KR102162548B1 - Hybrid Solar Cell with Improved Stability and Efficiency and the Fabrication Method Thereof - Google Patents

Abstract

The method of manufacturing a perovskite solar cell according to the present invention comprises the steps of: a) forming a chalcogenide of a trivalent metal on an electron carrier; b) forming the compound of the trivalent metal-chalcogen-halogen by contacting the chalcogenide with a halide of a trivalent metal and heat treatment; And c) contacting the compound with an organic halide to form a light absorber according to Formula 1.
(Chemical Formula 1)
AM(Chal)(Hal) ₂
In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- one in It is a halogen ion selected above.

Description

Hybrid Solar Cell with Improved Stability and Efficiency and the Fabrication Method Thereof}

The present invention relates to a hybrid solar cell having a light absorber including a compound having a perovskite structure and a method for manufacturing the same, and in detail, a perovskite solar cell having high stability and high efficiency without containing lead And it relates to a manufacturing method thereof.

Organometallic halide perovskite compound of perovskite structure is composed of organic cation (A), metal cation (M), and halogen anion (X), and is represented by the formula of AMX ₃ .

Currently, perovskite solar cells using organic/inorganic organometallic halides as light absorbers are the closest to commercialization among next-generation solar cells including dye-sensitized and organic solar cells, and an efficiency of up to 20% is reported (Korea Patent Publication No. 2014). -0035284), and interest in perovskite solar cells is increasing more and more.

Such a perovskite solar cell has an efficiency comparable to that of a silicon solar cell, has a very low material cost, and is excellent in commerciality because a low-temperature process or a low-cost solution process is possible. However, despite the excellent initial photoelectric conversion efficiency of the perovskite solar cell, it contains lead, which limits its practical use, and at the same time, the stability against heat and moisture is poor, and thus has improved stability for practical commercialization. Yet, there is a need for technology development for lead-free perovskite solar cells that do not use lead.

Republic of Korea Patent Publication No. 2014-0035284

An object of the present invention is to provide a perovskite solar cell that does not contain lead and has excellent stability against heat or moisture.

Another object of the present invention is to provide a method of manufacturing a perovskite solar cell that does not contain lead and has excellent stability against heat or moisture through a solution process having excellent commerciality.

The method of manufacturing a perovskite solar cell according to the present invention comprises the steps of: a) forming a chalcogenide of a trivalent metal on an electron carrier; b) forming the compound of the trivalent metal-chalcogen-halogen by contacting the chalcogenide with a halide of a trivalent metal and heat treatment; And c) contacting the compound with an organic halide to form a light absorber according to Formula 1.

(Chemical Formula 1)

AM(Chal)(Hal) ₂

In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- one in It is a halogen ion selected above.

In the method of manufacturing a perovskite solar cell according to an embodiment of the present invention, the trivalent metals are Sb, Bi, Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, One or two or more of V and Ti may be selected.

In the method of manufacturing a perovskite solar cell according to an embodiment of the present invention, the trivalent metal may be Sb, Bi, or Sb and Bi.

In the method of manufacturing a perovskite solar cell according to an exemplary embodiment of the present invention, step a) may be performed using a chemical bath deposition (CBD) method.

In the method of manufacturing a perovskite solar cell according to an embodiment of the present invention, the contact in step b) may be performed by applying a first solution in which a halide is dissolved.

In the method of manufacturing a perovskite solar cell according to an embodiment of the present invention, the application and heat treatment of the first solution are performed as a unit process, and the unit process may be repeatedly performed.

In the method for manufacturing a perovskite solar cell according to an embodiment of the present invention, the heat treatment may be performed at a temperature of 130 to 180°C.

The method of manufacturing a perovskite solar cell according to an embodiment of the present invention may further include removing a halide of an unreacted trivalent metal after step b) and before step c).

The method of manufacturing a perovskite solar cell according to an embodiment of the present invention may further include, after step c), d) forming an organic hole transporter.

In the method for manufacturing a perovskite solar cell according to an embodiment of the present invention, the organic hole transporter is one or two or more selected from thiophene, paraphenylene vinylene, carbazole and triphenylamine. Achieving polymers may be included.

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

The perovskite solar cell according to the present invention includes a light absorber according to Formula 1 below.

(Chemical Formula 1)

AM(Chal)(Hal) ₂

In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- one in It is a halogen ion selected above

In the perovskite solar cell according to an embodiment of the present invention, the trivalent metal ion of Formula 1 may be Sb, Bi, or Sb and Bi.

The perovskite solar cell according to the present invention does not contain lead and has remarkably excellent light stability, oxygen and moisture stability, and thermal stability.

The method of manufacturing a perovskite solar cell according to the present invention does not contain lead through a simple solution application and low temperature heat treatment, and a perovskite solar cell having remarkably excellent light stability, oxygen and moisture stability, and thermal stability. There is an advantage that can be manufactured.

Figure 1 (a) is a schematic diagram showing the most stable crystal structure of MASbSI ₂ derived using DFT (density functional theory) calculation, Figure 1 (b) is a simulated X-ray from the crystal structure of Figure 1 (a) A view showing a diffraction pattern (shown as a simulation) and an X-ray diffraction pattern (shown as an experience) of methylammoniumantimonysulfuriodide (MASbSI ₂ ) prepared in Example 1, and FIG. 1(c) is a MASbSI ₂ prepared in Example 1 Is a high-magnification transmission electron microscope observation photograph of, and FIG. 1(d) is a tau plot derived from the ultraviolet-visible (UV-Vis) absorption spectrum (inserted in FIG. 1(d)) of MASbSI ₂ prepared in Example 1 ( Tauc plot).
2 is a diagram showing an energy band diagram between the electron transport layers TiO ₂ and MASbSI ₂ and the hole transport layer PCPDTBT by measuring the energy level of MASbSI ₂ prepared in Example 1 using ultraviolet photoelectron spectroscopy (UPS) to be.
FIG. 3(a) is a scanning electron micrograph of observing the surface after forming MASbSI ₂ on the porous electron transport layer in Example 1, and FIG. 3(b) is a cross-sectional view of the solar cell manufactured in Example 1. The observed scanning electron micrograph, FIG. 3(c) is a diagram showing the current density-voltage curve of the solar cell manufactured in Example 1, and FIG. 3(d) is the AM1 of the solar cell manufactured in Example 1 It is a diagram showing an EQE (external quantum efficiency) spectrum under the .5G standard irradiation condition (100mW/cm ² ).
4 shows the solar cell manufactured in Example 1 was left under 60% relative humidity (room temperature condition), and short-circuit current density and photoelectric conversion efficiency (FIG. 4(a)) and open-circuit voltage and fill factor ( 4(b)) is a diagram showing values normalized to the initial (right after manufacturing) short-circuit current density, photoelectric conversion efficiency, open-circuit voltage, and fill factor, and FIG. 4(c) shows UV Under the standard irradiation conditions of AM 1.5G including irradiation (100mW/cm ² ) and a bias near the maximum power (0.49V), the short-circuit current density and photoelectricity of the solar cell manufactured in Example 1 according to light irradiation time It is a diagram showing the conversion efficiency, and FIG. 4(d) is a photoelectric conversion efficiency standardized by initial efficiency according to time when the solar cell manufactured in Example 1 was left in the dark at 80° C. and 40% relative humidity in the air. It is a diagram showing.
5 is a view showing a current density-voltage graph of the solar cell manufactured in Example 2.

Hereinafter, a perovskite solar cell of the present invention and a method of manufacturing the same will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

The applicant of the present invention has conducted a long-term in-depth study to develop a perovskite solar cell that does not contain lead and is stable from external factors such as heat and moisture, and perovskite compounds (organometallic halides of perovskite structure It was noted that the underlying cause of thermal, chemical (moisture, oxygen, etc.), optically unstable, is due to the weak binding force of halogen ions. Accordingly, research on replacing a divalent metal represented by Pb with a trivalent metal capable of satisfying the charge neutral condition was continuously conducted while introducing a chalcogen ion that provides a strong binding force compared to a halogen anion. The present invention has been completed by developing a chalcogenated lead-free perovskite compound that is thermally, chemically and optically stable and has a small energy bandgap and is more advantageous in absorbing sunlight.

In the present invention, a perovskite solar cell refers to a solar cell containing a perovskite compound as a light absorber, and the perovskite compound has a perovskite structure, organic cation (A), metal cation ( M) and an anion (X), based on a compound satisfying the formula of AMX ₃ , may mean a compound in which a chalcogen anion and a halogen anion are located at the site of X (anion) of MX ₆ octahedron.

The method of manufacturing a perovskite solar cell according to the present invention comprises the steps of: a) forming a chalcogenide of a trivalent metal on an electron carrier; b) forming the compound of the trivalent metal-chalcogen-halogen by contacting the chalcogenide with a halide of a trivalent metal and heat treatment; And c) contacting the compound with an organic halide to form a light absorber according to Formula 1.

(Chemical Formula 1)

AM(Chal)(Hal) ₂

(In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- in Is one or more selected halogen ions)

That is, the manufacturing method according to the present invention uses a chalcogenide of a trivalent metal as a chalcogen source, and reacts the chalcogenide of the trivalent metal with a halide of the trivalent metal to form a trivalent metal-chalcogen-halogen. After conversion to a compound, a compound of a trivalent metal-chalcogen-halogen and an organohalide are reacted to convert the light absorber according to Formula 1. By using a chalcogenide of a trivalent metal as a source of a chalcogen ion, through which it is converted into a compound of a trivalent metal-chalcogen-halogen, and then converted into a compound of Formula 1, chemically A compound of formula 1 can be prepared that is well defined, satisfies electrical neutrality, prevents the formation of unwanted abnormalities, and stably has a perovskite structure. In addition, through the above-described source of chalcogenide, a chalcogenide of a trivalent metal, conversion of a trivalent metal-chalcogen-halogen to a compound and conversion to a compound of Formula 1, low-temperature heat treatment of less than 200°C And using a simple solution application, the compound of Formula 1 may be prepared.

Since the compound of Formula 1 is based on a trivalent metal, that is, a perovskite compound containing only a trivalent metal as a metal ion, it is possible to manufacture a lead-free perovskite solar cell that does not contain Pb.

In addition, the compound of Formula 1 may have remarkably improved thermal, chemical and optical stability as the chalcogen ions having a very strong ionic binding force relative to the halogen ions form the compound in a ratio of 1 mole to 2 moles of the halogen ions.

The trivalent metal may be one or more selected from Sb, Bi, Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V, and Ti, but is not limited thereto.

Specifically, the trivalent metal (hereinafter, Mc) of the chalcogenide of the trivalent metal in step a) and the trivalent metal (hereinafter, Mh) of the halide of the trivalent metal are independently of each other Sb, Bi, Al, Ga , In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V and Ti may be selected from one or more than one.

In addition, Mc in step a) and Mh in step b) may be the same trivalent metal, or may be different trivalent metals. At this time, the case where Mc and Mh are different from each other includes not only the case where M1, which is a trivalent metal, and M2, which is another trivalent metal, which is different from M1, is Mh, as well as the case where M1 is Mc and Mh is M1 and M2. . In addition, by controlling the relative molar ratio of M1 and M2 in M1 and Mh of Mc, it is possible to control the molar ratio of M1 and M2 contained in Formula 1 to be finally prepared. As described above, a perovskite compound containing two or more trivalent metal ions in Formula 1 in a designed content ratio can be easily prepared through different Mh and Mc.

As described above, the trivalent metal may be one or more selected from Sb, Bi, Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V, and Ti, but, As antimony or bismuth chalcogenides such as Sb ₂ S ₃ , Sb ₂ Se ₃ , Bi ₂ S ₃ and Bi ₂ Se ₃ have appropriate band gap, high absorption efficiency, air/moisture stability and environmentally friendly properties, the chemical formula When M of 1 is Sb, Bi, or Sb and Bi, it is environmentally friendly, and at the same time, it is advantageous because it can have excellent thermal, chemical (including reaction with air or moisture) and optical (decomposition by photocatalyst) stability. Furthermore, when M in Formula 1 is Sb or Sb and Bi, it is advantageous because it can have significantly improved photoelectric conversion efficiency than any other trivalent metal combination, and when M is Sb and Bi, it is more than 50% than when M is Sb. It is more advantageous because it can have improved photoelectric conversion efficiency. When M includes both Sb and Bi, Formula 1 may be expressed as ASb _1-x Bi _x (Chal)(Hal) ₂ , where 0<x<1 is a real number.

Step a) the application of a dispersion of trivalent metal chalcogenide nanoparticles; Spray pyrolysis method (SPM); Chemical solution growth method (CBD; chemical bath deposition method); And a continuous chemical reaction method (SILAR; Successive Ionic Layer Adsorption and Reaction method); it may be performed by one or more selected methods. However, it is possible to form a trivalent metal chalcogenide that is in surface contact with the electron transporter and is strongly bound to the electron transporter, and even if the electron transporter is porous, the trivalent metal chalcogenide is uniformly formed on the outer surface and inner pores. To be able to do so, step a) is preferably performed by a method selected from one or more of the chemical bath deposition method (CBD) and the successive ionic layer adsorption and reaction method (SILAR). Further, when using the chemical solution growth method (CBD; chemical bath deposition method), when the electron carrier is porous, trivalent metal chalcogenide can be formed very uniformly over the entire area of the electron carrier compared to SILAR. It is more advantageous because trivalent metal chalcogenide can be formed even in the form of a layer covering the surface of the carrier (including the surface by pores).

As is known, in the case of SILAR, a precursor solution is prepared by dissolving a precursor of each element constituting a trivalent metal chalcogenide for each precursor, and then the electron transporter is alternately immersed for each precursor solution, and then the washing process is repeated. Trivalent metal chalcogenide can be formed. For example, when the trivalent metal chalcogenide is an antimony chalcogenide, Sb ₂ O ₃ , a precursor of Sb, is dissolved in a complex forming agent such as tartaric acid, and Na ₂ S ₂ O ₃ is a precursor of S. Sb ₂ S ₃ can be formed in the electron transporter using the used SILAR.

As is known, in the case of CBD, a precursor solution is prepared by dissolving a precursor of each element constituting a trivalent metal chalcogenide for each precursor, and then a mixed solution is prepared by mixing each precursor solution, and an electron transporter is added to the mixed solution. By impregnation, a trivalent metal chalcogenide can be prepared. At this time, it goes without saying that the trivalent metal chalcogenide can be formed on the electron transporter in the form of particles or layers by controlling the precursor concentration of the mixed solution or the impregnation time in the mixed solution. As a precursor used for CBD, chloride, iodide, fluoride, nitride, organic or inorganic may be used.For example, when the trivalent metal chalcogenide is an antimony chalcogenide, the precursor of Sb is a chloride of Sb. The precursor of S may be a sulfur-containing organic material or a sulfur-containing inorganic material, specifically Na ₂ S ₂ O ₃ , and the like, and the CBD temperature may be performed at 10° C. or less, specifically 3 to 10° C., but the present It goes without saying that the invention cannot be limited by the specific synthesis conditions of the trivalent metal chalcogenide known in the field of inorganic semiconductor-sensitized solar cells.

a) 3 the knife kojen product of metal to be formed in the step may satisfy the general formula of M ₂ (Chal) _3, M in _{M 2 (Chal) 3 (Mc} ) is Sb, Bi, Al, Ga, In, Tl , Sc, Y, La, Ce, Fe, Ru, Cr, V and Ti may be one or more selected from, and M ₂ (Chal) ₃ in Chal may be selected from S and Se one or more. In an advantageous example, the trivalent metal chalcogenide (trivalent metal chalcogenide) formed in step a) is Bi ₂ S ₃ , Bi ₂ Se ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , or It can be a mixture.

The trivalent metal chalcogenide formed in step a) may be in the form of particles having an average diameter of 0.5 nm to 10 nm or a film having a thickness of 0.5 nm to 20 nm.

Step b) may include a step of heat-treating and contacting a trivalent metal halide with an electron transporter in which the trivalent metal chalcogenide is formed.

In detail, the contact in step b) is easy to process and allows cost reduction, and furthermore, when the electron transport body is porous, the trivalent metal can be made homogeneous contact with the trivalent metal chalcogenide formed on the electron transport body. It is preferable to carry out by application of a solution (first solution) in which the halide of is dissolved.

3 is a halide of the metal can satisfy the formula M (Hal) _3, In this case, M (Hal) M (Mh ) of ₃ from _{M 2 (Chal) 3 M (} Mc) and independently, Sb, Bi , Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V and Ti may be selected one or more than one, hal of M (Hal) ₃ in I, Br and Cl More than one can be selected. In an advantageous example, the trivalent metal halide (trivalent metal halide) may be BiI ₃ , BiBr ₃ , BiCl ₃ , SbI ₃ , SbBr ₃ , SbCl _3, or a mixture thereof.

The concentration of the trivalent metal halide in the first solution may be 0.01 to 0.2M, but the present invention is not limited thereto, and the solvent of the first solution may be any polar organic solvent in which the metal halide is dissolved, specific examples , The solvent of the first solution is gamma-butyrolactone, formamide, dimethylformamide, diformamide, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, diethylene glycol, 1-methyl-2-pyrroli Don, N,N-dimethylacetamide, acetone, α-terpineol, β-terpineol, dihydro terpineol, 2-methoxy ethanol, acetylacetone, methanol, ethanol, propanol, ketone, methyl iso One or two or more may be selected from butyl ketone, etc., but is not limited thereto.

The application of the first solution may be any method commonly used for liquid or dispersion application.As a specific example, the application of the first solution is dip coating, spray coating, spin coating, bar coating, blade coating, comma coating, roll Coating, casting, screen printing, inkjet printing, electrostatic hydraulic printing, micro contact printing, imprinting, gravure printing, reverse offset printing, or gravure offset printing, etc., but are not limited thereto.

Heat treatment with M ₂ (Chal) ₃ M(Hal) ₃ is M(Chal)(Hal) (where M is Mc and Mh, Chal is one or more chalcogens selected from S and Se, and Hal is one or more halogen selected from I, Br, and Cl) ) Can be carried out at a temperature that can be converted to. Specifically, the heat treatment may be performed at a temperature of 130 to 180°C, more specifically 140 to 160°C. At this time, it goes without saying that the heat treatment may be performed in an inert gas atmosphere such as argon, helium, or nitrogen. The heat treatment time is M ₂ (Chal) ₃ + M(Hal) ₃ → M(Chal)(Hal) reaction can be completed in any degree. As a practical example, heat treatment may be performed for 30 seconds to 5 minutes, but the present invention is limited by the heat treatment time. Of course it cannot be.

In order to convert all trivalent metal chalcogenides formed on the electron transporter into a trivalent metal-chalcogen-halogen compound, that is, M(Chal)(Hal), the application and heat treatment of the above-described first solution are performed in one unit process. As a result, the unit process may be repeatedly performed. As a specific example, the unit process may be repeated 2 to 5 times, but it goes without saying that the present invention cannot be limited by the number of repetitions of the unit process.

After step b) is performed, a step of removing the halide of the unreacted trivalent metal, which is an unreacted residue, may be further performed. The removal of the unreacted residue can be performed by dissolving and removing the unreacted trivalent metal halide using a solvent that dissolves the halide of the trivalent metal, specifically, the solvent of the first solution described above.

After converting the trivalent metal chalcogenide to a compound of trivalent metal-chalcogen-halogen through step b), the trivalent metal-chalcogenide is brought into contact with the compound of the trivalent metal-chalcogen-halogen and the organic halide to Step c) of converting the halogen compound to the compound according to Formula 1 may be performed. At this time, for a more rapid and uniform conversion, an annealing may be further performed in step c). That is, step c) may include converting a compound of a trivalent metal-chalcogen-halogen into a compound according to Formula 1 by contacting and annealing a compound of a trivalent metal-chalcogen-halogen and an organic halide. .

The organic halide may mean a compound of a monovalent organic cation (A) and a halogen anion (Hal), and specifically, may satisfy the formula A (Hal). In Formula A (Hal), A is a monovalent cation, A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidium ion, and Hal is at least one in I, Br and Cl It may be a halogen of choice.

In terms of having a bandgap advantageous for solar absorption, the organic ammonium ion is represented by the formula of (R ₁ -NH ₃ ⁺ ) (R ₁ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl) or (R ₂ -C ₃ H ₃ N ₂ ⁺ -R ₃ ) (R ₂ is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, R ₃ is hydrogen or C1-C24 alkyl) It may satisfy the formula of. As a non-limiting and specific example, R ₁ may be C1-C24 alkyl, preferably C1-C7 alkyl, more preferably methyl. R ₂ may be C1-C24 alkyl and R ₃ may be hydrogen or C1-C24 alkyl, preferably R ₂ may be C1-C7 alkyl and R ₃ may be hydrogen or C1-C7 alkyl, More preferably R ₂ may be methyl and R ₃ may be hydrogen.

The amidinium ion is formamidinium (NH ₂ CH=NH ₂ ⁺ ) ion, acetamidinium (NH ₂ C(CH ₃ )=NH ₂ ⁺ ) or guamidinium (NH ₂ C(NH ₂ )=NH ₂ ⁺ ), but is not limited thereto.

The contact in step c) is easy to process and allows cost reduction, and furthermore, when the electron transporter is porous, the organic halogen is capable of homogeneous contact with the compound of the trivalent metal-chalcogen-halogen formed on the electron transporter. It is preferably carried out by application of a solution in which the cargo is dissolved (second solution).

The concentration of the organic halide in the second solution may be 0.01 to 1 M, but the present invention is not limited thereto, and the solvent of the second solution may be any organic solvent in which the organic halide is dissolved. In a specific example, the solvent of the second solution is t-butyl-alcohol (tert-Butyl Alcohol), 2-butanol (2-Butanol), isobutyl alcohol (Isobutyl alcohol), 1-butanol (1-Butanol), 2-propanol One or more solvents selected from (2-Propanol), 1-propanol, ethanol, and methanol may be used, but the present invention is not limited thereto.

The application of the second solution may also be a method commonly used for application of a liquid or dispersion phase.As a specific example, the application of the second solution is independent of the application of the first solution, dip coating, spray coating, spin coating, Bar coating, blade coating, comma coating, roll coating, casting, screen printing, inkjet printing, electrostatic hydraulic printing, micro contact printing, imprinting, gravure printing, reverse offset printing or gravure offset printing, etc. It is not limited. In addition, it goes without saying that the application of the second solution may be repeatedly performed so that all of the compounds of the trivalent metal-chalcogen-halogen formed on the electron transporter can be converted to the compound according to Formula 1.

As described above, for a more rapid and uniform reaction, annealing may be further performed after the contact between the trivalent metal-chalcogen-halogen compound and the organohalide is made by application of the second solution, and the annealing temperature is Although it may be a low temperature of 200° C. or less, specifically 100 to 200° C., it goes without saying that the present invention cannot be limited by whether or not annealing is performed or the annealing temperature. In addition, for complete conversion of the trivalent metal-chalcogen-halogen compound, the application and annealing of the second solution may be performed as a unit process, and the corresponding unit process may be repeatedly performed. As a specific example, the unit process may be repeated 2 to 5 times, but it goes without saying that the present invention cannot be limited by the number of repetitions of the unit process.

After step c) is performed, a step of removing unreacted organohalide, which is an unreacted residue of step c), may be further performed. The removal of the unreacted organic halide may be performed by dissolving and removing the unreacted organic halide using a solvent that dissolves the organic halide, specifically, a solvent of the second solution described above.

After step c), step d), which is a step of forming an organic hole transporter over the electron transporter on which the light absorber, which is a compound according to Formula 1, is formed may be further performed.

Step d) may be performed by applying and drying a solution containing an organic hole transport material (hereinafter, a hole transport solution) to cover the top of the electron transport body. The application of the hole transport solution may be any method commonly used for liquid or dispersion application, and specific examples include dip coating, spray coating, spin coating, bar coating, blade coating, comma coating, roll coating, casting, screen printing. , Inkjet printing, electrostatic hydraulic printing, micro contact printing, imprinting, gravure printing, reverse offset printing, or gravure offset printing, but are not limited thereto. The thickness of the hole transport layer formed by applying the hole transport solution may be 10 to 500 nm, but is not limited thereto.

The solvent of the hole transport solution may be a solvent in which an organic hole transport material is dissolved and does not chemically react with the compound of Formula 1. For example, the solvent of the hole transport solution may be a non-polar solvent, and as a practical example, toluene, chloroform, chlorobenzene, dichlorobenzene, anisole, xyl It may be any one or two or more selected from ren (xylene) and a hydrocarbon-based solvent having 6 to 14 carbon atoms.

The organic hole transport material of the hole transport solution may be a single molecule or a high molecular organic hole transport material, and in terms of excellent energy matching and durability with the light absorber, which is a compound according to Formula 1, thiophene, paraphenylene vinylene, carba It is preferable that it is a hole-transporting polymer selected from one or two or more sol-based and triphenylamine-based.

One non-limiting example of a single- or low-molecular organic hole transport material, such as pentacene, coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), zinc phthalocyanine (ZnPC), CuPC (copper phthalocyanine), TiOPC (titanium oxide phthalocyanine), Spiro-MeOTAD(2,2',7,7'-tetrakis(N,Np-dimethoxyphenylamino)-9,9'-spirobifluorene), F16CuPC(copper(II) 1 ,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine), Boron subphthalocyanine chloride (SubPc) and N3 (cis -di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)) may be mentioned, but the material is not limited thereto.

One example of a hole transporting polymer selected from one or two or more of thiophene-based, paraphenylenevinylene-based, carbazole-based, and triphenylamine-based polymers, 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]), P3OT(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-butylphenyl)diphenyl amine), Polyaniline, Spiro-MeOTAD ([2,22′,7,77′-tetrkis (N,N-di -p-methoxyphenyl amine)-9,9,9'-spirobi fluorine]), PCPDTBT(Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-B; 3,4-B'] dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]), Si-PCPDTBT(poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2 -b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl ) benzo([1,2-b:4,5-b']dithiophene)-2,6-diyl)-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)- 1,3-diyl)), PFDTBT(poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene )-alt-5,5-(4', 7, -di-2-thienyl-2',1', 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)-2,1,3-benzothiadiazole)-5,5′-diyl]), PSBTBT(poly[(4,4′- bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]) , PCDTBT(Poly [[9-(1-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,butylphenyl))bis(N,N′-phenyl-1,4-phenylene)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 one or two or more selected materials from their copolymers.

The electron transporter may be an electron conductive metal oxide used for electron transfer in a conventional quantum dot-based solar cell, a dye-sensitized solar cell, or a perovskite solar cell. As a specific example, the electron conductive metal oxide is 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. , Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide and SrTi oxide, one or more selected materials may be mentioned, but the present invention is not limited thereto. The electron transporter may be a dense film or a laminated film of a dense film and a porous film. When the electron transport body is a laminated film, the porous film may be a porous film made of particles of the electron conductive inorganic material described above. When the electron transporter includes a porous membrane, the specific surface area of the porous membrane may be 10 to 100 m ² /g, and the average particle diameter of the metal oxide particles forming the porous membrane may be 5 to 500 nm, but is limited thereto. It is not. In the case where the electron transporter is a laminated film of a dense film and a porous film, the electronic conductive metal oxide of the dense film and the electronic conductive metal oxide of the porous film may be of the same kind or different kinds of materials, and the thickness of the dense film is 10 nm or more. Substantially 10nm to 100nm, and more substantially 50nm to 100nm, the thickness of the porous film may be 50nm to 2㎛, substantially 100nm to 1.5 ㎛, more substantially 500 ㎚ to 1.5 ㎛, but must be It is not limited.

The method of manufacturing a solar cell according to an embodiment of the present invention may further include a) before step, forming an electron carrier on the first electrode; and after step c) or after step d), the second electrode Forming a; may include. In addition, when the electron transport layer is a laminated film, the forming of the electron transport body may include forming an electron transport film that is a dense film on the first electrode; And forming a porous electron transporter on the electron transport film.

Specifically, the electron transport layer, which is a dense layer, may be manufactured by forming a dense metal oxide layer (electron conductive metal oxide layer) through a vapor deposition process such as physical vapor deposition or chemical vapor deposition. The porous electron transporter may be prepared by applying a slurry containing electron conductive metal oxide particles on the dense metal oxide film, and drying and heat treatment of the applied slurry layer. Slurry application can be selected from screen printing, spin coating, bar coating, gravure coating, blade coating and roll coating. It may be performed in any one or two or more methods, but is not limited thereto. The heat treatment may be performed at 200 to 600° C. in air, but is not limited thereto.

The first electrode may be a transparent conductive electrode that is ohmic-bonded with the electron transport layer. As a specific example, the transparent conductive electrode is fluorine-containing tin oxide (FTO; Fluorine-doped Tin Oxide), indium-containing tin oxide (ITO; Indium-doped Tin Oxide), ZnO, carbon nanotube, graphene, and It may be any one or two or more selected from these composites, but is not limited thereto.

At this time, of course, a transparent substrate (support) that is a rigid substrate (support) or a flexible substrate (support) may be positioned under the first electrode. It may be a phthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetylcellulose (TAC), or polyethersulfone (PES) substrate, etc. It is not limited.

The second electrode may be a material selected from gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and a composite thereof, but is not limited thereto. It is sufficient if the second electrode is formed through a conventional metal deposition method used in a semiconductor process. For example, the second electrode may be formed through a vapor deposition process such as physical vapor deposition or chemical vapor deposition, and specifically, may be formed by thermal vapor deposition.

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

The perovskite solar cell according to the present invention includes a light absorber according to Formula 1.

(Chemical Formula 1)

AM(Chal)(Hal) ₂

In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- one in It is a halogen ion selected above. In Chemical Formula 1, it is advantageous that Chal is S ^2- which can further improve the stability of the solar cell by stronger ionic binding force.

In Formula 1, M may be one or more selected from Sb, Bi, Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V and Ti, and advantageously Sb, Bi Or it may be Sb and Bi. When M in Formula 1 contains both Sb and Bi, Formula 1 may be expressed as ASb _1-x Bi _x (Chal)(Hal) ₂ , where 0<x<1 is a real number.

Specifically, a solar cell according to an embodiment of the present invention includes a first electrode; An electron transport body positioned on the first electrode; A light absorber of Formula 1 positioned on the electron transporter; An organic hole transporter positioned on the electron transporter having light absorption; And a second electrode positioned on the organic hole transporter.

The light absorber may be in the form of particles that are dispersedly bound to the surface of the electron transporter (including the surface by pores), or in the form of a layer covering the surface of the electron transporter (including the surface by pores). The average diameter may be 0.5 nm to 10 nm, and the layered light absorber may have a thickness of 0.5 nm to 20 nm.

In the above description of the perovskite solar cell according to the present invention, the material, structure, shape, or size of the first electrode, electron transporter, organic hole transporter, and second electrode may be determined by manufacturing the perovskite solar cell described above. According to the same or similar method, the perovskite solar cell according to the present invention includes all the contents described above in the manufacturing method of the perovskite solar cell.

(Example 1)

After cutting a glass substrate (FTO; F-doped SnO ₂ , 8 ohms/sq, Pilkington, hereinafter FTO substrate) coated with fluorine-containing tin oxide (first electrode) into a size of 25 x 25 mm, etching the tip FTO was partially removed.

On the cut and partially etched FTO substrate, a TiO ₂ thin film with a thickness of about 50 nm was prepared as an electron transfer film by spray pyrolysis. Spray pyrolysis was performed using a TAA (Titanium acetylacetonate):EtOH (1:9v/v%) solution, and sprayed for 3 seconds on the FTO substrate placed on a hot plate maintained at 450°C and stopped for 10 seconds. The thickness was adjusted with.

TiO ₂ powder with an average particle size of 50 nm (prepared by hydrothermal treatment of a titanium perocomplex aqueous solution in which 1% by weight of TiO ₂ is dissolved at 250° C. for 12 hours), ethyl cellulose in ethyl alcohol at 10% by weight. 5ml was added per 1g of dissolved ethyl cellulose solution TiO _2, and mixing the Termini pinol (terpinol) was added 5 g per 1 g TiO ₂ and then, by removing the ethanol by distillation under reduced pressure to prepare a TiO ₂ powder paste.

On the TiO ₂ thin film of the substrate, the prepared TiO ₂ powder paste was coated by screen printing and heat-treated at 500° C. for 30 minutes, and then the heat-treated substrate was immersed in 20 mM TiCl ₄ aqueous solution and left for about 12 hours, and then deionized water Washed with ethanol, dried, and then heat-treated at 500° C. for 30 minutes to prepare a porous electron transport layer having a thickness of about 1 μm.

The first precursor solution dissolved by adding 0.65 g of SbCl ₃ (Junsei) to 2.5 mL of acetone and the second precursor solution dissolved 3.95 g of Na ₂ S ₂ O ₃ (Aldrich) in 25 mL of ion-exchanged water were mixed to prepare a mixed solution. The substrate on which the porous electron transport layer was formed was impregnated in the prepared mixed solution, and the Sb ₂ S ₃ coated on the porous electron transport layer was applied through the chemical solution growth method (CBD) in which it was left for 1.5 hours at a temperature of 10°C. A coating layer (about 10-20 nm thick) was formed.

A first solution in which SbI ₃ was dissolved in N, N-dimethylformamide (DMF) at a concentration of 0.1 M on the Sb ₂ S ₃ coating layer was spin-coated at 1000-2000 rpm for 60 seconds and then at 150° C. for 2 minutes in an Ar gas atmosphere. Heat treatment was performed to form an SbSI layer. The conversion from Sb ₂ S ₃ to SbSI was confirmed by a color change from dark brown to dark red. Thereafter, the remaining SbI ₃ was removed by ultrasonic cleaning in a DMF solution.

Thereafter, a second solution in which methyl ammonium iodide (MAI, MA = methyl ammonium) was dissolved in 2-propanol (IPA) at a concentration of 0.4 M on the SbSI layer was spin-coated at 1000-2000 rpm for 30 seconds, and then in an Ar gas atmosphere. Annealing at 150° C. for 5 minutes to form a MASbSI ₂ layer, and ultrasonic cleaning in a 2-propanol solution to remove residual MAI.

PCPDTBT(Poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-B;3,4-B'] dithiophene)-alt-4,7(2,1 ,3-benzothiadiazole)]) solution (10mg/mL) was used as a hole transport solution and spin-coated on MASbSI ₂ to form an organic hole transport layer, and PEDOT: PSS (poly(3,4-ethylenedioxythiophene) on the organic hole transport layer) ) poly(styrenesulfonate)) solution was applied to form an interface modification layer, and then 100 nm of Au was thermally evaporated to form a second electrode to prepare a solar cell.

Figure 1 (a) is a schematic diagram showing the most stable crystal structure of MASbSI ₂ derived using DFT (density functional theory) calculation, Figure 1 (b) is a simulated X-ray from the crystal structure of Figure 1 (a) X- ray diffraction pattern of the MASbSI ₂ prepared in (shown by simulation) and example 1 is a diagram showing a diffraction pattern (shown by the experiment), Figure 1 (c) is a high-power transmission of the MASbSI ₂ prepared in example 1 An electron microscope observation photograph, and FIG. 1(d) is a tauc plot derived from an ultraviolet-visible light (UV-Vis) absorption spectrum (inserted in FIG. 1(d)) of MASbSI ₂ prepared in Example 1 It is a diagram showing.

From Fig. 1(a), it can be seen that the most stable crystal structure is a structure in which sulfur is distributed along the Z axis of the octahedral unit, and the Sb-S bond is a longer bond (about 3.6 Å) and a shorter It is separated by a bond (about 2.27 Å), and it can be seen that the Sb-I bond length is about 3.16 Å.

As shown in Fig. 1(b), when comparing the diffraction pattern of the perovskite structure derived through DFT calculation and the diffraction pattern of the actually manufactured MASbSI _2, the ordering of the sulfur atom is slightly different and the diffraction peak However, it can be seen that the diffraction pattern of the perovskite structure derived through the DFT calculation and the diffraction pattern of the MASbSI ₂ prepared in Example are well matched. It can be seen that the well-crystallized MASbSI ₂ is prepared through the observation result of the transmission electron microscope of FIG. 1(c), which is consistent with the X-ray diffraction result of FIG.

1(d), which is a tau plot obtained using the UV-Vis absorption spectrum, it can be seen that the band gap of MASbSI ₂ prepared in Example 1 is 2.09 eV, and the absorption edge is about 600 nm. In addition, the material structure of MASbSI ₂ prepared in Example 1 was also confirmed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX) spectroscopy.

2 is a diagram showing an energy band diagram between the electron transport layers TiO ₂ and MASbSI ₂ and the hole transport layer PCPDTBT by measuring the energy level of MASbSI ₂ prepared in Example 1 using ultraviolet photoelectron spectroscopy (UPS) to be. As shown in FIG. 2, the conduction band minimum energy level (CBM) and valence band maximum energy level of MASbS _I 2 were 3.41 eV and 5.60 eV, respectively. As can be seen from FIG. 2, the energy level of MASbSI ₂ is in good agreement with the CBM of TiO ₂ and the highest occupied molecular orbital (HOMO) of PCPDTBT, and it can be seen that it can be effectively operated as a solar cell.

FIG. 3(a) is a scanning electron micrograph of observing the surface after forming MASbSI ₂ on the porous electron transport layer in Example 1, and FIG. 3(b) is a cross-sectional view of the solar cell manufactured in Example 1. The observed scanning electron micrograph, FIG. 3(c) is a diagram showing the current density-voltage curve of the solar cell manufactured in Example 1, and FIG. 3(d) is the AM1 of the solar cell manufactured in Example 1 It is a diagram showing an EQE (external quantum efficiency) spectrum under the .5G standard irradiation condition (100mW/cm ² ).

Through the scanning electron microscope observation of Figure 3 (a), MASbSI ₂ formed around the porous TiO ₂ of the structure can be understood substantially as it is maintained even after the MASbSI ₂ is formed, through which MASbSI ₂ the inside (the open pores of the porous TiO ₂ It can be seen that it is formed effectively on the surface). In addition, through the cross-sectional observation photograph of FIG. 3(b), it was confirmed that the hole transport material stably penetrated into the porous electron transporter (TiO ₂ ) in which MASbSI ₂ was formed and filled the inside of the porous electron transporter. In addition, through the linear EDX analysis results and the EDX mapping analysis results in the solid yellow line and the yellow dotted rectangle (randomly selected) of FIG. 3(b), it is shown that MASbSI ₂ is uniformly distributed throughout the porous electron carrier (TiO ₂ ). Confirmed.

3(c) is a current density-voltage graph of the solar cell manufactured in Example 1 under AM1.5G standard irradiation conditions (100mW/cm ² ), with a short-circuit current density (J _sc ) of 8.13mAcm ^-2 , open-circuit voltage It can be seen that (V _OC ) is 0.65V, the fill factor (FF) is 58.9%, and the photoelectric conversion efficiency (PCE) is 3.11%.

Looking at Fig. 3(d) showing the EQE spectrum of 300nm-600nm, the EQE spectrum of MASbSI ₂ agrees well with the absorption spectrum inserted in Fig. 1(d), and 600-850nm due to absorption of the hole transport material PCPDTBT. It can be seen that the EQE spectrum of the region appears.

Moisture, heat, and light stability of the solar cell prepared in Example 1 were tested.

4 shows the solar cell manufactured in Example 1 was left under 60% relative humidity (room temperature condition), and short-circuit current density and photoelectric conversion efficiency (FIG. 4(a)) and open-circuit voltage and fill factor ( 4(b)) is a diagram showing values normalized to the initial (right after manufacturing) short-circuit current density, photoelectric conversion efficiency, open-circuit voltage, and fill factor, and FIG. 4(c) shows UV Under the standard irradiation conditions of AM 1.5G including irradiation (100mW/cm ² ) and a bias near the maximum power (0.49V), the short-circuit current density and photoelectricity of the solar cell manufactured in Example 1 according to light irradiation time It is a diagram showing the conversion efficiency, and FIG. 4(d) is a photoelectric conversion efficiency standardized by initial efficiency according to time when the solar cell manufactured in Example 1 was left in the dark at 80° C. and 40% relative humidity in the air. It is a diagram showing.

As can be seen in Figs. 4(a) and 4(b), the solar cell equipped with MASbSI ₂ as a light absorber maintained at least 90% of the initial photoelectric conversion efficiency for 15 days. It can be seen that both factors remain very stable.

In addition, as can be seen from FIG. 4(c), after the initial increase in photoelectric conversion efficiency and short-circuit current density, it can be seen that the photoelectric conversion efficiency and short-circuit current density are maintained very stably.

In addition, through FIG. 4(d), it can be seen that 91% of the initial photoelectric conversion efficiency is maintained even when left for 30 days.

From the results of FIG. 4, it can be seen that the lead-free MASbSI _2- based solar cell has remarkably superior moisture stability, light stability, oxygen stability, and thermal stability compared to the conventional Pb and halogen-based perovskite solar cells. .

(Example 2)

In Example 1, instead of the DMF solution in which SbI3 was dissolved as the first solution, a solution in which BiI3 was dissolved in DMF at a concentration of 0.05M was used, and as the second solution, a solution in which MAI was dissolved in IPA at a concentration of 0.5M was used. A solar cell was manufactured in the same manner as in Example 1, except that a solution in which MAI was dissolved in IPA was used as a concentration.

5 is a view showing a current density-voltage graph of the solar cell manufactured in Example 2 under AM1.5G standard irradiation conditions (100mW/cm ² ). The manufactured solar cell has a short-circuit current density (Jsc) of 14.18mAcm ^-2 , open-circuit voltage (V _OC ) is 0.62V, fill factor (FF) is 59.0%, and photoelectric conversion efficiency (PCE) is 5.2%.

As described above, the present invention has been described by specific matters and limited embodiments and drawings, but this is provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is Those of ordinary skill in the relevant field can make various modifications and variations from this description.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later fall within the scope of the spirit of the present invention. .

Claims (12)

a) forming a chalcogenide of a trivalent metal on the electron transporter;
b) forming a compound of a trivalent metal-chalcogen-halogen by applying and heat treating a first solution in which a halide of a trivalent metal is dissolved on the chalcogenide; And
c) forming a light absorber according to Formula 1 by applying and annealing a second solution in which an organic halide is dissolved in the compound;
A method of manufacturing a perovskite solar cell comprising a.
(Chemical Formula 1)
AM(Chal)(Hal) ₂
(In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- in Is one or more selected halogen ions) The method of claim 1,
The trivalent metal is one or two or more selected from Sb, Bi, Al, Ga, In, Tl, Sc, Y, La, Ce, Fe, Ru, Cr, V, and Ti method for manufacturing a perovskite solar cell . The method of claim 2,
The method of manufacturing a perovskite solar cell wherein the trivalent metal is Sb, Bi, or Sb and Bi. The method of claim 1,
The step a) is a method of manufacturing a perovskite solar cell performed using a chemical solution growth method (CBD). delete The method of claim 1,
A method of manufacturing a perovskite solar cell in which the application and heat treatment of the first solution are performed as a unit process, and the unit process is repeatedly performed. The method of claim 6,
The heat treatment is performed at a temperature of 130 to 180 ℃ method of manufacturing a perovskite solar cell. The method of claim 1,
After step b) and before step c), a method of manufacturing a perovskite solar cell in which the step of removing the halide of the unreacted trivalent metal is further performed. The method of claim 1,
After the step c), d) forming an organic hole transporter; method of manufacturing a perovskite solar cell further comprising. The method of claim 9,
The organic hole transporter is a method of manufacturing a perovskite solar cell comprising one or two or more hole transport polymers selected from thiophene-based, paraphenylenevinylene-based, carbazole-based, and triphenylamine-based. A perovskite solar cell comprising a light absorber according to Formula 1.
(Chemical Formula 1)
AM(Chal)(Hal) ₂
(In formula 1, A is an organic cation monovalent, M is a trivalent metal ion, Chal is a knife kojen ion selected from one or more of S and Se ^{2- 2-,} Hal is I ^-, Br ^- and Cl ^- in Is one or more selected halogen ions) The method of claim 11,
The trivalent metal ion of Formula 1 is Sb, Bi, or Sb and Bi perovskite solar cell.

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