer 5 in chlorobenzene.

11 is a diagram showing CV data of Polymer 5.

Table 5 shows the physical properties of the polymer 5.

Mn Mw PDI 49160 61510 1.25 Band gap(f) HOMO (eV) 1.84 5.56

Preparation Example 6. Preparation of Polymer 6

In a microwave reactor vial, 5 ml of chlorobenzene (CB), 0.35 mmol of compound A, 0.7 mmol of compound B, 0.35 mmol of compound G, bis(dibenzylideneacetone)palladium(0) Pd ₂ (dba ) ₃ (Tris(dibenzylideneacetone)dipalladium(0)) 12.8mg, tri-(o-tolyl)phosphine, 17mg) was added and reacted for 1 hour at 150°C. After the mixture was cooled to room temperature and poured into methanol, the solid was filtered, Soxhlet extraction was performed with methanol, acetone, hexane, and chloroform, and the chloroform portion was again precipitated in methanol to filter out the solid.

12 is a view showing UV data of Polymer 6.

In FIG. 12, UV data of polymer 6 in a film state and measured UV data of polymer 6 in a solution state are shown.

At this time, the UV data in the film state is the UV data measured after dissolving the copolymer 6 in chlorobenzene and manufacturing it into a film through the spin coating method, and the UV data in the solution state is measured after dissolving the polymer 6 in chlorobenzene. UV data.

13 is a diagram showing CV data of Polymer 6.

Table 6 shows the physical properties of the polymer 6.

Mn Mw PDI 24100 48800 1.94 UV _edge (nm) Band gap(f) HOMO (eV) 667 1.86 5.3

Preparation Example 7. Preparation of Polymer 7

In a microwave reactor vial, 10 ml of chlorobenzene (CB), 0.5 mmol of compound BDT, 0.5 mmol of compound thiophene, 0.9 mmol of compound TPD, 0.1 mmol of DPP, Pd ₂ (dba) ₃ (Tris(dibenzylideneacetone)dipalladium (0)) 18.3 mg, tri-(o-tolyl) phosphine (tri-(o-tolyl) phosphine, 24.35 mg) was added and reacted at 150° C. for 1 hour. After the mixture was cooled to room temperature and poured into methanol, the solid was filtered and Soxhlet extraction was performed with methanol, acetone, hexane, and chloroform, and the chloroform portion was again precipitated in methanol to filter the solid to obtain a polymer 7.

14 is a view showing UV data of polymer 7.

Specifically, FIG. 14 shows (1) UV data measured after dissolving Polymer 4 in chlorobenzene to prepare a film through a spin coating method, UV data measured after annealing (1) at 100° C., and Polymer 4 These are UV data measured after dissolving in chlorobenzene.

15 is a diagram showing CV data of Polymer 7.

Table 7 shows the physical properties of the polymer 7.

UV _edge (nm) Band gap(f) HOMO (eV) LUMO (eV) 920 1.35 5.25 3.9

In Tables 1 to 7, Mn is a number average molecular weight, Mw is a weight average molecular weight, PDI is molecular weight distribution, UV _edge is UV absorption edge, Band gap(s) is a band gap in a solution state, Band gap (f) is It means the band gap in the film state.

Example 1-1. Preparation of organic-inorganic hybrid solar cells

An organic-inorganic hybrid solar cell was prepared with a nip structure of ITO/ZnO NP/PCBM/Perovskite/polymer 1/MoO _{3 /Ag.}

Specifically, ITO is a bar type, and a glass substrate (11.5 Ω/□) coated with 1.5 cm × 1.5 cm is ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface is washed with ozone for 10 minutes. After treatment, ZnO NPs (ZnO nanograde N-10 2.5wt% in 1-butanol, filtered in 0.45㎛ PTFE) were made, and this ZnO NP solution was spin-coated at 5000 rpm for 40 seconds, then 80℃ An electron injection layer was formed by heat treatment for 10 minutes at 1000 rpm to remove the remaining solvent, and 20 mg/ml of PCBM was spin-coated at 1000 rpm for 60 seconds to form an electron transport layer. _{Then, PbI 2 (Lead (II)} iodide, 99.9985%, Alfa Aesar) 0.759g and MAI (Methylammonium iodide, Dyesol) toluene to prepare a ₃ MAPbI 0.262g dissolved in dimethylformamide (DMF) 1ml to 35wt% concentration The photoactive layer was formed by dissolving it and dripping, and a solution (7 mg/ml) of the polymer 1 in chlorobenzene was spin-coated at 2000 rpm for 40 seconds to form a hole transport layer. MoO ₃ was thermally vapor-deposited at a rate of 0.2 Å/s at 10 ^-7 Torr to a thickness of 2 nm, and then 100 nm of Ag was deposited at a rate of 1 Å/s inside the thermal evaporator to form a nip-structured organic-inorganic hybrid solar cell was prepared.

Example 1-2. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Example 1-1, except that Polymer 2 was spin-coated at 1000 rpm for 40 seconds instead of Polymer 1 as the hole transport layer.

Examples 1-3. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Example 1, except that Polymer 7 was spin-coated at 1500 rpm for 40 seconds instead of Polymer 1 as the hole transport layer.

The photoelectric conversion characteristics of the organic-inorganic hybrid solar cells prepared in Examples 1-1 to 1-3 were ^{measured under 100 mW/cm 2} (AM 1.5) conditions, and the results are shown in Table 8 below.

V _oc
(V) J _sc
(mA/cm ² ) FF
(%) PCE
(%) Example 1-1 1.090
15.413
64.796
10.884 Example 1-2 1.095
16.914
60.966
11.295 Examples 1-3 1.047
13.685
72.795
10.430

Comparative Example 2-1. Preparation of organic-inorganic hybrid solar cells

An organic-inorganic hybrid solar cell was prepared with a nip structure of ITO/ZnO NP/PCBM/Perovskite/polymer 1/MoO _{3 /Ag.}

Specifically, ITO is a bar type, and a glass substrate (11.5 Ω/□) coated with 1.5 cm × 1.5 cm is ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface is washed with ozone for 10 minutes. After treatment, ZnO NPs (ZnO nanograde N-10 2.5wt% in 1-butanol, filtered in 0.45㎛ PTFE) were made, and this ZnO NP solution was spin-coated at 5000 rpm for 40 seconds, then 80℃ An electron injection layer was formed by heat treatment for 10 minutes in a chlorobenzene to remove the remaining solvent, and 20 mg/ml of PCBM in chlorobenzene was spin-coated at 5000 rpm for 40 seconds, and then spin-coated at 1000 rpm for 60 seconds to form an electron transport layer. _{Then, PbI 2 (Lead (II)} iodide, 99.9985%, Alfa Aesar) 0.759g and MAI (Methylammonium iodide, Dyesol) toluene to prepare a ₃ MAPbI 0.262g dissolved in dimethylformamide (DMF) 1ml to 35wt% concentration The photoactive layer was formed by dissolving it and dripping, and a solution (7 mg/ml) of the following P3HT in chlorobenzene was spin-coated at 1000 rpm for 40 seconds to form a hole transport layer. MoO ₃ was thermally vapor-deposited at a rate of 0.2 Å/s at 10 ^-7 Torr to a thickness of 2 nm, and then 100 nm of Ag was deposited at a rate of 1 Å/s inside the thermal evaporator to form a nip-structured organic-inorganic hybrid solar cell. was prepared.

Example 2-1. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that the polymer 1 was spin-coated at 2000 rpm for 40 seconds instead of the P3HT as the hole transport layer.

Example 2-2. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that Polymer 2 was used instead of P3HT as the hole transport layer.

Example 2-3. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that Polymer 3 was spin-coated at 2000 rpm for 40 seconds instead of P3HT as the hole transport layer.

Example 2-4. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that Polymer 4 was spin-coated at 2000 rpm for 40 seconds instead of P3HT as the hole transport layer.

Example 2-5. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that the polymer 5 was spin-coated at 1500 rpm for 40 seconds instead of the P3HT as the hole transport layer.

Example 2-6. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that the polymer 6 was spin-coated at 2000 rpm for 40 seconds instead of the P3HT as the hole transport layer.

Example 2-7. Preparation of organic-inorganic hybrid solar cells

It was prepared in the same manner as in Comparative Example 2-1, except that the polymer 7 was spin-coated at 1500 rpm for 40 seconds instead of the P3HT as the hole transport layer.

The photoelectric conversion characteristics of the organic-inorganic hybrid solar cells prepared in Comparative Example 2-1 and Examples 2-1 to 2-7 ^{were measured under 100 mW/cm 2} (AM 1.5) conditions, and the results are shown in Table 9 below. was shown.

V _oc
(V) J _SC
(mA/cm ² ) FF
(%) Average PCE (%) Comparative Example 2-1 0.925 15.709 64.269 9.339 Example 2-1 1.058 16.080 56.991 10.228 Example 2-2 1.071 12.779 71.276 10.042 Example 2-3 1.006 15.574 61.908 9.686 Example 2-4 1.042 14.96 66.141 10.305 Example 2-5 1.051 15.883 69.312 11.545 Example 2-6 1.071 15.462 64.913 10.707 Example 2-7 1.074 15.396 62.884 10.380

In Table 9, the organic-inorganic hybrid solar cells of Examples 2-1 to 2-7 have better open circuit voltage, charge rate and energy conversion efficiency than the organic-inorganic hybrid solar cells using P3HT of Comparative Example 1 as a hole transport layer. can be known

Where V _oc is an open circuit voltage, J _sc is a short circuit current, FF is a fill factor, and PCE(η) is energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively, and the higher these two values, the higher the efficiency of the solar cell is. Also, the fill factor is a value obtained by dividing the area of a rectangle that can be drawn inside the curve by the product of the short-circuit current and the open-circuit voltage. By dividing these three values by the intensity of the irradiated light, energy conversion efficiency can be obtained, and a higher value is preferable.

As a result of Tables 8 and 9, it can be confirmed that the organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification exhibits high photoelectric conversion efficiency.

101: substrate
102: cathode
103: photoactive layer
104: hole transport layer
105: anode

Claims (13)

cathode;
an anode provided to face the cathode;
a photoactive layer comprising a compound having a perovskite structure provided between the cathode and the anode; and
An organic-inorganic hybrid solar cell comprising a hole transport layer comprising a polymer represented by any one of the following Chemical Formulas 1-1 to 1-6 provided between the anode and the photoactive layer:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6,
l is the mole fraction, a real number with 0≤l < 1,
m is the mole fraction, a real number with 0≤m < 1,
o is the mole fraction, a real number with 0 ≤ o < 1,
p is the mole fraction, a real number with 0≤p < 1,
n is the number of repetitions of the unit, and is an integer from 1 to 10,000,
X1 to X5, X8 to X19, X61, X71, X81, X82, X111, X211, X131, X132, X141, X151 and X161 are the same as or different from each other, and each independently S, Se, O, CRR' or NR; ,
Y1 to Y4 are the same as or different from each other, and are each independently N or CR",
Ar1 to Ar4, R1 to R4, R7 to R24, Ar11, Ar21, R51, R61, R71, R72, R81, R82, R111, R112, R121, R122, R131, R141, R211, R, R' and R" are same or different from each other, and each independently hydrogen; deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amide group; substituted or unsubstituted alkyl group; substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkylsulfoxy group; Substituted or unsubstituted aryl A sulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine group a fin oxide group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
L1 to L4, L11 and L21 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
In Formulas 1-1 to 1-5, l+m=1,
In Formula 1-6, l+m+o+p=1. The organic-inorganic hybrid solar cell of claim 1 , wherein the compound of the perovskite structure is an organo-metal halide compound of the perovskite structure. The organic-inorganic hybrid solar cell according to claim 1, wherein the compound of the perovskite structure is represented by the following Chemical Formula 6:
[Formula 6]

In Formula 6,
Q is C _n H _2n+1 NH ₃ ⁺ , NH ₄ ⁺ , HC(NH ₂ ) ₂ ⁺ , Cs ⁺ , NF ₄ ⁺ , NCl ₄ ⁺ , PF ₄ ⁺ , PCl ₄ ⁺ , CH ₃ PH ₃ ⁺ , CH ₃ AsH ₃ ⁺ , CH ₃ SbH ₃ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ and SbH ₄ ⁺ is a monovalent cation selected from,
M is Cu ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ²⁺ , Mn ²⁺ , Cr ²⁺ , Pd ²⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Bi ²⁺ , Pb ²⁺ and It is a divalent metal ion selected from ^{Yb 2+,}
X is a halogen ion,
n is an integer from 1 to 9; The method according to claim 2, wherein the organo-metal halogen compound is CH ₃ NH ₃ PbI _x Cl _y , CH ₃ NH ₃ PbI _x Br _y , CH ₃ NH ₃ PbCl _x Br _y and CH ₃ NH ₃ PbI _x F _{y The} group consisting of 1 or 2 or more selected from
x is a real number between 0 and 3,
y is a real number between 0 and 3,
wherein x+y=3, an organic-inorganic hybrid solar cell. The organic-inorganic hybrid solar cell of claim 1 , wherein the polymer is a random polymer. delete delete delete delete delete The organic-inorganic hybrid solar cell according to claim 1, wherein the polymer is represented by any one of the following compounds 1-1 to 1-7:
[Compound 1-1]

[Compound 1-2]

[Compound 1-3]

[Compound 1-4]

[Compound 1-5]

[Compound 1-6]

[Compound 1-7]

In the compounds 1-1 to 1-7,
The definitions of l, m, n, o and p are the same as those defined in Formulas 1-1 to 1-6. The organic-inorganic hybrid solar cell of claim 1 , wherein the photoactive layer has a thickness of 10 nm to 2,000 nm. The organic-inorganic hybrid solar cell of claim 1, wherein the hole transport layer has a thickness of 10 nm to 2,000 nm.

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