KR102647777B1 - Method for manufacturing perovskites photovoltaic cell, perovskites photovoltaic cell manufactured therefrom, and solar cell comprising the same - Google Patents

Abstract

The present invention relates to a photoelectric conversion device, and more specifically, to a method of manufacturing a perovskite photoelectric conversion device, a perovskite photoelectric conversion device manufactured thereby, and a solar cell including the same.

Description

Method for manufacturing perovskite photoelectric conversion elements, perovskite photoelectric conversion elements manufactured thereby, and solar cells comprising the same

The present invention relates to a photoelectric conversion device, and more specifically, to a method of manufacturing a perovskite photoelectric conversion device, a perovskite photoelectric conversion device manufactured thereby, and a solar cell including the same.

A solar cell converts solar energy into electrical energy and generates electrical energy using the photovoltaic effect that absorbs solar energy and generates electrons and holes.

Various methods have been proposed for such solar cells, and among them, solar cells using perovskite material, known as a material with the same crystal structure as calcium titanium oxide (CaTiO ₃ ), as a light absorption layer are receiving attention. .

Perovskite solar cells are a third-generation solar cell that combines silicon wafer-based technology and thin-film technology. Compared to other types of solar cells, they have characteristics such as high absorption coefficient, variable band gap, and rapid growth. In addition, perovskite solar cells are superior to silicon solar cells in terms of price, rigidity, weight, and efficiency.

Meanwhile, perovskite provided in solar cells generally has a three-dimensional crystal structure, and perovskite with this crystal structure is used as a light absorption layer. In addition, solar cells generally have a structure in which an electron transport layer and a hole transport layer are arranged on both sides of a perovskite light absorption layer with a three-dimensional crystal structure.

The electron transport layer and the hole transport layer are made of organic or inorganic materials, and metal oxides are widely used as an example of the inorganic material. However, due to the lack of compatibility between the two materials, the interface between the electron transport layer or hole transport layer, which is a metal oxide, and the perovskite light absorption layer with a three-dimensional crystal structure, the entire surface of the metal oxide layer is a perovskite layer with a three-dimensional crystal structure. There is a problem of surface coverage in the manufacturing process that does not completely cover this, poor interface characteristics, and separation easily occurs at the interface, ultimately reducing the efficiency and durability of the solar cell.

Registered Patent Publication No. 10-1561284

The present invention was developed to solve the above problems, and is a perovskite photoelectric conversion layer designed to have better photoelectric conversion efficiency and durability by improving the interface characteristics between the perovskite light absorption layer and the hole transport layer and/or electron transport layer. The purpose is to provide a device manufacturing method and a perovskite photoelectric conversion device manufactured using the same.

Another object of the present invention is to provide a solar cell using the perovskite photoelectric conversion device according to the present invention, which is designed to have excellent photoelectric conversion efficiency and durability.

In order to solve the above-described problem, the present invention includes the following steps: (1) forming an electron transport layer or hole transport layer, which is a first metal oxide layer, on a first electrode; (2) the first metal oxide layer is represented by the following formula (1) forming a first multi-functional layer having a perovskite having a two-dimensional crystal structure by processing a solution containing a compound, (3) processing a perovskite precursor solution on the first multi-functional layer forming a light absorption layer including perovskite with a three-dimensional crystal structure, (4) forming a hole transport layer or an electron transport layer on the light absorption layer, and (5) forming a light absorption layer on the hole transport layer or electron transport layer. A method for manufacturing a perovskite photoelectric conversion device including the step of forming two electrodes is provided.

[Formula 1]

[AB][X]

Here, [AB] is a monovalent organic cation, X is a monovalent anion,

A is -PO(OH) ₂ , -CO(OH), or -Si(OH) ₂ , and B is -(R ₁ R ₂ R ₃ R ₄ N) or -(R ₇ R ₈ N=CH-NR ₉ R ₁₀ ), where R ₁ is C1 to C20. or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₅ R ₆ , where R ₅ is C1 to C20 substituted or unsubstituted alkylene, or C6 to C20 substituted or unsubstituted arylene. and R ₆ is C6 to C20 substituted or unsubstituted arylene, or C1 to C20 substituted or unsubstituted alkylene, and R ₂ , R ₃ and R ₄ are each independently hydrogen or C1 to C20 substituted or unsubstituted Ring alkylene, C6 to C20 substituted or unsubstituted arylene, and R ₇ is C1 to C20 substituted or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₁₁ R ₁₂ , where R ₁₁ is C1 to C20 substituted or unsubstituted alkylene, or C6 to C20 substituted or unsubstituted arylene, and R ₁₂ is C6 to C20 substituted or unsubstituted arylene, or C1 to C20 substituted or unsubstituted alkyl. ren, R ₈ , R ₉ and R ₁₀ are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl, and X is one of I ^- , Br ^- , Cl ^- and F ^- Either the halogen anion or the SCN ^- anion.

According to one embodiment of the present invention, when treating a solution containing the compound represented by Formula 1 in step (2), the compound represented by Formula 1 may be adsorbed to the first metal oxide layer.

Additionally, the perovskite having the three-dimensional crystal structure may be a compound represented by the following formula (2).

[Formula 2]

[L][M][N] ₃

Here, L is a monovalent organic cation , a monovalent metal cation, or a mixture thereof, M is a divalent metal cation, and N is at least one anion.

In addition, between steps (3) and (4), forming a perovskite layer with a two-dimensional crystal structure to remove surface defects of the perovskite with a three-dimensional crystal structure and forming a passivation layer. Any one or more steps may be further included.

In addition, the present invention is provided with a first electrode, an electron transport layer or hole transport layer that is a first metal oxide layer formed on the first electrode, and a perovskite having a two-dimensional crystal structure formed on the first metal oxide layer. A first multi-functional layer, a light absorption layer having a perovskite with a three-dimensional crystal structure formed on the first multi-functional layer, a hole transport layer or electron transport layer formed on the light absorption layer, and on the hole transport layer or electron transport layer. It includes a formed second electrode, and the wavelength range from the second wavelength, which is the shortest wavelength at which photoluminescence (PL) occurs, to the first wavelength is based on the first wavelength with the maximum intensity in the photoluminescence (PL) spectrum for each wavelength. Provided is a perovskite photoelectric conversion element formed to be larger than the wavelength range from the third wavelength, which is the longest wavelength at which photoluminescence occurs, to the first wavelength.

According to one embodiment of the present invention, the wavelength range from the second wavelength to the first wavelength may have a wider wavelength range exceeding 60% of the wavelength range from the third wavelength to the first wavelength.

In addition, the present invention is provided with a first electrode, an electron transport layer or hole transport layer that is a first metal oxide layer formed on the first electrode, and a perovskite having a two-dimensional crystal structure formed on the first metal oxide layer. A first multifunctional layer, a light absorption layer having a perovskite with a three-dimensional crystal structure formed on the first multifunctional layer, a hole transport layer or electron transport layer formed on the light absorption layer, and a hole transport layer or electron transport layer formed on the hole transport layer or electron transport layer. A perovskite photoelectric conversion device including a second electrode and generating photoluminescence at a wavelength of 600 nm is provided.

According to one embodiment of the present invention, the perovskite having the three-dimensional crystal structure may be a perovskite that emits photoluminescence at a wavelength of 400 to 600 nm.

Additionally, the perovskite having the two-dimensional crystal structure may be adsorbed on the first metal oxide layer.

In addition, the first metal oxide layer is a metal containing one type of metal selected from the group consisting of Ni, V, Mo, Cu, Ti, Sn, Zn, Nb, Ta, W, In, Ga, Nd, Pb, and Cd. It may contain oxides or at least two types of metal oxides.

In addition, a perovskite layer having a two-dimensional crystal structure may be further provided on the light absorption layer to remove surface defects of the perovskite having a three-dimensional crystal structure.

Additionally, the present invention provides a perovskite solar cell including a perovskite photoelectric conversion device according to the present invention.

Additionally, the present invention provides a silicon-perovskite tandem solar cell including a silicon photoelectric conversion element and a perovskite photoelectric conversion element according to the present invention disposed on the silicon photoelectric conversion element.

The method of manufacturing a perovskite photovoltaic device according to the present invention implements a perovskite layered structure that is difficult to manufacture through a solution process, and through this, a hole transport layer or electron layer formed of a metal oxide adjacent to the perovskite light absorption layer. As the interface properties between transport layers are improved, a photoelectric conversion device with excellent photoelectric conversion efficiency and long-term stability can be implemented. In addition, compared to photoelectric conversion devices using a perovskite light absorption layer with a conventional three-dimensional crystal structure, it is possible to implement a photoelectric conversion device with a wider bandgap toward short wavelengths, so it can be widely applied to solar cells.

1 and 2 are cross-sectional schematic diagrams of a perovskite photoelectric conversion device according to an embodiment of the present invention.
Figures 3 and 4 are cross-sectional schematic diagrams of a silicon-perovskite tandem solar cell according to an embodiment of the present invention.
Figures 5 and 6 show the light absorption spectrum and PL spectrum by wavelength of the perovskite photoelectric conversion device according to Example 1 and Comparative Example 1.
Figure 7 is a schematic diagram expressing the bidentate or tridentate bond between the electron transport layer or hole transport layer, which is the first metal oxide layer, and the anchoring group of the compound represented by Formula 1 in the perovskite photoelectric conversion device according to an embodiment of the present invention. .
Figure 8 is an example spectrum for explaining the maximum intensity, first wavelength, second wavelength, and third wavelength in the PL spectrum.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein.

Referring to FIG. 1, the perovskite photoelectric conversion device 100 according to an embodiment of the present invention includes a first electrode 10 and a first metal oxide layer formed on the first electrode 10. An electron transport layer or hole transport layer 20, a first multi-functional layer 30 having a perovskite with a two-dimensional crystal structure formed on the first metal oxide layer, and a first multi-functional layer 30 formed on the first multi-functional layer 30. A light absorption layer 40 having a perovskite having a three-dimensional crystal structure, a hole transport layer or electron transport layer 50 formed on the light absorption layer 40, and a hole transport layer or electron transport layer 50 formed on the hole transport layer or electron transport layer 50. It is implemented including a second electrode 60.

The perovskite photoelectric conversion device 100 having this structure is formed through the following manufacturing method, but is not limited thereto.

The perovskite photoelectric conversion device 100 according to an embodiment of the present invention includes the steps of (1) forming an electron transport layer or hole transport layer 20, which is a first metal oxide layer, on the first electrode 10, ( 2) forming a first multi-functional layer 30 having a perovskite with a two-dimensional crystal structure by treating the first metal oxide layer with a solution containing a compound represented by the following formula (1), ( 3) forming a light absorption layer 40 including perovskite having a three-dimensional crystal structure by processing a perovskite precursor solution on the first multi-functional layer 30, (4) the light absorption layer (40) forming a hole transport layer or electron transport layer 50 on the hole transport layer, and (5) forming a second electrode 60 on the hole transport layer or electron transport layer 50. .

First, in step (1) of the present invention, a step of forming an electron transport layer or a hole transport layer 20, which is a first metal oxide layer, is performed on the first electrode 10.

The first electrode 10 can be used without limitation in the case of a transparent electrode commonly used in solar cells. As non-limiting examples, ITO (Induim Tin Oxide), FTO (Fluorine doped Tin Oxide), ATO (Sb ₂ O ₃ doped Tin Oxide), GTO (Gallium doped Tin Oxide), ZTO (tin doped zinc oxide), ZTO: may include gallium doped ZTO (Ga), indium gallium zinc oxide (IGZO), indium doped zinc oxide (IZO), and/or aluminum doped zinc oxide (AZO). The thickness, length, and width of the first electrode may be the thickness, length, and width of a typical transparent electrode used in a solar cell, and the present invention is not particularly limited thereto.

The first electrode 10 may be formed on a substrate. The substrate serves as a support and may be a rigid or flexible substrate. In addition, the substrate may be a known substrate used in the art, and examples thereof include transparent plastic made of materials such as polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, aromatic polyester, or polyimide. A substrate, glass substrate, quartz substrate, silicon substrate, etc. can be used. The thickness of the substrate may be that of a typical substrate used in solar cells, and the present invention is not particularly limited thereto.

An electron transport layer or hole transport layer 20, which is a first metal oxide layer, is formed on the first electrode 10, and when the first metal oxide layer is the electron transport layer 20, it is provided on the light absorption layer 40 to be described later. The layer is the hole transport layer 50, and when the first metal oxide layer is the hole transport layer 20, the layer provided on the light absorption layer 40 is the electron transport layer 50.

The first metal oxide layer may include a known metal oxide layer used as a hole transport layer or an electron transport layer. As an example of this, in the case of a hole transport layer, the first metal oxide layer may include a metal oxide containing one type of metal selected from the group consisting of Ni, V, Cu, and Mo, or at least two types of these metal oxides.

Or, in the case of an electron transport layer, the first metal oxide layer is a metal oxide containing one type of metal selected from the group consisting of Ti, Sn, Zn, Nb, Ta, W, In, Ga, Nd, Pb, and Cd, or at least two types. may include oxides of these metals.

The first metal oxide layer may be formed by a conventional method, for example, through deposition or heat treatment after processing a paste containing metal oxide nanoparticles on the first electrode. At this time, the method of processing the paste on the first electrode may be a conventional coating method, for example, any one of spin coating, dip coating, and spray coating. It could be a way.

The thickness of the first metal oxide layer may vary depending on the material of the first metal oxide layer and whether the first metal oxide layer is a hole transport layer or an electron transport layer, and the present invention is not particularly limited thereto.

Next, in step (2) according to the present invention, the first metal oxide layer is treated with a solution containing a compound represented by the following formula (1) to form a first multi-functional layer having a perovskite with a two-dimensional crystal structure. The step of forming (30) is performed.

In the case of a typical perovskite photoelectric conversion device, it is common to form a perovskite layer with a three-dimensional crystal structure, which is a light absorption layer, after step (1) described above. The perovskite layer having the three-dimensional crystal structure is formed by treating it with a solution containing a perovskite precursor. In this case, if the surface treated with the solution is a metal oxide, the solution forms the metal oxide layer as desired. Due to insufficient surface coverage or poor interface characteristics between the formed perovskite layer and the metal oxide layer, the efficiency of the solar cell is reduced and/or separation easily occurs at the interface, which ultimately affects the efficiency, long-term stability, and durability of the solar cell. There is a problem with this deterioration.

In order to prevent this, the present invention forms a first multi-functional layer 30, which is a perovskite layer with a two-dimensional crystal structure, on a hole transport layer or an electron transport layer, which is a metal oxide layer, and through this, the metal oxide layer and the light absorption layer, Fe. By increasing the interfacial properties and interfacial connectivity between loskite layers, durability and long-term stability can be improved, and improved photoelectric conversion efficiency can be achieved.

This will be explained with reference to FIGS. 5 and 6. As can be seen in FIG. 5, the photoelectric conversion element of Example 1 is provided with a first multi-functional layer and the photoelectric conversion element of Comparative Example 1 is not provided with a first multi-functional layer. It can be seen that the light absorption area is almost the same between the two. However, as shown in Figure 6, depending on the presence or absence of the first multi-functional layer, the photoelectric conversion device of Example 1 has the effect of increasing the band gap of the light absorption layer compared to the photoelectric conversion device of Comparative Example 1, and specifically, the photoelectric conversion device of Example 1 It can be seen that the device generates photoluminescence even at a wavelength of 600 nm, but the photoelectric conversion device of Comparative Example 1 has a photoluminescence wavelength exceeding 650 nm. In addition, the photoelectric conversion device of Example 1 exhibits superior solar cell efficiency compared to the photoelectric conversion device of Comparative Example 1 (see Table 1), which is achieved by combining the first metal oxide layer and the three-dimensional crystal structure through the first multi-functional layer. This is the result of improved interfacial properties and interfacial connectivity between perovskites.

Meanwhile, the first multi-functional layer 30 is a perovskite having a two-dimensional crystal structure, and a light absorption layer 40 having a perovskite having a three-dimensional crystal structure is provided on the first multi-functional layer 30. This layered structure is difficult to manufacture using manufacturing methods known in the art. In other words, both perovskite with a two-dimensional crystal structure and perovskite with a three-dimensional crystal structure are manufactured through a solution process in which a solution containing a precursor material capable of forming the perovskite is treated, 3 As the solvent used to produce perovskite with a two-dimensional crystal structure dissolves the perovskite with a two-dimensional crystal structure, a perovskite layer with a three-dimensional crystal structure has been conventionally used on a perovskite layer with a two-dimensional crystal structure. Perovskite could not be formed, and it was either a mixture of perovskite with a two-dimensional crystal structure in a single layer and perovskite with a three-dimensional crystal structure, or on perovskite with a three-dimensional crystal structure. Only a structure in which perovskites with a two-dimensional crystal structure were layered could be implemented. However, the inventor of the present invention claims that it is possible to process a precursor solution for forming a perovskite with a three-dimensional crystal structure on a perovskite with a two-dimensional crystal structure formed from a solution containing a compound represented by the following formula (1). 1 A perovskite with a two-dimensional crystal structure is formed without dissolving due to adsorption through bidentate or tridentate cross-linking between the metal component of the metal oxide layer and the 'A' portion, which is the anchoring group of the compound represented by the following formula (1). It was found that perovskite with a three-dimensional crystal structure can be stably formed on the top of the layer, and that this can improve the interfacial characteristics and interfacial connectivity between the metal oxide layer and the perovskite with a three-dimensional crystal structure. This led to the present invention.

[Formula 1]

[AB][X]

Here, [AB] is a monovalent organic cation, and X is a monovalent anion. Here, A is PO(OH) ₂ , -CO(OH), or -Si(OH) ₂ , and B is -(R ₁ R ₂ R ₃ R ₄ N) or -(R ₇ R ₈ N=CH-NR ₉ R ₁₀ ), where R ₁ is C1 to C20. or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₅ R ₆ , where R ₅ is C1 to C20 substituted or unsubstituted alkylene, or C6 to C20 substituted or unsubstituted arylene. and R ₂ , R ₃ , and R ₄ are each independently hydrogen or a C1 to C20 substituted or unsubstituted alkylene, a C6 to C20 substituted or unsubstituted arylene, and R ₆ is a C6 to C20 substituted or unsubstituted alkylene. Arylene, or C1 to C20 substituted or unsubstituted alkylene, and R ₇ is C1 to C20 substituted or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₁₁ R ₁₂ , where R ₁₁ is C1 to C20 substituted or unsubstituted alkylene, or C6 to C20 substituted or unsubstituted arylene, and R ₁₂ is C6 to C20 substituted or unsubstituted arylene, or C1 to C20 substituted or unsubstituted alkyl. and R ₈ , R ₉ and R ₁₀ are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl. Here, the substituted alkylene (or alkyl) or substituted arylene (or allyl) that can be used as R ₁ to R ₁₂ may have a known substituent used in perovskite photoelectric conversion devices, so the present invention relates to this. Detailed explanations are omitted.

Additionally, in the compound represented by Formula 1, X is any one of I ^- , Br ^- , Cl ^- and F ^- halogen anion or SCN ^- anion.

In the compound represented by Formula 1, the anchoring group, which is part A, induces bidentate bridging, hydrogen bonding including bidentate bridging, or tridentate binding with the metal component of the metal oxide layer, forming a two-dimensional crystal structure. By allowing the perovskite to be adsorbed on the metal oxide layer, the interfacial characteristics and interfacial connectivity between the metal oxide layer and the perovskite with a three-dimensional crystal structure can be improved (see FIG. 7). Meanwhile, aliphatic polyhydric alcohols as anchoring groups can also be adsorbed to the metal oxide layer, but are easily desorbed, so it may be difficult to improve the interface characteristics and interfacial connectivity between the metal oxide layer and the perovskite with a three-dimensional crystal structure.

Since the compound represented by the above-mentioned formula 1 can be synthesized by various methods using known organic reactions, the present invention is not particularly limited thereto. As an example of this, if the compound represented by Formula 1 is 4-phosphonobenzenaminium iodide, hydroiodic acid (HI) and ethanol are added to 4-aminopropylphosphonic acid as shown in the reaction formula below. After mixing, the mixture is stirred for 30 minutes to 3 hours, and after the reaction is completed, ether is added and the resulting organic precipitate is filtered.

[Reaction formula]

Meanwhile, the solution containing the compound represented by the above-described formula 1 can be used without limitation in any known solvent capable of dissolving the compound represented by formula 1, for example, isopropyl alcohol, ethanol, and THF (Tetrahydrofuran). And one or more organic solvents selected from the group consisting of chlorobenzene may be used.

A method of treating the first metal oxide layer with a solution containing the compound represented by Formula 1 can use a known coating method, for example, spin coating and spray coating.

After treating the first metal oxide layer with a solution containing the compound represented by Formula 1, perovskite with a two-dimensional crystal structure can be realized through heat treatment. In this case, the heat treatment is, for example, at a temperature of 70 to 130 ° C. It can be performed for 5 to 60 minutes.

The thickness of the first multi-functional layer 30 including perovskite having an implemented two-dimensional crystal structure may be 1 nm to 100 nm, which may be more advantageous in achieving the purpose of the present invention.

Next, in step (3) according to the present invention, a perovskite precursor solution is processed on the first multi-functional layer 30 to form a light absorption layer 40 having a perovskite with a three-dimensional crystal structure. Follow the steps as instructed.

The perovskite provided in the light absorption layer 40 is a general perovskite applied to the light absorption layer of solar cells, and may be a perovskite with a three-dimensional crystal structure. For example, it is a compound represented by the following formula 2: It may contain a perovskite material.

[Formula 2]

[L][M][N] ₃

Here, L may be a monovalent organic cation, a monovalent metal cation, or a mixture of these, and specifically includes amines, ammonium, Group 1 metals, Group 2 metals, and/or other cations or cation-like compounds. It can be done, for example, formamidinium (FA), methylammonium (MA. methylammonium), FAMA, CsFAMA or (R ₁₃ R ₁₄ R ₁₅ R ₁₆ N) ⁺ (where, R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a C1 to C5 linear alkyl group, a C3 to C5 branched alkyl group, a phenyl group, an alkylphenyl group, an alkoxyphenyl group or an alkyl halide.), (Rb _0.05 FA _0.95 ) ⁺ , (Ｃｓ _{０． １} （ＦＡ _０．８ ＭＡ _０．２ ） _０．９ ) ⁺ etc. On the other hand, when monovalent organic cations and monovalent inorganic cations are mixed to form monovalent cations, these monovalent organic cations and monovalent inorganic cations are each independent, and after mixing, together with M and N, they form a three-dimensional perovskite. can be formed.

The M is a divalent metal cation, Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Sn ²⁺ , Pb ²⁺ , Bi ²⁺ , Ge ²⁺ , Ti ²⁺ , Eu ²⁺ and Zr It may include 1 or 2 types selected from ²⁺ .

^{In addition , ​ ​} X may be I _x Br _Y Cl _Z SCN _3-x+y+z (0≤x+y+z≤3).

The compound represented by Formula 2 is specifically FAPbI _x Br _3-x (0≤x≤3), MAPbI _x Br _3-x (0≤x≤3), Cs _b MA _1-a FA _a Pb _1-b I _x Br _3-x (0≤x≤3), CH ₃ NH ₃ PbX ₃ (X = Cl, Br, I _, BrI ₂ , or Br ₂ I), CH ₃ NH ₃ Sn or I), CH(=NH)NH ₃ PbX ₃ (X=Cl, Br, I, BrI ₂ , or Br ₂ I), CH(=NH)NH ₃ SnX ₃ (X=Cl, Br or I), etc. It can be.

In addition, the light absorption layer may be a single layer made of the same perovskite material, or may be a multilayer structure in which multiple layers each made of different perovskite materials are stacked, and may be made of one type of perovskite material. Inside the light absorption layer, a different type of perovskite material other than the one type of perovskite material having a pillar shape such as a pillar shape, a plate shape, a needle shape, a wire shape, or a rod shape may be included.

The light absorption layer 40 including perovskite having a three-dimensional crystal structure can be formed by processing a perovskite precursor solution on the first multi-functional layer 30. Specifically, the perovskite precursor solution may be a solution containing organic halide (LN) and metal halide (MN ₂ ).

The perovskite precursor solution can implement a perovskite with a three-dimensional crystal structure in two ways. Specifically, organic halide (LN) and metal halide (MN ₂ ) are mixed in an organic solvent at an appropriate known ratio. The mixed solution is treated on the first multi-functional layer 30 and then heat-treated at 50 to 130° C. (method 1), or a solution containing metal halide (MN ₂ ) is treated on the first multi-functional layer 30. It can then be heat treated at 50 to 150°C to form a metal halide layer, and then treated with a solution containing organic halide (LN) on the metal halide layer and heat treated again at 50 to 160°C (second method).

The thickness of the light absorption layer 40 implemented may be the thickness of a light absorption layer in a typical perovskite photoelectric conversion device, and may be, for example, 400 to 600 nm, but the present invention is not particularly limited thereto.

According to one embodiment of the present invention, a perovskite layer having a two-dimensional crystal structure for removing surface defects of perovskite with a three-dimensional crystal structure between step (3) described above and step (4) described later. forming (70) and forming a passivation layer (not shown); Any one or more steps may be further included. That is, after forming the perovskite layer 70 with a two-dimensional crystal structure on the light absorption layer 40, step (4) described later is performed, or the perovskite layer 70 with a two-dimensional crystal structure is formed. After forming the light absorption layer 40, a passivation layer may be further formed and step (4) described later may be performed, or a passivation layer may be formed on the light absorption layer 40 and step (4) described later may be performed. .

Here, the perovskite layer 70 having a two-dimensional crystal structure can be formed by processing a solution containing a perovskite precursor having a known two-dimensional crystal structure. In addition, the perovskite layer having the two-dimensional crystal structure may be treated with a solution containing the compound represented by Chemical Formula 1 for forming the first multi-functional layer described above to form a second multi-functional layer.

In addition, the passivation layer (not shown) is used to passivate the light absorption layer made of perovskite material, and may be implemented with a known material used in perovskite photoelectric conversion devices. For example, the passivation layer is Al ₂ O ₃ , SnO ₂ , TiO ₂ , ZnO, NiO, MoO3, CuO, CuGaO ₂ , Y ₂ O ₃ , SiN _x , SiO ₂ , Ta ₂ O ₅ , TFBA, AlF _x , LiF And it may include at least one of PbI ₂ .

Next, in step (4) according to the present invention, a hole transport layer or an electron transport layer 50 is formed on the light absorption layer 40.

The hole transport layer or electron transport layer 50 may be made of a typical hole transport layer or electron transport layer material used in perovskite photoelectric conversion devices, and may be formed of, for example, an organic material or an inorganic material.

When an electron transport layer is provided, the inorganic materials that can be used may be known inorganic materials used in solar cell electron transport layers, examples of which include metal oxides, metal sulfides, metal selenides, metal tellurium compounds, perovskites, amorphous Si, n-type Group IV semiconductor, n-type Group III-V semiconductor, n-type Group II-VI semiconductor, n-type Group I-VII semiconductor, n-type Group IV-VI semiconductor, n-type Group V-VI semiconductor, n-type Group II -V semiconductors, any of which may be doped or undoped. Additionally, it may generally be selected from metal oxides, metal sulfides, metal selenides, and metal tellurium compounds.

Specifically, the metal oxide may be one or more metal oxides containing titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium as a metal component. Additionally, the metal sulfide may be one or more of cadmium, tin, copper, and zinc sulfide. Additionally, the metal selenide compound may be one or more of cadmium, zinc, indium, and gallium selenide, and a more specific example may be Cu(In,Ga)Se ₂ . Additionally, the metal tellurium compound may be one or more of cadmium, zinc, and tin tellurium compounds, and a more specific example may be CdTe.

In addition, when an electron transport layer is provided, organic materials that can be used may be known organic materials used in solar cell electron transport layers, for example, fullerene or fullerene derivatives, perylene or derivatives thereof. Organic electron transport material, or poly{[N,N0-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,50-(2 ,20-bithiophene)}(P(NDI2OD-T2)).

On the other hand, when a hole transport layer is provided, the inorganic materials that can be used may be known inorganic materials used in solar cell hole transport layers, and examples include oxides of nickel, vanadium, copper, or molybdenum; CuI, CuBr, CuSCN, or CIS; perovskite; amorphous Si; p-type group IV semiconductors, p-type group III-V semiconductors, p-type group II-VI semiconductors, p-type group I-VII semiconductors, p-type group IV-VI semiconductors, p-type group V-VI semiconductors, and p-type group semiconductors. It may contain an inorganic hole transporter containing a II-V semiconductor, and this inorganic material may be doped or undoped.

In addition, when a hole transport layer is provided, organic materials that can be used may be known organic materials used in solar cell hole transport layers, such as chalcone derivatives, styrylanthracene derivatives, fluorene derivatives, hydrazone derivatives, and stilbene derivatives. , silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidine-based compounds, porphyrin-based compounds, phthalocyanine-based compounds, polythiophene derivatives, polypyrrole derivatives, polyparaphenylenevinylene derivatives, pentacene ( pentacene), coumarin 6 (coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC (zinc phthalocyanine), CuPC (copper phthalocyanine), TiOPC (titanium oxide phthalocyanine), Spiro-MeOTAD (2, 2',7,7'-tetrakis(N,N-p-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), SubPc(boron subphthalocyanine chloride), N3(cisdi(thiocyanato)-bis(2,2'-bipyridyl-4,4'- dicarboxylic acid)-ruthenium(II), P3HT (poly[3-hexylthiophene]), MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctylacyl)]-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-pmethoxyphenyl amine)-9,9,9′-spirobi fluorine]), CuSCN, CuI , 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 -(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl), 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]), 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- cobenzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate), PTAA (poly(triarylamine)), 2-PACz, and/or MeO-2PACz. It can be included.

The hole transport layer or electron transport layer 50 manufactured using the above-mentioned inorganic or organic material can be manufactured using a known method. In addition, the thickness of the formed hole transport layer or electron transport layer 50 can also be adopted or appropriately changed to the thickness of the hole transport layer or electron transport layer 50 used in the solar cell, so the present invention is not particularly limited thereto.

Next, in step (5) according to the present invention, the step of forming the second electrode 60 on the hole transport layer or electron transport layer 50 is performed.

The second electrode 60 may be a known electrode used in solar cells, for example, selected from Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C and conductive polymers. It can be formed by coating or depositing one or more materials. In addition, the second electrode 60 may be formed as one layer by mixing at least two types of materials described above, or may be formed as a multilayer structure in which at least two types of materials each form a single layer and these single layers are stacked. You can. In addition, the thickness of the second electrode 60 can be adjusted to the thickness of the second electrode used in the solar cell or can be appropriately changed, so the present invention is not particularly limited thereto.

Meanwhile, according to another embodiment of the present invention, as shown in FIG. 2, the perovskite photoelectric conversion device 110 has a light absorption layer 40 and a hole transport layer or electron transport layer 50 when the second metal oxide layer. The perovskite layer 70 having a two-dimensional crystal structure may be provided as a perovskite layer 70 having a two-dimensional crystal structure formed through a compound represented by the above-mentioned formula 1. In this case, the two-dimensional crystal structure The perovskite layer 70 having a function as a multi-functional layer can further improve the interface characteristics and interface connectivity between the light absorption layer and the hole transport layer or electron transport layer 50, which is the second metal oxide layer.

The perovskite photoelectric conversion devices (100, 110) manufactured through various embodiments of the present invention described above include a light absorption layer (40) and a first metal oxide layer (electron transport layer or hole transport layer) through the first multi-functional layer (30). 20) As the interfacial characteristics and interfacial connectivity are improved, it is possible to have a wider bandgap where photoluminescence occurs at a shorter wavelength, for example, 600 nm, and improved photoelectric conversion efficiency and long-term stability. You can have it. At this time, as an example, perovskite with a three-dimensional crystal structure used in the light absorption layer may be a perovskite that emits photoluminescence in the range of 400 nm to 600 nm.

In addition, due to the provision of the first multi-functional layer, the present invention implements an asymmetric spectrum in the short and long wavelengths based on the first wavelength, which is the wavelength at the peak when the intensity of PL is the highest, as can be seen through the PL spectrum shown in FIG. Specifically, in the photoluminescence (PL) spectrum for each wavelength, photoluminescence occurs in the wavelength range from the second wavelength, which is the shortest wavelength at which photoluminescence (PL) occurs, to the first wavelength, based on the first wavelength with the maximum intensity. An asymmetric spectrum that is larger than the wavelength range from the third wavelength, which is the longest wavelength, to the first wavelength is implemented, and the band gap can be wider toward the short wavelength. At this time, for example, the wavelength range from the second wavelength to the first wavelength may have a wider wavelength range exceeding 60% of the wavelength range from the third wavelength to the first wavelength. At this time, if the maximum intensity, first wavelength, second wavelength, and third wavelength in the PL spectrum are explained with reference to FIG. 8, the wavelength (a) at the PL maximum intensity (PL _max ) in the PL spectrum is the first wavelength, The shortest wavelength (b) at which photoluminescence (PL) occurs is the second wavelength, and the longest wavelength (c) at which photoluminescence (PL) is generated is the third wavelength.

In addition, the present invention includes a perovskite solar cell using the above-described perovskite photoelectric conversion elements (100, 110), and is further provided with the configuration of a known perovskite solar cell in addition to the perovskite photoelectric conversion element. can do.

In addition, the present invention enables the implementation of a silicon-perovskite tandem solar cell using the above-described perovskite photoelectric conversion device, and when explained with reference to FIGS. 3 and 4, the silicon-perovskite tandem solar cell The batteries 1000 and 1100 may be implemented by disposing a silicon photoelectric conversion element 200 and perovskite photoelectric conversion elements 100' and 110' on top of the silicon photoelectric conversion element 200.

At this time, the perovskite photoelectric conversion elements (100', 110') have a transparent electrode between the hole transport layer or electron transport layer (50) of the above-described perovskite photoelectric conversion elements (100, 110) and the second electrode (60). By further providing (80), the transparent electrode (80) is the same as the description of the first electrode (10) described above, so detailed description will be omitted.

Additionally, the silicon photoelectric conversion element 200 may be a known silicon-based solar cell, a known heterojunction silicon solar cell, or a known homojunction silicon solar cell. As an example of this, when the silicon photoelectric conversion element 110 is a heterojunction silicon solar cell, very thin amorphous intrinsic silicon (i a-Si:H) is passivated on the front and back surfaces of the n-type crystalline silicon substrate. It is formed in layers, and a p-type high-concentration amorphous silicon (p a-Si:H) layer is formed on the front as an emitter layer, and a high-concentration amorphous silicon (n+ a-Si:H) layer is formed on the back as a back electric layer. It can have a structure. Or, in the case of a homojuction crystalline silicon solar cell, 3 further comprising a two-layer structure including an emitter layer disposed on the first side of the crystalline silicon substrate, or a back electric layer disposed on the second side of the crystalline silicon substrate. It may also have a layered structure.

The present invention will be described in more detail through the following examples, but the following examples do not limit the scope of the present invention, and should be interpreted to aid understanding of the present invention.

<Example 1>

A 2.5 cm The cleaned ITO conductive transparent substrate was partially etched with an IR laser and then 30 nm of NiOx was formed as a hole transport layer using a deposition process.

Afterwards, 200 ㎕ of the solution containing the compound represented by Chemical Formula 1-1 prepared in Preparation Example 1 was dropped onto NiOx, spin-coated at 3000 rpm for 30 seconds, and then heat treated at 100°C to form a first multifunctional layer.

Afterwards, 100㎕ of a 1.4M perovskite precursor solution with a composition of Cs _0.1 (FA _0.75 MA _0.25 ) _0.9 Pb (I _0.75 Br _0.23 Cl _0.02 ) ₃ was dropped onto the first multi-functional layer, spin-coated at 5000 rpm for 30 seconds, and then again. 300㎕ of ethyl acetate was added dropwise, maintained at 5000rpm for 3 seconds, and heat treated at 100°C for 20 minutes to form a light absorption layer with a final thickness of 500nm.

Afterwards, a 13 nm thick C60 layer was formed as an electron transport layer on the formed light absorption layer using thermal evaporation equipment. 200㎕ of a solution of 1mg of bathocuproine dissolved in 1ml of IPA was dropped onto the formed electron transport layer, then spin-coated at 4000rpm for 30 seconds to form an exciton blocking layer, and then a second electrode made of Ag with a thickness of 100nm was formed using thermal evaporation equipment. A perovskite photoelectric conversion device was manufactured.

*Preparation example 1

(4-aminophenyl)phosphonic acid (1.00 g, 5.34 mmol), Hydriodic acid (1.36 g, 10.68 mmol), and ethanol (100 mL) were added to a 250 mL flask and stirred for 1 hour. After the reaction was completed, 50 ml of ether was added to obtain an organic precipitate, which was filtered to obtain 4-phosphonobenzenaminium iodide product, a compound represented by the following formula 1-1, with a yield of 95%.

1H NMR (300 MHz, Chloroform-d) δ 6.80~7.07 (d, J = 7.5 Hz, 2H), 7.09~7.24 (t, J = 7.5 Hz, 2H), 4.8~5.0 (s, J = 8.2 Hz, 2H), 7.2 (t, J = 8.5 Hz, 2H).

[Formula 1-1]

Afterwards, 4 mg of synthesized 4-phosphonobenzenaminium iodide was dissolved in 1 ml of isopropyl alcohol (IPA) to prepare a solution containing the compound represented by Formula 1-1.

<Comparative Example 1>

A perovskite photoelectric conversion device was manufactured in the same manner as in Example 1, except that the production of the first multi-functional layer was omitted and a light absorption layer was formed on the NiO _x hole transport layer.

<Experimental Example 1>

The current-voltage characteristics and efficiency of the perovskite photoelectric conversion device according to Example 1 and Comparative Example 1 were measured, and the results are shown in Table 1 below.

Voc(V) Jsc(mA/㎠) FF(%) Best eff.(%) Avg. eff.(%) Example 1 1.178 21.323 80.61 20.25 20.18 Comparative Example 1 1.154 20.642 75.94 18.41 18.10

As can be seen from Table 1, the photoelectric conversion device of Example 1 is improved compared to the photoelectric conversion device of Comparative Example 1 in all solar cell efficiency parameters due to the provision of the first multi-functional layer, which is a perovskite with a two-dimensional crystal structure. You can check that.

<Experimental Example 2>

The light absorption spectra by wavelength measured using a UV-vis meter for the perovskite photoelectric conversion devices according to Example 1 and Comparative Example 1 are shown in FIG. 5.

In addition, the PL spectrum of the perovskite photoelectric conversion devices according to Example 1 and Comparative Examples 1 and 2 was measured using photoluminescence spectroscopy, and the results are shown in Table 2 and Figure 6.

Example 1 Comparative Example 1 First wavelength (㎚) ７３５ ７３５ Second wavelength (㎚) ５９０ ６５０ Third wavelength (㎚) ８２０ ８２０ A(%) 70.6 0 600㎚ PL occurrence or not ○ ×

Here, A is calculated by the following equation.

[ceremony]

As can be seen through Table 2, Figures 5 and 6,

The light absorption area between the photoelectric conversion elements according to Example 1 and Comparative Example 1 was almost the same. However, the photoelectric conversion device of Example 1, which has a metal oxide layer and a first multi-functional layer of perovskite with an adsorbed two-dimensional crystal structure, generates photoluminescence even at a wavelength of 600 nm, but the photoelectric conversion device of Comparative Example 1 It can be seen that the device generates photoluminescence at a wavelength exceeding 650 nm, and through this, it can be confirmed that the band gap in the photoelectric conversion device of Example 1 is further increased compared to the photoelectric conversion device of Comparative Example 1. . In addition, the photoelectric conversion device according to Comparative Example 1 has an A value of 0% calculated through the above equation in the PL spectrum, and the spectrum is almost symmetrical based on the wavelength with the maximum intensity. However, the photoelectric conversion device according to Example 1 has a PL spectrum of 0%. In the spectrum, the A value calculated through the above equation is 70.6%, which shows that the spectrum has an asymmetric spectrum that is wider toward short wavelengths based on the wavelength with the maximum intensity.

Although one embodiment of the present invention has been described above, the spirit of the present invention is not limited to the embodiment presented in the present specification, and those skilled in the art who understand the spirit of the present invention can add components within the scope of the same spirit. , other embodiments can be easily proposed by change, deletion, addition, etc., but this will also be said to be within the scope of the present invention.

Claims (14)

(1) forming an electron transport layer or a hole transport layer, which is a first metal oxide layer, on the first electrode;
(2) forming a first multi-functional layer including perovskite having a two-dimensional crystal structure by treating the first metal oxide layer with a solution containing a compound represented by the following formula (1);
(3) forming a light absorption layer including perovskite having a three-dimensional crystal structure, which is a compound represented by the following formula (2) by treating the perovskite precursor solution on the first multi-functional layer;
(4) forming a hole transport layer or electron transport layer on the light absorption layer; and
(5) forming a second electrode on the hole transport layer or the electron transport layer; a perovskite photoelectric conversion device manufacturing method comprising:
[Formula 1]
[AB][X]
Here, [AB] is a monovalent organic cation, X is a monovalent anion,
A is -PO(OH) ₂ , -CO(OH), or -Si(OH) ₂ , and B is -(R ₁ R ₂ R ₃ R ₄ N) or -(R ₇ R ₈ N=CH-NR ₉ R ₁₀ ),
Here, R ₁ is C1 to C20 substituted or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₅ R ₆ , where R ₅ is C1 to C20 substituted or unsubstituted alkylene, or C6. ~ C20 substituted or unsubstituted arylene, R ₆ is C6 ~ C20 substituted or unsubstituted arylene, or C1 ~ C20 substituted or unsubstituted alkylene, R ₂ , R ₃ , R ₄ are each independently Hydrogen, substituted or unsubstituted alkylene with C1 to C20, substituted or unsubstituted arylene with C6 to C20,
R ₇ is C1 to C20 substituted or unsubstituted alkylene, C6 to C20 substituted or unsubstituted arylene, or R ₁₁ R ₁₂ , where R ₁₁ is C1 to C20 substituted or unsubstituted alkylene, or C6 to is a C20 substituted or unsubstituted arylene, and R ₁₂ is a C6 to C20 substituted or unsubstituted arylene, or a C1 to C20 substituted or unsubstituted alkylene,
R ₈ , R ₉ and R ₁₀ are each independently hydrogen, substituted or unsubstituted C1-C20 alkyl, or substituted or unsubstituted aryl,
X is any one of I ^- , Br ^- , Cl ^- and F ^- halogen anion or SCN ^- anion,
[Formula 2]
[L][M][N] ₃
Here, L is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, M is a divalent metal cation, and N is at least one anion. According to paragraph 1,
A method of manufacturing a perovskite photoelectric conversion device, characterized in that when a solution containing the compound represented by Formula 1 is treated in step (2), the compound represented by Formula 1 is adsorbed to the first metal oxide layer. delete According to paragraph 1,
Between steps (3) and (4)
Forming a perovskite layer with a two-dimensional crystal structure to remove surface defects of the perovskite with a three-dimensional crystal structure; and
forming a passivation layer; A method of manufacturing a perovskite photoelectric conversion device further comprising any one or more steps. first electrode;
An electron transport layer or hole transport layer that is a first metal oxide layer formed on the first electrode;
A first multi-functional layer including perovskite having a two-dimensional crystal structure formed on the first metal oxide layer;
A light absorption layer having a perovskite having a three-dimensional crystal structure, which is a compound represented by the following formula (2), formed on the first multi-functional layer;
A hole transport layer or electron transport layer formed on the light absorption layer; and
It includes a second electrode formed on the hole transport layer or the electron transport layer,
Based on the first wavelength with the maximum intensity in the photoluminescence (PL) spectrum by wavelength, the wavelength range from the second wavelength, which is the shortest wavelength at which photoluminescence (PL) occurs, to the first wavelength, is the longest wavelength at which photoluminescence (PL) occurs. Perovskite photoelectric conversion element formed larger than the wavelength range from the third wavelength to the first wavelength:
[Formula 2]
[L][M][N] ₃
Here, L is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, M is a divalent metal cation, and N is at least one anion. According to clause 5,
A perovskite photoelectric conversion device, characterized in that the wavelength range from the second wavelength to the first wavelength has a wider wavelength range exceeding 60% of the wavelength range from the third wavelength to the first wavelength. first electrode;
An electron transport layer or hole transport layer that is a first metal oxide layer formed on the first electrode;
A first multi-functional layer including perovskite having a two-dimensional crystal structure formed on the first metal oxide layer;
A light absorption layer having a perovskite having a three-dimensional crystal structure, which is a compound represented by the following formula (2) formed on the first multi-functional layer, and generating photoluminescence at 400 to 600 nm;
A hole transport layer or electron transport layer formed on the light absorption layer; and
It includes a second electrode formed on the hole transport layer or the electron transport layer,
Perovskite photoelectric conversion device that generates photoluminescence at a wavelength of 600 nm:
[Formula 2]
[L][M][N] ₃
Here, L is a monovalent organic cation, a monovalent metal cation, or a mixture thereof, M is a divalent metal cation, and N is at least one anion. delete According to clause 5 or 7,
A perovskite photoelectric conversion device, characterized in that the perovskite having the two-dimensional crystal structure is adsorbed on the first metal oxide layer. According to clause 5 or 7,
The first metal oxide layer is a metal oxide containing one type of metal selected from the group consisting of Ni, V, Mo, Cu, Ti, Sn, Zn, Nb, Ta, W, In, Ga, Nd, Pb and Cd, Or a perovskite photoelectric conversion device containing at least two types of these metal oxides. According to clause 5 or 7,
A perovskite photoelectric conversion device further comprising a perovskite layer having a two-dimensional crystal structure on the light absorption layer to remove surface defects of the perovskite having a three-dimensional crystal structure. According to clause 11,
A perovskite photoelectric conversion device further comprising a passivation layer on the perovskite layer having the two-dimensional crystal structure. A perovskite solar cell comprising the perovskite photoelectric conversion element according to claim 5 or 7. Silicon photoelectric conversion element; and
A silicon-perovskite tandem solar cell comprising a perovskite photoelectric conversion element according to claim 5 or 7 disposed on the silicon photoelectric conversion element.

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