WO2015099412A1

WO2015099412A1 - Precursor of inorganic/organic hybrid perovskite compound

Info

Publication number: WO2015099412A1
Application number: PCT/KR2014/012727
Authority: WO
Inventors: 석상일; 노준홍; 전남중
Original assignee: 한국화학연구원
Priority date: 2013-12-23
Filing date: 2014-12-23
Publication date: 2015-07-02

Abstract

The preset invention relates to a precursor of an inorganic/organic hybrid perovskite compound, and the precursor of the inorganic/organic hybrid perovskite compound according to an embodiment of the present invention contains organic positive ions, metal positive ions, halogen negative ions, and guest molecules (GM).

Description

Specification

Name of Invention: Inorganic / Organic Hybrid Perovskite Compound

Precursor

Field of technology

[1] The present invention relates to precursors of non-organic hybrid perovskite compounds

Specifically, the present invention relates to a light absorber precursor material of a solar cell including an inorganic / organic hybrid perovskite compound as a light absorber.

[2]

Background

[3] Organic / organic hybrid perovskite compounds, also referred to as organometal halide perovskite compounds, consist of organic cations (A), metal cations (M), and halogen anions (X). becomes, ^"it is a substance represented by the formula medicinal chemistry AMX ₃ having a perovskite structure in detail. The inorganic / organic hybrid pe ^ skite compound represented by the chemical formula of AMX ₃ is a form of A organic cation interposed in a three-dimensional network of MX ₆ octahedron. Iemu / Organic Hybrid

Perovskite compounds have the advantage of self-assembling and self-assembling crystallization, which allows the processing of hot solutions.However, the crystallization rate is very fast and it is difficult to control the self-assembly characteristics. There is a problem that is difficult to manufacture dense thin films with.

[4] In order to solve this problem ^", by coating a metal halide (MX ₂₎ solution

Sequential formation of metal halide membranes, application of organic halide (AX) solutions on metal halide membranes to form MX ₂ and AX laminated layers, and then reflexion of the bilateral membranes to form organic / organic hybrid perovskite compound membranes. A sequential deposition method has been proposed (Chem. Mater. 13, 3283 (2001)). However, this sequential deposition method is, firstly, a thick metal halogen that does not have a very high solubility of the MX ₂ represented by Pbl ₂ . Secondly, there is a problem in the production of cargo membranes, and secondly, even if the MX ₂ solution is maintained at a high temperature, even if a thick membrane of 200 nm or more is obtained, there is a problem that it is not sufficiently reflected by the thickness in the reaction step with AX. Membrane mirrors made of uranium _: Radical / organic hybrid finally obtained due to the large volume change of the right and left membranes

The problem is that the surface roughness of the perovskite compound film is very large.

In solar cells equipped with a light absorbing layer, it can be a decisive factor that degrades the performance index of the cell.

[5] Detailed description of the invention

Technical task

[6] An object of the present invention is to provide an inorganic / organic hybrid perovskite compound precursor and a membrane thereof capable of producing an inorganic / organic hybrid perovskite compound film by reaction.

[7] In detail, the purpose of the present invention is thick radish / organic hybrid perovskite

The present invention provides an inorganic / organic hybrid perovskite compound precursor capable of producing a compound film, a film of coarse grains, and a film having a dense and smooth surface.

[8] Another object of the present invention is to prepare an inorganic / organic hybrid perovskite compound film using an inorganic / organic hybrid perovskite compound precursor.

It is to provide a manufacturing method.

[9] Another object of the present invention is to prepare an inorganic / organic hybrid perovskite compound film prepared using an organic / organic hybrid perovskite compound precursor.

It is to provide a solar cell including the light absorption layer and a manufacturing method thereof.

[10]

Task solution

[11] The precursors of the inorganic / organic hybrid perovskite compounds according to the present invention contain organic cations, metal cations, halogen anions and guest molecules (GM).

[12] The precursor according to one embodiment of the present invention is X-ray diffraction using Cu-? Α rays.

In the measurement, diffraction peaks can be detected at diffraction angles 2Θ of 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °.

In the precursor material according to an embodiment of the present invention, the guest molecule may be a solvent for dissolving the inorganic / organic hybrid perovskite compound.

According to one embodiment of the present invention, the precursor may be a solvent compound between an inorganic / organic hybrid perovskite compound and a solvent.

In the precursor material according to one embodiment of the present invention, the guest molecule may be a solvent containing one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine.

[16] In the precursor material according to an embodiment of the present invention, the guest molecule

Ν, Ν-dimethylacetamide (Dimethylacetaniid), 1,4-dioxane, diethylamine, ethylacetate,

Tetrahydrofuran, pyridine, methanol, ethanol, dichlorobenzene, glycerin,

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

The precursor material according to the embodiment of the present invention may satisfy the following Formula 1. [18] (Formula 1)

[19] AM (GM) „X ₃

[20] A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium ion _. It is a divalent metal ion, X is halogen or silver, and is a real number with 0 <η <3.

[21] In the precursor according to one embodiment of the present invention, in Formula 1, X is Xv _y> X ^b _y ,

X ^a and X ^b are different halogen ions selected from iodine ion (I), chlorine ion (C1-) and bromine ion (Br), and y may be a real number with 0 <y <l.

The precursor material according to the embodiment of the present invention may be for a solar cell light absorber.

[23] The present invention relates to a dispersion or a precursor containing the above precursor.

Containing ink.

[24] The present invention provides a method for manufacturing a solar cell photoabsorber using the above-described precursors.

Include.

[25] A method of manufacturing a light absorber according to an embodiment of the present invention comprises the steps of applying or depositing a precursor material on the substrate to form a precursor material layer; and applying energy to the precursor material layer to volatilize guest molecules. Removing; may include.

[26]

Effects of the Invention

[27] The precursor material according to the present invention is a single bulb material, which is free from organic hybrids.

Perovskite compounds can be prepared and can be converted into inorganic / organic hybrid perovskite compounds by removal of guest molecules, making it possible to produce inorganic / organic hybrid perovskite compound films with fine and excellent crystallinity. There is this.

[28] It is a very simple process to remove guest molecules.

As it is possible to manufacture dense membranes of perovskite compounds, a dense membrane of high quality inorganic / organic hybrid perovskite compounds can be produced at low cost, and the membrane quality does not change sensitively with the change of process variables. It is very easy to maintain the quality, and has the advantage of making a large-area obligation / dense film of organic hybrid perovskite compound.

[29] In addition, when using the precursor material according to the present invention, organic / organic hybrid

As it is possible to form a perfect film of the light absorber which is a perovskite compound, it is easy to control the thin film formation of the organic / organic hybrid perovskite compound, thereby making a thin film transistor, a light emitting diode, a sensor It can be used in various applications such as solar cells.

[30]

Brief description of the drawings

1 shows X-ray diffraction results of precursor material powders prepared according to one embodiment of the present invention. City limits,

2 is an FTIR transmission of a precursor material powder prepared according to one embodiment of the present invention.

Spectrum,

FIG. 3 is a diagram showing the results of X-ray diffraction according to temperature of precursor material powders prepared according to one embodiment of the present invention.

4 is a diagram showing the X-ray diffraction results of the precursor material thin film manufactured according to an embodiment of the present invention,

FIG. 5 is a scanning electron microscope photograph of the perovskite compound thin film prepared from the precursor material thin film manufactured according to the embodiment of the present invention.

[36]

Mode for Carrying Out the Invention

[37] The precursors of the present invention will be described in detail with reference to the accompanying drawings. The drawings presented below are provided as examples for the purpose of fully conveying the idea of the present invention to the person skilled in the art. Thus, the present invention may be embodied in other forms, not limited to the drawings presented below. These may be exaggerated to clarify the spirit of the present invention, unless otherwise defined in the technical terminology and scientific terminology used, which means that those with ordinary knowledge in the technical field to which the present invention belongs usually understand. In the following description and accompanying drawings, descriptions of the known functions and configurations that may unnecessarily obscure the subject matter of the present invention are omitted.

[38] The present invention relates to a Korean application number 2013-0110020 and a Korean application number.

Includes all content of heading 2013-0110025.

[39] The present applicant is responsible for converting a radiant / organic hybrid perovskite compound into a light absorber.

Much research has been conducted to improve the efficiency of perovskite-based solar cells, including inorganic and organic hybrid perovskite compounds.

It has been found that the photoelectric conversion efficiency of solar cells is greatly improved when filling the pores of the electron transporter and having a dense film with a smooth surface covering the porous electron transporter.

[40] One of the main advantages of the organic / organic hybrid perovskite compound is that it can be applied with a solution coating method. However, crystallization to an organic / organic hybrid perovskite compound is possible with the solution coating method. The reality is that the speed is very fast, it is difficult to control the self-assembly characteristics, and it is very difficult to manufacture a dense film with a flat surface.

[41] Radical / organic hybrid using solution coating method based on the above findings

In order to solve the limitations of the film quality of perovskite compound membranes, research has been conducted. As a result, the process advantages of conventional radish / organic hybrid perovskite compounds can be retained, while the high quality dense membrane forms of organic / organic hybrids. A precursor capable of producing a perovskite compound film was found and the present invention has been filed.

[42] In the present invention, the inorganic / organic hybrid perovskite compound contains monovalent organic cations (A), divalent metal cations (M), and halogen anions (X), and has a perovskite structure. It can mean a compound with.

[43] In detail, the organic / organic hybrid perovskite compound is located at the center of a unit cell in the M-perovskite structure, and X is located at the center of each side of the unit cell, with M being the center. to form a head-octahydro Ron (octahedron) structures, a may be located at each corner (corner) of a unit of Sal. If above it again, ΜΧ _ή

The octahedron may be in a corner-shearing three-dimensional network where A organic cations are intercalated.

[44] In the description below, organic / organic hybrid perovskite compounds

Also referred to as perovskite compound. In addition, the precursor of the inorganic / organic hybrid perovskite compound is referred to as the precursor material.

The perovskite compound may satisfy the following formula (1).

[46] (Formula 1)

[47] AMX ₃

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

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

In Chemical Formula 1, the organic ammonium silver may satisfy the following Chemical Formulas 1-1 to 1-2.

[50] (Formula 1-1)

[51] R, -NH ₃ ⁺

In formula 1-1, R, is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.

[53] (Formula 1-2)

[54] R ₂ -H ₃ N ₂ l ₃

In formula 1-2, R ₂ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, R ₃ is hydrogen or C1-C24 alkyl.

In Chemical Formula 1, the amidinium-based ions may satisfy the following Formula 1-3.

[57] -3)

In formula 1-3, R ₄ to R ₈ are independently of each other hydrogen, alkyl of C1-C24, cycloalkyl of C3-C20 or aryl of C6-C20.

[60] In Formula 1, A may be an organic ammonium silver, an amidinium group ion, or an organic ammonium silver or an amidinium ion. In the case of containing both an organic ammonium ion and an amidinium ion, The charge mobility of the perovskite compound can be significantly improved.

[61] When A contains both organic ammonium ions and amidinium ions, the total molar number of monovalent organic cations is 1, and contains 0.7 to 0.95 amidinium ions and 0.3 to 0.05 organic ammonium ions. In other words, in Formula 1, A is A _x) A, A a is an amidinium ion, A ^b is an organic ammonium ion, and X can be a real number from 0.3 to 0.05. The molar ratio of organoammonium ions, i.e., 0.7 to 0.95 moles of amidinium-based ions: 0.3 to 0.05 moles of organic ammonium ions, is capable of absorbing very broad wavelengths of light, This is the range where separation, faster optoelectronics and light holes can be made.

[62] R ₂ to R ₃ of Formula 1-2 and / or R ₄ to R _S of Formula 1-3 are

It may be appropriately selected according to the use of the perovskite compound, i.e., the light absorbing layer of the solar cell.

In detail, the unit cell size of the perovskite compound is related to the band gap and may have a bandgap energy of 1.5 to 1.1 eV suitable for use as a solar cell in a small unit size. When considering a bandgap energy of 1.5 to 1.1 eV, which is suitable for use, in Formula 1-1, R, may be C1-C24 alkyl, specifically C1-C7 alkyl, more specifically methyl. At -2 R ₂ can be C1-C24 alkyl and R ₃ can be hydrogen or C1-C24 alkyl, specifically ¾ can be C1-C7 alkyl and ¾ can be hydrogen or C1-C7 alkyl, more specifically ¾ may be methyl and R ₃ may be hydrogen. Further, in formula 1-3, R 4 to R ₈ are independently of each other hydrogen, amino or C 1 -C ₂₄ alkyl, specifically hydrogen, amino or C 1 -C 7 alkyl, More specifically hydrogen, amino or methyl, more specifically R4 hydrogen , Amino or methyl and R ₅ is hydrogen to a number of days. More specifically, and as a non-limiting example, an amidinyl you umgye ions formamidinium nium _{(formamidinium, NH 2 CH = NH} 2 +) ions,

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

Guamidinium, NH ₂ C (NH ₂ ) = NH ₂ ⁺ ).

[64] As described above, specific examples of the organic cationic (A) are an example of the use of the perovskite compound film, that is, the application to the light absorbing layer of sunlight, and the design and emission of the wavelength band of the light to be absorbed. when using the light-emitting layer of the device design of the emission wavelength band, in the case of using a semiconductor device of the transistors in consideration of the energy band gap and the threshold voltage (threshold voltage) of formula 1-2, such as of formula 1-1 R ₂ ~ R ₃ And / or ¾ to ¾ of formula 1-3 may be appropriately selected. [65] In Formula 1, M is a divalent metal ion days. A specific example, M is M is ^{^{Cu 2 +, Ni 2+, Co}} 2+, Fe 2+, Mn 2+, Cr 2+, Pd 2 ^{It may be} one or more metal ions selected from ⁺ , Cd ²⁺ , Ge ²⁺ , Sn ²⁺ , Pb ²⁺ and Yb ²⁺ .

In Formula 1, X is a halogen anion. The halogen anion may be selected from one, two or more of I, Br, F, and C1-. Specifically, the halogen anion is iodine (I), chlorine (C1-). ) And bromine ions (Br) may contain one or more selected ions. More specifically, halogen anions may contain iodine ions and bromine ions. Halogen anions contain both iodide and bromine ions. In this case, the crystallinity and moisture resistance of the perovskite compound can be improved.

[67] As a specific example, in Formula 1, X may be X _y) X ^b _y , and X ^a and X ^b may be each other.

Different halogen ions (different halogen ions selected from iodine ion (1), chlorine ion (C1-) and bromine ion (Br)), and y may be a real number of 0 <y <l. Where X may be X _y) X ^h _y , X ^a iodine ion, X ^b is bromine ion, y may be a real number of 0.05 ≦ y ≦ 0.3, specifically 0.1 ≦ x ≦ 0.15. Deterioration by moisture can be significantly prevented and the crystallinity of the perovskite compound can be improved.

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

As an example of a perovskite compound, the perovskite compound may be selected from CH ₃ NH ₃ PbI _x Cl _y (real number of 0 ≦ _x ≦ ₃ , real number of 0 ≦ _y ≦ 3 and x + y = 3), CH ₃ NH ₃ PbI _x Br _y (0≤x≤3 real number, 0≤y≤3 real number and x + y = 3), CH ₃ NH ₃ PbCl _x Br _y (0≤x≤3 real number, 0≤y ≤ 3 phosphorus and x + y = 3), CHsNHsPblj O x S phosphorus, 0 ≦ y ≦ 3 phosphorus and x + y = 3), NH ₂ CH = NH ₂ PbI _x Cl _y (0 ≦ _x ≦ 3 Number of people, 0 ≤ y ≤ 3 people and x + y = 3), NH ₂ CH = NH ₂ PbI _x Br _y (0 ≤ _x ≤ ₃ people ᅳ 0 ≤ y ≤ 3 people, and x + y = 3) _{_{), NH 2 CH = NH 2}} PbCl x Br y (0≤x≤3 room number, room number 0≤y≤3 and x + y = 3), NH 2 CH = NH 2 PW x F y (0≤x ≤ 3 real number, 0 ≤ y ≤ 3 real number and x + y = 3), NH ₂ CH = NH 2 _(l . _X) CH ₃ NH _3x Pb (I _(l . _Y) Br _y ) ₃ (x is 0 <χ <1 real number, y is 0 <y <l real number), NH ₂ CH = NH 2 ₍₁ - _x) CH ₃ NH _3x Pb (I ₍₁ _ _y) Br _y ) ₃ (x is 0.05 ≤ x ≤ 0.3 real number, y is 0.05 ≤ y ≤ (). 3 real number), NH ₂

(0 ≦ _x ≦ ₃ real number, 0 ≦ _y ≦ ₃ real number and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbI _x Br _y (0 ≦ _x ≦ ₃ real number, 0 ≦ y ≤ 3 phosphorus and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbCl _x Br _y (0 ≤ _x ≤ ₃ phosphorus, 0 ≤ y ≤ 3 phosphorus and x + y = 3), NH ₂ C (CH ₃ ) = NH ₂ PbI _x F _y (real number 0 ≦ _x ≦ ₃ , real number 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (CH ₃ ) = NH _{2 (1 -x)} CH ₃ NH _3x Pb (I ₍₁ - _y) Br _y ) ₃ (x is 0 <χ <1 real number, y is 0 <y <l real number), NH ₂ C (CH ₃ ) = NH _{2 (l} . _X) CH ₃ NH _3x Pb (I ₍₁ _ _y) Br _y ) ₃ (x is a real number with 0.05 ≦ x ≦ 0.3, y is

0.05 <y <0.3 real number), NH ₂ C (CH ₃ ) = CH _{2 (lx)} CH ₃ NH _3x Pb (I _(lx) Br _x ) ₃ (x is a real number where 0.05≤x≤0.3), NH ₂ C (NH ₂ ) = NH ₂ PbI _x Cl _y (real number 0 ≦ _x ≦ 3, real number 0 ≦ _y ≦ 3 and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PbI _x Br _y (0 ≦ _x ≦ ₃ real number, 0 ≦ _y ≦ 3 real number and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PbCl _x Br _y (0 ≦ _x ≦ ₃ real number, 0 ≦ y ≤ 3 real number and x + y = 3), NH ₂ C (NH ₂ ) = NH ₂ PbI _x F _y (0 ≤ _x ≤ 3 real number, 0 <y <3 real number and x + y = 3), NH ₂ C (NH ₂ ) = NH _{2 (1} _ _x) CH ₃ NH _3x Pb (I ₍₁ - _y) Br _y ) ₃ (x is a real number that is sid and y is 0 <y <l ), NH ₂ C (NH ₂ ) = NH _{2 (l} _ _x) CH ₃ NH _3x Pb (I ₍₁ _ _y) Br _y ) ₃ (x is Real number with 0.05 ≦ x ≦ 0.3, and y is real number with 0.05 ≦ y ≦ 0.3) or NH ₂ C (NH ₂ ) = C ₀ . _X) CH ₃ NH 3 _x Pb (I ₍₁ _ _x ) Br _x ) ₃ ( _X is a real number of 0.05 ≦ _x ≦ 0.3).

According to one embodiment of the present invention, the precursor is a precursor of the perovskite compound described above, and an organic cation, a metal cyanide, a halogen cyanide (X), and a guest molecule (hereinafter, GM). In the precursor according to one embodiment of the present invention, the organic cationic silver, metal ions and halogen anions contained in the precursor are

Since the perovskite compound may be identical to the monovalent organic cations (A), divalent metal ions (M) and halogen anions (X) described above, a detailed description thereof is omitted.

[70] In the crystal structure, the precursor material is amorphous, crystalline, or amorphous and crystalline.

It may be a common substance. Specifically, the precursor material may be crystalline.

In detail, the precursor material according to the embodiment of the present invention is diffracted at an X-ray diffraction measurement using Cu-Koc rays, at a refraction angle 2Θ of 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °. Peaks can be detected, where peaks in the range of 5 ° ≤2Θ≤40 °

Peak strengths of 8.9 to 9.5 ° or 7 to 7.5 ° may be the highest.

[72] The precursor material according to one embodiment of the present invention is transferred to a sharp perovskite phase.

GM, which can prevent conversion, may be in the form of a complex formed by coexistence with A organic cations, M metal cations, and X halogen anions, i.e., the precursors are those in which GM contains A organic cations, M metal cations, and X halogen anions. It may be in the form of a complex formed in combination with a perovskite compound (ΑΜΧ ₃ ).

Specifically, the bond between the perovskite compound and the GM may be a non-covalent bond, and GM is non-covalently bound to one or more selected cations from monovalent organic cations (A) and divalent metal cations (M). It may be a state.

In the precursor material according to one embodiment of the present invention, the guest molecule may be a solvent that dissolves the perovskite compound. Accordingly, the precursor material may be a perovskite compound and a solvent compound and a solvent compound thereof. Solvent compounds may mean higher order compounds formed between molecules or ions of the solute (perovskite compound) and the molecules or ions of the solvent.

In this case, the solvent for dissolving the perovskite compound may mean a polar organic solvent, and at 20 ° C 1 atm, solubility of the perovskite compound is 0.5 M or more, specifically, 0.8 M or more. Can mean.

[76] If the precursor is a solvent compound of the perovskite compound and the solvent that dissolves it, it can be homogeneously and quickly removed at low temperatures and converted into a perovskite compound. The solvent may be a non-covalently bound solvent compound of the skye compound and the GM, and the GM may be a solvent containing one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine containing a non-covalent electron pair.

[77] at least one element selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine; As an example of a solvent containing and dissolving a perovskite compound,

Ν, Ν-dimethylacetamide (Dimethylacetamid), 1,4-dioxane, diethylamine, ethylacetate,

Tetrahydrofuran, pyridine, methanol, ethanol, dichlorobenzene, glycerin and

Dimethyl sulfoxide (DMSO), Ν, Ν-dimethylformamide (DMF; dimethylformamide) or mixtures thereof, i.e. guest molecules

Tetrahydrofuran, pyridine, methanol, ethanol, dichlorobenzene, glycerin,

One or more may be selected from dimethyl sulfoxide (DMSO) and Ν, Ν-dimethylformamide (DMF), in which the volume is converted to perovskite compounds upon removal of GM. In terms of preventing membrane damage due to changes, the guest molecule is preferably dimethyl sulfoxide (DMSO).

The precursor according to an embodiment of the present invention may satisfy the following formula (2).

[79] (Formula 2)

[80] AM (GM) _n X ₃

In Formula 2, A is an organic ammonium ion, an amidinium group,

Or organic ammonium ions and amidinium-based ions, M is a divalent metal ion, X is a halogen ion, and a real number of 0 <n <3. In Formula 2, A, Μ, and X are represented by Formula 1. The same as A, Μ and X described above.

That is, the precursor according to Chemical Formula 2 is removed by GM by external energy, and can be converted into a perovskite compound according to Chemical Formula 1.

In this case, as described above in the perovskite compound, in Formula 2, A is A _x) A b _x , A ^a is an amidinium-based ion, A ^b is an organic ammonium ion, and X is 0. A real number of <χ <1, specifically, may be a real number of 0.05≤x≤0.3.

Independently, in Formula 2, X is X _y ᅳ X ^b _y , X is a different halogen ion selected from iodine chlorine ion (C1-) and bromine ion (Br), and y is 0 < In the formula 2, X is X _y) X ^b _y , X ^{a is} iodine ion, X ^b is a brine ion, y is a real number of 0 <> 1, specifically, 0.05 It may be a real number ≤ y ≤ 0.3, more specifically 0.1 ≤ y ≤ 0.15.

In the perovskite compound precursor according to one embodiment of the present invention,

Perovskite Compounds By the energy applied to the precursor, the guest molecules are removed and converted into crystalline perovskite compounds.

In other words, since the precursor is a complex compound of perovskite compound and GM, it is converted into pure perovskite compound by removing GM by energy application. Can be switched.

The precursor material according to one embodiment of the present invention may be for a solar cell light absorber.

[88] The present invention relates to a dispersion or a precursor containing the above-mentioned precursor.

In addition to the precursors and dispersion mediums described above, the dispersions or inks may, of course, contain further known additives so that they may have properties suitable for the application or printing method.

The precursor is a non-solvent dripping of a first solution containing an organic cation, a metal cation, a halogen ion and a guest molecule according to the stoichiometric ratio of the perovskite compound; and a solid obtained by the drop. Recovery and drying; the precursor is a complex of perovskite compound and GM, and the precursor is similar to the perovskite compound in organic solvents (solubility, etc.). Therefore, it can be used as the solvent of the solvent system 1, which dissolves the normal perovskite compound. As long as the solvent that dissolves the precursor material is a solvent that dissolves the perovskite compound and is easily volatile-removable, Can be used.

Gamma-butyrolactone (GBL),

L-Methyl-2-pyrolidinone, but the present invention is not limited by this.

When the precursor is a solvent compound, the solvent of the first solution may be a guest molecule, ie, the first solution may be prepared by dissolving an organic cation, a metal cation, and a halogen ion in a solvent that is a guest molecule.

[91] At this time, the precursor material is similar to the perovskite compound for organic solvents.

As it can have the same properties (solubility, etc.), the nonsolvent can mean an organic solvent that does not dissolve the perovskite compound, meaning that it does not dissolve the perovskite compound at 20 ^o C 1 atm, An organic solvent having a solubility of perovskite compound of less than 0.1 M, specifically less than 0.01 M, and more specifically less than 0.001 M may be used.

[92] An example of a nonsolvent in which the first solution is deposited is a nonpolar organic solvent.

Non-polar organic solvents are pentine, nucleene, cyclonuxene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1, One or more organic solvents may be selected from 2-dichlorobenzene, tert-butyl alcohol, 2-butanol, isopropanol and methyl ethyl keron, but the present invention is not limited by non-solvents. It is possible to improve the productivity by increasing the concentration of the content of the C solution 1, but the concentration of the first solution may be any concentration so long as the stoichiometric ratio is satisfied within the solubility range of each solute.

[93] The recovery of solid phase is sufficient using the method used for normal solid-liquid separation, for example, but not limited to filtering, centrifugation, etc. Drying does not limit the precursors to thermal and safe damage. Range is sufficient. For example, drying It can be performed at room temperature to 50 ° C.

[94] The present invention provides a method for manufacturing a solar cell photoabsorber using the above-described precursors.

Include.

According to one aspect of the present invention, there is provided a method of manufacturing a light absorber, the method comprising: applying or depositing a precursor material on a substrate to form a precursor material layer; and applying energy to the precursor material layer to volatilize guest molecules. Removing; may include.

[96] For example, a dispersion or ink in which a precursor material is dissolved or a perovskite compound precursor material is applied onto a substrate and then dried to form a precursor layer, followed by removing GM from the precursor layer. The layer can be converted to a perovskite compound layer.

[97] In another embodiment, when the precursor is a solvent compound, organic cationic, metallic cationic and halogen ions according to the stoichiometric ratio of the perovskite compound or perovskite compound are added to the guest molecule (GM) phosphorus solvent. After dissolving to prepare a solution, the prepared solution is applied onto the substrate and the non-solvent is reapplied to the coating film, whereby a precursor layer containing the precursor can be produced.

In this case, the application of the solution, the dispersion or the ink may be screen printing;

Spin coating; Bar coating; Gravure coating; It can be carried out by one or more of the chosen methods in blade coating and roll coating, but it is recommended to be performed with spin coating, given the superior commerciality of processing large areas in a short time.

[99] The energy applied to the precursor layer may include thermal energy, light energy, vibration energy, etc. The amount of energy applied is sufficient to break the bond between the perovskite compound and the GM and to remove the volatilization of the GM. For example, by heating the precursor to more than 100 ^o C, it is possible to convert the perovskite compound precursor to a perovskite compound and, in the case of heating the bulb layer above 130 ° C, in a very short time. The upper limit of the heat treatment for converting the precursor to the perovskite compound may be such that the substrate to form the perovskite compound is not thermally damaged. The heat treatment can be carried out at 100 to 200 ° C. The heat treatment time is sufficient to allow the precursor to be sufficiently converted to perovskite compound, taking into account the heat treatment temperature. A tablet of example, the heat treatment time, but the number of days from 1 minute to ₃₀ minutes, and the invention is not be limited by the heat treatment time is a matter of course.

[100] This is described as a reaction relationship as follows.

[101] Reaction: A + M + 3X + n (GM)-> AM (GM) _n X ₃ (0 <n <number of triplets)-> AMX ₃

[102] Dense perovskite compounds that are difficult to control kinetics of crystallization when crystallized from A + M + 3X-> AMX ₃ by volatilization of A, M, and X solvents in solution There is a problem that it is difficult to form a membrane. In the reaction relationship of precursors according to one embodiment of the present invention, perovskite is not directly formed. It is easy to control perovskite formation kinetics because the perovskite precursor (AM (GM) „X ₃ ) is produced first and then the perovskite is formed by the removal of GM. It is possible to form perovskite films with low surface roughness.

[103] The substrate on which the precursor layer is formed is based on its use, and the basic structure necessary for the operation of electronic devices, optical devices, solar cells, or sensors, etc., and other components (structures) other than the perovskite compound film are already present. It can be a formed substrate.

Hereinafter, the solar cell as an example, the detailed structure and manufacturing method will be described.

The substrate includes a support body substrate; a first electrode positioned on the substrate; and a substrate positioned on the first electrode.

Electron transport;

In other words, the substrate on which the precursor layer is formed is sequentially formed of a substrate, a first electrode, and an electron carrier.

It may include stacked laminates.

The substrate may be a rigid substrate or a flexible substrate. In one embodiment, the substrate may be a rigid substrate or polyethylene comprising a glass substrate.

Terephthalate (PET); polyethylene naphthalate (PEN): polyimide (PI);

Polycarbonate (PC); polypropylene (PP); triacetylsalose (TAC);

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

[108] The first electrode may be a conductive electrode in ohmic contact with the electron carrier.

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

The electrode material may be one or more selected from gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and a combination thereof. In one non-limiting example, the first electrode is transparent. In the case of an electrode, fluorine-containing tin oxide (FTO;

Inorganic conductive electrodes such as Fouorine doped Tin Oxide), Indium doped Tin Oxide (ITO), ZnO, CNT (Carbon Nano-Lube), and Graphene, and organic conductive electrodes such as PEDOT: PSS. When providing a transparent solar cell, it is preferable that the first electrode is a transparent electrode, and when the first electrode is an organic conductive electrode, it is better when providing a flexible solar cell or a transparent solar cell.

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

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

The electron carrier located on the first electrode may be an electron conductive organic material layer or an inorganic material. Electroconductive organics may be organics used as ^η- type semiconductors in conventional organic solar cells. In one specific and non-limiting example, the electroconductive organics are fullerenes (C60, C70, C74, C76, C78, C82). , C95),

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

Fulleren-derivative 'PB I (polybenzimidazole),

It may contain PTCBI (3,4,9,10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ (tetra uorotetracyanoquinodimethane), or a combination thereof. Electroconductive inorganic materials are commonly used in quantum dot-based solar cells or dye-sensitized solar cells. It may be an electron conductive metal oxide used for the transfer. In one embodiment, the electron conductive metal oxide may be an n-type metal oxide semiconductor. Non-limiting example of n-type metal oxide semiconductor, Ti oxide, Ζη oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide, Yr oxide, La One or more selected from oxides, V oxides, A1 oxides, Y oxides, Sc oxides, Sm oxides, Ga oxides, In oxides and SrTi oxides, and their mixtures or composites thereof. Can be.

[111] In its structure, the electron transporter can be either a porous layer or a dense layer.

The electron transporter may be a film of the above-mentioned electron conductive organic material or a dense film (fihn) of the electron conductive inorganic material. The porous electron transporter may be formed of particles of the above-described electron conductive inorganic material. It can be 50 nm to ΙΟμπι, specifically 50 nm to lOOOnm. If the electron carrier is porous, its specific surface area can be 10 to 100 mVg, and the average particle diameter of the metal oxide particles forming the electron carrier can be 5 to 500 nm. The porosity (apparent porosity) of the porous electron transporter can be 30% to 65%, specifically 40% to 60%.

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

The electron transport film may be further equipped. The electron transport film may play a role of transferring electrons simultaneously with the role of preventing the direct contact between the light absorber and the first electrode. The electron transport film may have a porosity on the energy band diagram.

It is acceptable if the electrons are spontaneously movable from the metal oxide to the first electrode through the electron transfer film. In one non-limiting and specific example, the electron transfer film may be a metal oxide thin film, and the metal oxide of the metal oxide thin film may be a metal of the porous metal oxide. The oxide may be the same material as the oxide. In detail, the metal oxide thin film may be formed of Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide. , Yr oxide, La oxide, V oxide, A1 oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, a mixture of these stones, and combinations thereof may be one or more selected materials. Can be substantially greater than lOrnn, more practically between 10 nm and 100 nm, and more substantially between 50 nm and 100 nm. The electron transporter may be formed by application or deposition. Specifically, the electron transporter may be dried by applying a solution in which the electron transporter material is dissolved or a dispersion (or slurry) in which the electron transporter material is dispersed, or selectively heat-treated the dried product. The deposition can be made using physical vapor deposition or chemical vapor deposition.

[114] For example, the porous electron transporter, more specifically, the electron transporter

Slurry containing metal oxide particles may be applied over the first electrode, dried and heat-treated. The coating of the slurry may be carried out by screen printing; Spin coating; Bar coating; Gravure coating; It can be carried out in one or more selected ways in blade coating; and roll coating.

[115] However, it is, of course, possible that the electron carriers can be formed using a method of forming porous electron carriers of metal oxides known in conventional dye-sensitized positive cells or organic solar cells.

Subsequently, as described above on the porous electron transporter of the substrate, a precursor layer is formed and energy is applied to the light absorbing layer of the perovskite compound.

The converting step can be performed.

[117] Fills the pores of the porous electron transporter, forms a precursor layer in the form of a membrane covering the porous electron transporter, converts it into a perovskite compound, fills the pores of the porous electron transporter, and covers the entire surface of the porous electron transporter. A light absorbing layer having a dense membrane structure can be produced, wherein the thickness of the dense membrane is lmn to

May be ΙΟμτ.

Subsequently, the hole transport layer and the second electrode are sequentially disposed on the dense layer of the light absorption layer.

The forming step can be performed.

[119] The hole transport layer is an organic hole transport material, specifically, monomolecular and high molecular organic.

Hole transport material (hole conducting organic material) ^ may be included. Organic hole transport material is a conventional non-conductor based solar cell that uses inorganic J semiconductor quantum dots as dyes.

Any organic hole transport material used may be used. However, polymer organic matters in terms of energy matching and stability with a light absorber, a perovskite compound, may be used.

Good hole transport material.

[12 is a non-limiting example of a monomolecular to small molecule organic hole transport material.

Pentacene, coumarin 6,

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

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

1,2,3,4,8,9,10, 1,15, 16,17, l8,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and One or more of N 3 (cis-di (thiocyanato) -bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) -ruthenium (II)), but is not limited thereto. .

[121] The organic hole transport material is preferably a polymer (hole conducting polymer), which not only ensures stable solar cell operation, but also improves power generation efficiency by energy matching with a light absorber. As the hole conductive polymer, thiophene-based, paraphenylenevinylene-based, carbazole-based and triphenylamine-based materials may be selected.

At least one or more selected from triphenylamines is preferred,

It may be triphenylamine-based. As a non-limiting example of a polymer organic hole transport material,

P3HT (poly [3-hexylthiophene]), MDMO-PPV (poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV (poly [2-methoxy

-5- (2 "-ethylhexyloxy) -p-phenylene vinylene]), P30T (poly (3-octyl thiophene)), POT (poly (octyl thiophene)), P3DT (poly (3-decyl thiophene)), P3DDT ( poly (3-dodecyl thiophene), PPV (poly (p-phenylene vinylene)),

TFB (poly (9,9'-dioctylfluorene-co-N- (4-buty lpheny l) diphenyl amine), Polyaniline, Spiro-MeOTAD ([2,22 ', 7,77'-tetrkis (N, N-di -p-raethoxyphenyl amine) -9,9,9'-spirobi fluorine]), PCPDTBT (Poly [2, 1,3-benzothiadiazole-4,7-diyl [4,4-bis (2-ethylhexyl-4H-cyclopenta)] [2, 1 -b: 3, 4-b '] dithiophene-2,6-diyl]],

Si-PCPDTBT (poly [(4,4 ^, -bis (2-ethylhexyl) dithieno [3,2-b: 2 ', 3'-d] silole) -2,6-diyl-alt- (2, l, 3-benzothiadiazole) -4,7-diyl]), PBDTTPD (poly ((4,8-diethylhexyloxyl)

benzo ([l, 2-b: 4,5-b '] dithiophene) -2,6-diyl) -alt-((5-octylthieno [3,4-c] pyrrole-4,6-dione)-l , 3-diyl)), PFDTBT (poly [2,7- (9- (2-ethylhexyl) -9-hexyl-fluorene) -alt-5,5- (4 ', 7, -di-2-thienyl- 2 ', l', 3'-benzothiadiazole)]),

PFO-DBT (poly [2,7-.9,9- (dioctyl-fluorene) -alt-5,5- (4 ', 7'-di-2-.thienyl-2', 1 ',

3'-benzothiadiazole)]),

PSiFDTBT (poly [(2,7-dioctylsilafluorene) -2,7-diyl-alt- (4,7-bis (2-thienyl) -2, l, 3-benzot hiadiazole) -5,5'-diyl]) ,

PSBTBT (poly [(4,4'-bis (2-ethylhexyt) dithieno [3,2-b: 2 ', 3'-d] silole) -2,6-diyl-alt- (2, l, 3- b enzothiadiazole) -4,7-diyl]), PCDTBT (Poly [[9- (l-octylnonyl) -9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole- 4,7-diyl-2,5-thiophenediyl]),

PFB (poly (9,9'-dioctylfluorene-co-bis (N, N '-(4, butylphen ^ 1,

4-pheny lene) diamine), F8BT (poly (9,9'-dioctylfluorene-co-benzothiadiazole), PEDOT (poly (3,4-ethylenedioxythiophene)), PEDOT: PSS (poly (3,4-ethylenedioxythiophene) poly ( styrenesulfonate)), PTAA (poly (triarylamine)),

Poly (4-butylphenyl-diphenyl-amine) and their copolymers may include one or more selected materials.

[122] As a non-limiting and specific example, the thickness of the hole transport layer may be between l (] nm and 500 mn. ' [123] The hole transport layer may further include additives commonly used to improve properties such as nonconductor-based solar cells or organic solar cells that use conventional non-conductor quantum dots as dyes to improve conductivity of organic-based hole conductive layers. Yes, of course. In one non-limiting example, the hole carriers are tertiary butyl pyridine (TBP), lithium bis (trifluoro methanesulfonyl) imide (LiTFSI), and

One or more additives selected from Tris (2- (lH-pyrazol-l-yl) pyridine) cobalt (III) may further contain additives, and may contain from 0.05 mg to lOOmg additive per lg organic hole transporter. Of course, the present invention can not be limited by the presence or absence of additives in the hole transport layer, the type of additives and the content of the additives.

The second electrode may be used as long as it is a material commonly used as an electrode material of a front electrode or a back electrode in a solar cell. In one non-limiting example, when the second electrode is an electrode material of a back electrode, the second electrode may be used. It may be one or more materials selected from silver, silver, platinum, guaradium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide and combinations thereof. In one non-limiting example, the second electrode may be a transparent electrode. In this case, the second electrode may be made of non-mechanical conductivity such as fluorine-containing tin oxide (FTO), indium doped tin oxide (ITO; It may be an electrode, or an organic conductive electrode such as PEDOT: PSS. If you want to provide a transparent solar cell, a flexible solar cell or transparent solar is required if the second electrode is ¾, which is a transparent electrode, and the second electrode is an organic conductive electrode. Better than when you want to provide a battery.

The second electrode may be formed by using deposition or coating.

It may be formed using physical vapor deposition or chemical vapor deposition, and may be formed by thermal evaporation. The application can be carried out by applying a solution of the electrode material or a dispersion of the electrode material to the substrate, followed by drying or optionally drying the dried film. However, the lower 12 electrodes are used for the front electrode or the back electrode in a conventional solar cell. Of course, it can be formed using the method used to form.

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

According to an embodiment of the present invention, a solar cell includes a substrate and a first electrode positioned on the substrate;

A porous electron transporter positioned on the first electrode; a light absorbing layer comprising a perovskite art compound, which is a dense film covering the pores of the porous electron transporter and covering the porous electron transporter; a hole transporting layer located on the light absorbing layer; and on the hole transporting layer And a second electrode positioned therein, wherein the perovskite compound may be produced by removing the GM of the precursor material.

[128] The dense film of the perovskite compound in the light absorption layer may be lnm to ΙΟμπι.

[129] In the description of the solar cell, the perovskite compound, the hole transporter, the electron transporter, the first electrode, the second electrode, the first substrate, and the second substrate are similar or similar to those described in the foregoing manufacturing method. Therefore, a detailed explanation of this is omitted. [130]

[131] (Comparative Example 1)

[132] Pbl ₂ powder was introduced into a methylsulfoxide (DMSO) solvent and the mixture was stirred at 60 ^° C. for 2 hours.

Agitated to prepare a 0.8 M PbI ₂ -DMSO solution.

After drop-wise, the precipitated powder was collected by filter paper and dried for 1 hour at room temperature.

[133]

[134] (Example 1)

[135] production of perovskite precursors

[136] CH ₃ NH ₃ I (hereinafter referred to as MAI) and Pbl ₂ powder were introduced into a solvent of dimethyl sulfoxide (DMSO) at a stoichiometric ratio of 1: 1, and stirred at 60 ^° C. for 2 hours to give 8 M CH _3. A NH ₃ I-PbI ₂ -DMSO solution was prepared. The solution was dropped-wise in luene, and then the precipitated powder was collected and separated by filter paper and dried at room temperature for 1 hour.

The powder prepared in Comparative Example 1, the precursors MAI, Pbl ₂ and the powder obtained in Example 1 were subjected to X-ray diffraction analysis using Cu Ka rays, which are shown in FIG. 1.

As can be seen in Figure 1, the powder prepared in Example 1 (Pbl ₂ in Figure 1

(MAIXDMSO) does not contain the precursor phases of MAI and Pbl ₂ material. The powder prepared in Comparative Example 1 is PbI ₂ (DMSO) ₂ as reported by H. Miyatnae. Chemistry Lett., 9, 663, 1980). The XRD results of this PbI ₂ (DMSO) _{2 and} the XRD results of the powder prepared in Example 1 showed that the powder obtained in Example 1 was different from the PbI ₂ (DMSO) ₂ phase. In other words, the powder obtained in Example 1 exhibited strong diffraction peaks at diffraction angles 2Θ, 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °. The powder obtained in Example 1 was also found. It can be seen that peaks at 7 to 7.5 °, where 2Θ is 5 to 40 °, have the largest diffraction intensity. The XRD results show that the powder prepared in Example 1 is MAI, Pbl ₂ , PbI ₂ (DMSO). We can see that it is a new compound that is different from the _two phases.

2 shows Fourier transform infrared of the powder prepared in Example 1;

The absorption spectra of each IR are shown and the absorption spectra of the IR show the absorption of S-0, CH, and NH bonds. The powder prepared in Example 1 is MAI and DMSO. Evidence that it does not contain any, also in Figure 2 it can be seen that the absorption by the C = C bond does not occur, which indicates that the leuene is not contained in the powder. XRD and FTIR results show that the powder obtained in Example 1 is a MAI-PbI ₂ -DMSO mixed crystal.

Elemental analysis was performed for accurate composition analysis. As a result, each mass ratio was H = 1.6%, C = 4.6%, N = 2.0%, 0 = 2.2%, and S = 3.7%. Based on this, the mass ratio of the other stations was estimated to be 85.9%. A mixed crystal of CH ₃ NH ₃ I, Pbl ₂ and C 2¾SO (DMSO) was assumed to be 1: 1: 1. 1.7%, C = 5.2%, N = 2.0%, O = 2.3%, S = 4.6%, Pb = 29.7%, I = 54.5%, which is similar to the result of elemental analysis.

Through this, the powder prepared in Example 1 is a crystal formed by the reaction of MAI-PbI ₂ -DMSO in a 1: 1: 1, MAPb (C ₂ H ₆ SO) I ₃ (= C ₃ H ₁₂ NSOPbI ₃ This is an example in which A is MA, M is Pb, GM is DMSO, X is I, and n = l in AM (GM) nX ₃ presented in Formula 2.

[142] Pure perovskite of this MAPb (DMSO) I ₃ perovskite precursor

XRD analysis was performed according to the heat treatment temperature to examine the transition to the phase and this is shown in FIG. 3. XRD analysis was performed in-situ, and the analysis was performed after maintaining for 1 minute for each temperature section shown. Referring to FIG. 3, at room temperature (RT), pure MAPb (DMSO) was similar to the result of FIG. It can be seen that the I ₃ perovskite precursor phase is retained, but as the heat treatment temperature increases, the precursor is converted to the perovskite phase. The XRD spectra at 100 ° C show a weakening of the peaks below the characteristic peak of the precursor, and at the same time a peak near 14 °, a perovskite feature, which is around 100 ^° C. The result shows that L GM is removed by thermal energy and the perovskite precursor is being converted to pure perovskite. At 130 ° C, only pure perovskite diffraction peaks are observed, which is pure perovskite. It tells us that the lobesites were formed, that is, the DMSO that existed as GM was completely eliminated, indicating that pure perovskites were formed.

[143]

[144] (Example 2)

[145] precursor thin film manufacturing

Using the method described in Example 1, but using gamma butyrolactone (GBL) as an additional mixed solvent, a MAI-PbI ₂ -DMSO solution was prepared. That is, the volume ratio of GBL'OMSO was 7: 3 and a solution of 0.8 M concentration was prepared based on MAPbI ₃ .

[147] The prepared MAI-PbI ₂ -DMSO solution (total 1 ml) was collectively applied (injected) at the center of rotation on a fused silica substrate, and spin coating was started at 5000 rpm. After 50 seconds, the non-solvent toluene (lmL) was applied to the center of rotation of the porous electrode in the spin state, and then spun coating was further performed for 5 seconds. and dried for a time. Then, the temperature and 25% of 25 ⁰ C and heat treated at a temperature and pressure conditions of 100 ° C for 30 minutes perovskite compound thin film was formed on the phosphorescent light absorber. in the manufacture of a light absorbing thin film surrounding environment The costume humidity was maintained.

[148]

[149] (Comparative Example ¾

A thin film was prepared in the same manner as in Example 1, except that 100% gamma-butyrolactone (hereinafter, GBL) was used except for DMSO (MAI-PbI ₂ -GBL solution) except for DMSO. [151]

[152] Figure 4 before heat treatment to 100 ^° C in Example 2 (Fig. 4 (a)) and Comparative Example 2 (Fig. 4 (b))

The XRD spectrum of the prepared thin film shows that in Example 2, the precursor material-specific pick was observed in the manufactured thin film, but this pick was not observed when pure GBL was used. It can be seen that a membrane of (DMSO) I ₃ perovskite precursor was formed.

FIG. 5 is a scanning electron micrograph of the perovskite membrane after heat treatment in Example 2 (FIG. 5 (a)) and Comparative Example 2 (FIG. 5 (b)). According to the relationship, the perovskite compound was formed through the precursor phase, and in Comparative Example 2, the perovskite compound was directly formed in the solution. As shown in FIG. 5, the perovskite membrane was formed in the precursor thin film. It can be seen that the perovskite compound is formed in the form of a dense and perfect film when converted to.

[154]

[155] (Example 3)

[156] fabrication of porous Ti0 ₂ thin film substrates

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

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

[158] A 50 nm thick ΤΪ02 dense film was prepared by spray pyrolysis on a cut and partially etched FTO substrate. The spray pyrolysis was performed using a TAA (Titanium acetylacetonate): EtOH (l: 9 v / v) solution. The thickness was adjusted by repeating the method of spraying for 3 seconds and stopping for 10 seconds on the FTO substrate on the hot plate maintained at 450 ° C.

[159] Ethyl cellulose (ethyl cellulose) in 50 nm Ti0 ₂ powder (prepared with an aqueous solution of titanium peroxocomplex dissolved in 1% by weight on a Ti02 basis at 250 ° C for 12 hours). after the 10% by weight with ethyl selreul dissolved in ethyl alcohol, the sum of the agarose solution, a common by adding 5 ml per Ti0 ₂ powder lg, adding the hotel pinol (terpinol) 5 g per 1 g Ti0 ₂ powder, ethyl alcohol Ti0 ₂ paste was prepared by distillation under reduced pressure.

[160] Added Ti0 ₂ powder paste ethanol (l (Ti0 ₂ powder

Paste) weight ratio of 3 (ethanol)) to prepare a 1 ^ 0 ₂ slurry for spin coating. On a Ti0 ₂ thin film on a FTO substrate, spin coated with 100 rpm using a spin coating Ti0 ₂ slurry, followed by heat treatment at 500 ° C for 60 minutes, and then immersing the heat treated substrate in a 30 mM T1C14 aqueous solution at 60 ° C. After leaving for 30 minutes, washed and dried with deionized water and ethanol, and then heat treated at 500 ° C. for 30 minutes to prepare a 300 nm porous Ti0 ₂ thin film (porous electron transporter). The surface area was 33 m ² / g and the porosity (apparent porosity) was 50%.

In Example 2, the fused silica is manufactured and replaced by a porous electron transporter. A light absorbing layer of the perovskite compound was prepared on the electron transporter in the same manner as in Example 2. Thereafter, leuene dissolved in PTAA (poly (triarylamine), EM index, Mw = 17,500 g / mol) above the light absorbing layer was prepared. A hole transport layer was formed by spin coating the solution [15 mg (PTAA) / lmL] at 3000 rpm for 60 seconds, in which 2.31 mg of Lithium Bis (Trifluoro methanesulfonyl) Imide (LiTFSI) and 6.28 mg of TBP (PTB) were added to the PTAA solution. tertiary butyl pyridine) was then added to the upper part of the hole transport layer by vacuum evaporation of Au using a thermal evaporator of high vacuum (less than 5xlO- ⁶ torr), whereby Au electrode (second electrode) having a thickness of 70 nm was formed. To form a solar cell.

[162]

[163] (Comparative Example 3)

A solar cell was manufactured in the same manner as in Example 3, but a fused silica was prepared in Comparative Example 2. A perovskite compound was prepared in the same manner as in Comparative Example 2 on the porous electron carrier. A light absorbing layer was prepared.

[165] The solar cell prepared in Example 3 and Comparative Example 3 was prepared using AM 1.5 (100 mA / cm ² ).

The photoelectric conversion characteristics were measured under the conditions, and the results are shown in Table 1. The perovskite compound film prepared in Example 3 had a dense thin film covering 100% of the upper surface of the electron transporter. In this case, it was an incomplete film that could not cover the upper surface of the electron transporter to 100%. Thus, in Example 3, it showed better Jsc, Voc, and FF values and excellent photoelectric conversion efficiency.

[Table 1] Performance index of the solar cell manufactured in Example 3 and Comparative Example 3

As described above, the present invention has been described in terms of specific matters and limited embodiments and drawings, but the present invention is provided only to help general understanding of the present invention, and the present invention is not limited to the above embodiments. In the field of the present invention, those with ordinary knowledge can make various modifications and variations from these materials.

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

[170]

Claims

[Claim 1] A precursor of a non-organic hybrid perovskite compound containing organic cation, metal cation, halogen anion, and guest molecule (GM).

[Claim 2] In paragraph 1,

The precursor material is a precursor material in which diffraction peaks are detected at diffraction angles 2Θ of 6.2 to 6.8 ⁰ , 7 to 7.5 ^ᄋ , and 8.9 to 9.5° in X-ray diffraction measurement using Cu-Koc rays.

[Claim 3] In paragraph 1,

The guest molecule is a precursor that is a solvent that dissolves the inorganic/organic hybrid perovskite compound.

[Claim 4] In clause 3,

The precursor material is a solvate between a non-organic hybrid perovskite compound and a solvent.

[Claim 5] In paragraph 3,

The guest molecule is a solvent precursor containing one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bromine, and iodine.

[Claim 6] In paragraph 3,

The guest molecule is

Ν,Ν-Dimethylacetamid,

1,4-dioxane, diethylamine, ethyl acetate, tetrahydrofuran, pyridine, methanol, ethanol,

dichlorobenzene, glycerin,

Dimethyl sulfoxide (DMSO) and

One or more precursors selected from Ν,Ν-dimethylformamide (DMF).

[Claim 7] In paragraph 3,

The precursor material satisfies the following formula (1).

(Formula 1)

AM( _GM ) _n

(A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion, M is a divalent metal ion, )

[Claim 8] In clause 7,

In ^the _above formula ( ¹ ⁾ _, It is an ion, and y is a real number precursor with 0<y<l.

[Claim 9] In paragraph 1,

The precursor material is a precursor material for solar cell light absorber.

[Claim 10] A dispersion containing the precursor according to any one of claims 1 to 9.

[Claim 11] A method of manufacturing a solar cell light absorber using the precursor material of any one of claims 1 to 9.

[Claim 12] In clause 11,

Forming a precursor material layer by applying or depositing the precursor material on the substrate; and

Applying energy to the precursor layer to volatilize and remove guest molecules;

Method for manufacturing a solar cell light absorber comprising.