WO2020174972A1

WO2020174972A1 - Photoelectric conversion element and production method for photoelectric conversion element

Info

Publication number: WO2020174972A1
Application number: PCT/JP2020/002820
Authority: WO
Inventors: 良太三島; 将志日野; 智巳目黒; 淳志若宮; ミンアンチョン
Original assignee: 株式会社カネカ; 国立大学法人京都大学
Priority date: 2019-02-27
Filing date: 2020-01-27
Publication date: 2020-09-03
Also published as: JP7244031B2; JPWO2020174972A1

Abstract

Provided is a perovskite-type photoelectric conversion element in which light enters a light absorption layer from a side on which a hole transport layer is disposed. This photoelectric conversion element has a light absorption layer containing a compound having a perovskite-type structure, an electron transport layer disposed on one side of the light absorption layer, and a hole transport layer provided on the other side of the light absorption layer, wherein the hole transport layer is a vapor deposition layer that contains an organic material, has a thickness of 50 nm or less, and has an absorption peak wavelength of 400 nm or less.

Description

Specification

Title of invention: Photoelectric conversion element and method for manufacturing photoelectric conversion element

The present invention relates to a photoelectric conversion element and a method for manufacturing a photoelectric conversion element.

Background technology

[0002] Solar cells using perovskite-type crystals of organic metal as a light absorption layer (perovskite-type solar cells) can achieve high conversion efficiency, and many reports have been made in recent years (eg, Patent Document 1 and Non-Patent Document 1). As the organic metal, for example, a compound represented by the general formula RN H ₃ MX ₃ (wherein R is an alkyl group, M is a divalent metal ion, and X is a halogen) is used. There is. Above all, a belovsky type crystal such as CH ₃ NH ₃ P bX ₃ (X: halogen) can be formed at low cost by solution coating such as spin coating. Therefore, perovskite-type solar cells using such perovskite-type crystals are drawing attention as low-cost and high-efficiency next-generation solar cells.

[0003] A bevelskite solar cell typically has a hole transport layer on one side and an electron transport layer on the other side of the above-described light absorption layer. As a material for forming the hole transport layer, an organic material such as Spiro-Me TAD is generally used. Since the hole transport layer formed of S p i r 〇 — M e T A D can absorb light, it is usually arranged on the side opposite to the light incident side with respect to the light absorbing layer. On the other hand, it may be desirable that the light is incident on the light absorption layer from the side where the hole transport layer is arranged.

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 2014_72327

Non-patent literature

[0005] Non-Patent Document 1: G. Hodes, Science, 342, 317-318 (2013). 〇 2020/174972 2 (:171? 2020/002820 Summary of invention)

Problems to be Solved by the Invention

In view of the above, an object of the present invention is to provide a belovskite-type photoelectric conversion element in which light is incident on the light absorption layer from the side where the hole transport layer is arranged. Means for solving the problem

According to one aspect of the present invention, a photoelectric conversion element is provided. This photoelectric conversion device includes a light absorption layer containing a compound having a perovskite structure, an electron transport layer arranged on one side of the light absorption layer, and a hole arranged on the other side of the light absorption layer. And a hole transporting layer containing an organic material, having a thickness of 50 nm or less and an absorption peak wavelength of 400 _n or less, and the organic material is: General formula (1):

[Chemical 1]

(In the formula, 8 represents a hydrogen atom or an organic group,

Represents a substituent comprising an organic group not containing nitrogen same or different, 8 ² represents a substituent the ^_ or different,

Are the same or different and represent a substituent consisting of an organic group containing no nitrogen, 1 is an integer of 0 to 4, 2 is an integer of 0 to 2, and 3 is an integer of 0 to 4. )

And/or the general formula (2): 〇 2020/174972 卩(: 171-1? 2020/002820

[Chemical 2]

(In the formula, 8 represents a hydrogen atom or an organic group,

Are the same or different and represent a substituent consisting of an organic group containing no nitrogen,

⁵ represents a substituent comprising a containing having no organic group nitrogen same or different, 8 ⁶ Represents a substituent same ^_ or different, 4 represents an integer of 〇_～ 4, 5 of 〇_～ 3 Represents an integer, and 6 represents an integer from 0 to 3. )

The light is incident on the light absorption layer from the side on which the hole transport layer is arranged.

[0008] In one embodiment, the absorption edge wavelength of the hole transport layer is 450 n or less.

In one embodiment, the molecular weight of the organic material is 270 or more and 200 or less.

In one embodiment, the hole transport layer is substantially free of dopant.

In one embodiment, the photoelectric conversion element has a transparent electrode arranged on a side of the hole transport layer opposite to a side on which the light absorption layer is arranged.

In one embodiment, the photoelectric conversion element has a buffer layer arranged between the hole transport layer and the transparent electrode.

In one embodiment, the photoelectric conversion element has a transparent electrode arranged on a side of the electron transport layer opposite to a side on which the light absorption layer is arranged.

In one embodiment, the photoelectric conversion element is another photoelectric conversion element. 〇 2020/174972 4 卩 (：171? 2020 /002820

It further has a conversion unit.

In one embodiment, the other photoelectric conversion unit includes a crystalline silicon substrate.

[0009] According to another aspect of the present invention, a method for manufacturing a photoelectric conversion element is provided. This method for manufacturing a photoelectric conversion element includes forming a light absorbing layer containing a compound having a perovskite structure on one side of a substrate, and depositing a vapor deposition material containing an organic material on one side of the substrate. And forming a hole transport layer having a thickness of 50 _n or less and an absorption peak wavelength of 400 n or less, wherein the organic material has the following general formula (1):

[Chemical 3]

(In the formula, 8 represents a hydrogen atom or an organic group,

² are the same or different and represent a substituent,

Are the same or different and represent a substituent consisting of an organic group containing no nitrogen, 01 1 represents an integer from 0 to 4, 01 2 represents an integer from 0 to 2, 01 3 represents an integer from 0 to 4. Represent )

And/or the general formula (2): 〇 2020/174972 卩(: 171-1? 2020/002820

[Chemical 4]

(In the formula, 8 represents a hydrogen atom or an organic group,

⁵ is the same or different and represents a substituent consisting of an organic group containing no nitrogen, 8 ⁶ is the same or different and represents a substituent, 4 is an integer from 0 to 4, 5 is an integer from 0 to 3. Represents, and 6 represents an integer from 0 to 3. )

Is a compound represented by.

[0010] In one embodiment, the method for manufacturing a photoelectric conversion element includes forming a transparent electrode on the side of the hole transport layer opposite to the side on which the light absorption layer is arranged.

Effect of the invention

[001 1] According to the present invention, it is possible to provide a perovskite photoelectric conversion element in which light is emitted from the side where the hole transport layer is arranged with respect to the light absorption layer.

Brief description of the drawings

[0012] [Fig. 1] Fig. 1 is a schematic cross-sectional view of a photoelectric conversion element in one embodiment of the present invention.

FIG. 2 is a schematic sectional view of a photoelectric conversion element according to another embodiment of the present invention.

FIG. 3 is a schematic cross-sectional view of a laminated photoelectric conversion element according to an embodiment of the present invention.

FIG. 4 is a graph showing measurement results of external quantum efficiency of Example 1 and Comparative Example 1. \¥0 2020/174972 6 卩 (: 17 2020 /002820

FIG. 5 is a graph showing the measurement results of external quantum efficiency before and after the formation of the antireflection layer.

MODE FOR CARRYING OUT THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0014] FIG. 1 is a schematic cross-sectional view of a photoelectric conversion element according to an embodiment of the present invention. A photoelectric conversion element (typically, a solar cell) 100 is a substrate (transparent substrate) 10, a first electrode layer 21, an electron transport layer 30 and a compound having a perovskite structure ( Hereinafter, a light absorption layer 40 containing a perovskite compound), a hole transport layer 50, and a second electrode layer 22 are provided in this order. The electron transport layer 30 includes a blocking layer 31 and a porous carrier layer 32.

[0015] The electrode layers 21 and 22 arranged on both sides of the light absorption layer 40 are both transparent electrode layers. Therefore, as shown by the arrow in the figure, light may be incident on the light absorption layer 40 from the first electrode layer 21 (substrate 10) side or from the second electrode layer 22 side. It may be incident, or may be incident from the first electrode layer 21 side and the second electrode layer 22 side. As will be described later, since the hole transport layer 50 can suppress optical absorption loss, from the side where the hole transport layer 50 is arranged with respect to the light absorption layer 40 (in the illustrated example, , And from the side of the second electrode layer 22) Even if light is incident, the photoelectric conversion efficiency can be excellent.

[0016] Although not shown, the photoelectric conversion element 100 may have other layers.

Specific examples of the other layer include a buffer layer arranged between the hole transport layer 50 and the second electrode layer 22. Another specific example of the other layer is an antireflection layer (antireflection layer) capable of preventing reflection of incident light. The antireflection layer is typically arranged as the outermost layer on the light incident side of the photoelectric conversion element 100. In the illustrated example, it may be arranged on the outside of the substrate 10 and/or the second electrode layer 22 (the side opposite to the side on which the light absorption layer 40 is arranged).

[0017] The substrate 10 is typically composed of a transparent substrate such as glass or a film capable of transmitting light. Examples of the glass include non-alkali glass. 〇 2020/174972 7 卩(：171? 2020/002820

Be done. Examples of the film include Mingo film, aramid film, and polyimido film.

The [0018] The transparent electrode layer, for example, fluorine-doped tin oxide (Ding 〇), Suzudo - flop indium oxide (丨Ding 〇), single layer material such as zinc oxide (Z _n 〇), or a laminate thereof A laminated body constituted by The thickness of the transparent electrode layer varies depending on its structure, but is typically 10

Is. The transparent electrode layer can be formed by any appropriate film forming method depending on the forming material. For example, it is formed by a spray pyrolysis method or a grasshopper method.

[0019] The electron transport layer 30 can be formed of any appropriate material. Examples of the material for forming the electron transport layer include inorganic materials represented by metal oxides such as titanium oxide, zinc oxide, niobium oxide, zirconium oxide, and aluminum oxide, and fullerene-based materials such as 〇巳1\/1. Examples of the material include organic materials such as perylene-based materials. Among these, inorganic materials are preferably used. Donors may be added to the electron transport layer. As a specific example, when titanium oxide is used as the material for forming the electron transport layer, yttrium, europium, terbium, etc. are used as the donor.

In the example shown in FIG. 1, the electron transport layer 30 includes the blocking layer 31. The blocking layer 31 can function as a seed layer. Specifically, the blocking layer 31 can promote the growth of the layer as a scaffold when forming the light absorption layer 40 (perovskite compound layer), for example. Blocking layer 3 1 is preferably titanium oxide (Ding丨〇 _2), comprising a metal oxide such as zinc oxide (Z _n 〇). Preferably rather the blocking layer 3 1 is composed of a compact Ding丨〇 _2. According to such a form, for example, the surface of the first electrode layer 21 can be densely covered. The thickness of the blocking layer 31 is preferably, for example, from the viewpoint of optical and electron injection,

More preferably

It is 111.

As shown in FIG. 1, the electron transport layer 30 preferably includes a porous carrier layer 32 in addition to the blocking layer 31. The porous carrier layer 32 is a blocking layer. 〇 2020/174972 8 卩 (：171? 2020 /002820

It is arranged on the side where the light absorption layer 40 is arranged with respect to 31. The porous carrier layer 32 can function as a scaffold for the light absorption layer 40. In addition, the porous carrier layer 32 can increase the surface area of the light absorption layer 40 to allow the light absorption layer 40 to absorb more light.

The porous carrier layer 32 preferably contains the components contained in the blocking layer 31. According to such a form, the adhesion between the blocking layer 3 1 and the porous carrier layer 3 2 can be improved. As a result, the adhesion between the electron transport layer 30 and the light absorption layer 40 can be improved. Specifically, as the porous support layer 3 2 of the forming material, it is preferable to use a metal oxide, among others, it is preferable to use a Ding I 〇 ₂ and eight丨₂ 〇 _2. The thickness of the porous carrier layer 32 is preferably 50 nm to 3001^111, more preferably

With such a range, for example, optical absorption loss can be reduced. Further, the light absorption layer 40 can be formed well.

[0023] The electron transport layer 30 can be formed by any appropriate method depending on its configuration, forming material, and the like. Examples of the forming method include a vacuum evaporation method, a dry method such as a XX method and a sputtering method, and a wet process such as a spin coating method, a spray method and a bar coating method.

[0024] The photoelectric conversion element 100 is typically manufactured by sequentially laminating each layer on the substrate 10. As shown in FIG. 1, in the configuration in which the electron transport layer 30 is arranged on the substrate 10 side of the light absorption layer 40, the electron transport layer 30 is formed first, and then the light absorption layer 40 is formed. It According to such a stacking order, the porous carrier layer 32 capable of functioning as a scaffold for the light absorption layer 40 can be favorably formed.

[0025] For example, when light is incident only on the light absorption layer 40 from the side on which the hole transport layer 50 is arranged (in the illustrated example, from the second electrode layer 22 side), the electron transport layer The transparency of 30 can be set low. In this case, the electron transport layer 30 can be thickened.

[0026] The light absorption layer 40 contains a berovskite compound. Berobusukai DOO compounds, for example, the general formula 1 \ 1 1 ^to 1 ₃ 1 \ / 1 say yes ₃ or 〇 ^1-1

Represented by ₂ 1 \ / 1 say yes _3. In the ceremony

, Is an alkyl group, preferably an alkyl group having 1 to 5 carbon atoms, 〇 2020/174972 9 卩(：171? 2020/002820

Further, it is preferably a methyl group. In the formula, IV! is a divalent metal ion, and preferably is 3 n. In the formula, X is a halogen, and specifically, ◯ B r _s丨 can be mentioned. All three Xs in the formula may be the same halogen element, or a plurality of halogen elements may be mixed. For example, the spectral sensitivity characteristics can be changed by changing the type and ratio of halogen. In the above formula

Instead of ₂ , it is also possible to partially use an alkali metal (for example, 0 3, [¾, [<]).

[0027] The thickness of the light absorption layer 40 is, for example,

For example, from the viewpoint of light absorption efficiency and exciton diffusion length, the thickness of the light absorption layer 40 is preferably

[0028] The half-value width of the diffraction peak (2 0 = 1 4 °) of 6 "○ 3 1 <丨 16 (丨丨丨)" of the light absorption layer 40 by X-ray diffraction method is typically ○. 1 6 to 0 .25

The light absorption layer 40 can be formed by the dry process or the wet process described above. The light absorption layer 40 is formed, for example, by applying a coating solution (for example, a solution) containing a material forming a perovskite compound by a spin coating method or the like. Specifically, when 〇 1 ^~ 1 ₃ 1\1 1 ^~ 1 ₃ ?匕丨₃ is adopted as a perovskite compound, it can be used in a solvent such as dimethyl sulfoxide, 1\1, 1\1—dimethylformamide. by a solvent solution obtained by mixing lead iodide and methyl iodide ammonium was applied by a spin coating method, heating the resulting coating film, Rei_1 ^~ 1 ₃

The crystallinity can be improved by bringing a poor solvent into contact with the surface of the coating film.

The light absorption layer 40 can also be formed by combining the dry process and the wet process described above. For example, by forming a thin film of lead iodide by a vacuum deposition method and contacting its surface with a solution of methylammonium iodide in isopropyl alcohol,

Examples of the method of bringing the solution into contact with the surface of the thin film include a method of applying the solution by spin coating and a method of immersing the thin film in the solution. For example, after 〇 2020/174972 10 卩(：171? 2020/002820

Due to the texture structure (irregular structure) of the silicon substrate described above, the immersing method is preferably used from the viewpoint of uniformly contacting the solution, such as when the surface contacting the solution has irregularities.

The hole transport layer 50 is composed of a vapor deposition layer containing an organic material. The vapor-deposited layer can be excellent in film forming property. Further, by adopting the vapor deposition layer, a film having a high density can be obtained and the thickness of the hole transport layer 50 can be reduced. As a result, optical absorption loss can be suppressed. In addition, the use of additives such as dopants is suppressed, which can contribute to the improvement of the life of the photoelectric conversion element.

The thickness of the hole transport layer 50 is preferably 50 n or less, more preferably 45 nm or less, and further preferably 40 n.

It is particularly preferably 35 or less. On the other hand, the thickness of the hole transport layer 50 is preferably 20 n or more, more preferably 15 n or more, further preferably 10 n or more, particularly preferably 5 n 01 or more. With such a range, it is expected that the internal electric field will be sufficiently secured to improve the performance.

The absorption peak wavelength of the hole transport layer 50 is preferably 400 n or less. Within such a range, the photoelectric conversion efficiency can be excellent even if light is incident on the light absorption layer 40 from the side where the hole transport layer 50 is arranged. The absorption peak wavelength refers to a wavelength at which the extinction coefficient has a maximum value and the absorption coefficient has a maximum value, and is obtained, for example, by measuring an absorption spectrum with an ultraviolet-visible spectrophotometer.

The absorption edge wavelength of the hole transport layer 50 is preferably 450 n or less.

Within such a range, for example, even if light is incident on the light absorption layer 40 from the side where the hole transport layer 50 is arranged, the photoelectric conversion efficiency can be excellent. As described above, in the hole transport layer 50, the use of additives such as a dopant can be suppressed, so that optical absorption loss can be suppressed, and such an absorption edge wavelength can be satisfactorily achieved. The absorption edge wavelength means, for example, a wavelength indicating the absorption edge of the absorption spectrum measured by an ultraviolet-visible spectrophotometer.

[0035] The vapor deposition layer is compared with a coating layer formed by a solution method using the same organic material. 〇 2020/174972 11 卩(：171? 2020/002820

As a result, the compactness can be increased. For example, many pinholes are observed in the coating layer formed by the solution method, whereas formation of pinholes can be suppressed in the vapor deposition layer. Further, as described above, since the use of the additive such as the dopant can be suppressed in the hole transport layer 50, the formation of the protrusion due to the additive can be suppressed. The proportion of pinholes and protrusions on the surface of the hole transport layer 50 is, for example, 30% or less. The proportion occupied by pinholes and protrusions can be determined by counting foreign matter by observing the surface with a scanning electron microscope (3*1\/1), for example.

The vapor deposition layer may have excellent film stability. Specifically, the vapor-deposited layer may have a higher glass transition temperature (Cho 9) as compared with a coating layer formed by the solution method using the same organic material.

[0037] Of the organic material contained in the hole transport layer 50,

For example, in view of the relationship with the adjacent layer, it is preferably 5.606 V-1.706 V, and more preferably 1.560-6 to 4.906 V. 1-of the organic materials contained in the hole transport layer 50

Is preferably, for example, from the relationship with the adjacent layer, 1.36 V/~-I 406 V, and more preferably 1.006 V-1.606 V. In addition,

For example, it can be measured by atmospheric photoelectron spectroscopy.

[0038] Band gap of the organic material contained in the hole transport layer 50

〇 gap) is preferably 2. 76 V or more, more preferably 3. 06 V or higher, particularly preferably 3. 1 ₆ V or more. This is because the absorption edge can be set to the ultraviolet region to suppress optical absorption loss. On the other hand, the band gap of the organic material contained in the hole transport layer 50 is, for example, 4.

The voltage is preferably 56 V or less, more preferably 4.06 or less, and particularly preferably 3.56 V or less. The band gap is confirmed by, for example, spectroscopic ellipsometry or spectrophotometer.

As the organic material contained in the hole transport layer 50, any suitable organic material can be adopted as long as a vapor deposition layer can be formed. Organic material contained in the hole transport layer 50 20/174972 12 2020 /002820

Is preferably represented by the general formula (1)

[Chemical 5]

(In the formula, 8 represents a hydrogen atom or an organic group,

² are the same or different and represent a substituent,

And/or the general formula (2):

[Chemical 6]

(In the formula, 8 represents a hydrogen atom or an organic group,

Represents a substituent having an organic group which does not have, and 8 ⁶ represents the same or different substituents. 〇 2020/174972 13 卩(：171? 2020/002820

However, 01 4 represents an integer from 0 to 4, 01 5 represents an integer from 0 to 3, and 6 represents an integer from 0 to 3. )

The compound represented by This is because the vapor deposition layer can be formed well. Specifically, a very dense vapor deposition film can be formed. In addition, it can contribute to improvement of photoelectric conversion efficiency. In particular,

◯ can be satisfied satisfactorily. In addition, the band gap can be well satisfied, optical absorption loss can be suppressed, and sensitivity (particularly, sensitivity to light having a short wavelength (for example, light having a wavelength of ₄₂₀ nm or less)) can be excellent. In addition, it may have a high hole mobility. As a result, it can contribute to the suppression of the use of additives such as dopants.

[0040] In the above general formulas (1) and (2),

Represents a substituent. Specific examples of the substituent include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group and the like. Of these, an unsubstituted alkyl group is preferable.

[0041] The alkyl group may be linear, branched, or cyclic. It is preferably linear or branched. The carbon number of the alkyl group is, for example, 1 to 20, preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 (specifically, methyl group, ethyl group, n-proton, etc. Pill group or isopropyl group).

[0042] The alkoxy group may be linear, branched, or cyclic. It is preferably linear or branched. The carbon number of the alkoxy group is, for example, 1 to 20, preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3 (specifically, a methoxy group, an ethoxy group,

-Propoxy group or isopropoxy group).

The aryl group may be a group derived from a monocyclic aromatic ring or a group derived from a polycyclic aromatic ring. The carbon number of the aryl group is, for example, 6 to 22, preferably 6 to 18, more preferably 6 to 14 and particularly preferably 6 to 10 (specifically, a phenyl group, 1 — Naphthyl group, 2-naphthyl group, etc.).

The above-mentioned aryloxy group may be a group derived from a monocyclic aromatic ring, or a polycyclic aromatic ring. 〇 2020/174972 14 卩 (：171? 2020 /002820

It may be a ring-derived group. The carbon number of the aryloxy group is, for example, 6 to 22, preferably 6 to 18, more preferably 6 to 14 and particularly preferably 6 to 10 (specifically, a phenyloxy group, 1-naphthyl Oxy group, 2-naphthyloxy group, etc.).

When there are a plurality of (when 1 is 2 or more), the plurality may be the same or different.

When there are two or more (2 is 2 or more), two or more ² may be the same or different.

When there is more than one (when 3 is 2 or more), the plurality of may be the same or different.

If there is more than one (O 14 is 2 or more, they may be the same or different.

If there are multiple

A plurality of may be the same or different.

If there is a number (6 is 2 or more), the two or more may be the same or different. Also,

May be the same or different from each other.

In the above general formula (1), 1 represents the number of substituents and is an integer from 0 to 4. In one embodiment,

(Only hydrogen atom) is preferable. This is because the hole transport layer 50 is a vapor deposition layer, and thus the hole transport layer (vapor deposition layer) 50 can be formed regardless of solubility in an organic solvent, for example.

[0047] In the above general formula (1),

Is an integer from 0 to 2. In one embodiment,

[0048] In the above general formula (1),

Is an integer from 0 to 4. In one embodiment,

[0049] In the general formula (2), 4 represents the number of substituents ^4, it is an integer of 〇_～ 4. In one embodiment,

(Only hydrogen atom) is preferable. This is because the hole transport layer 50 is a vapor deposition layer, and thus the hole transport layer (vapor deposition layer) 50 can be formed regardless of solubility in an organic solvent, for example. 〇 2020/174972 1 5 卩 (: 171? 2020 /002820

[0050] In the above general formula (2), 5 represents the number of the substituents ⁵ , and is an integer from 0 to 3. In one embodiment, (hydrogen atom only) is preferred. This is because the hole transport layer 50 is a vapor deposition layer, and thus the hole transport layer (vapor deposition layer) 50 can be formed regardless of solubility in an organic solvent, for example.

[0051] In the above general formula (2),

It represents the number of, and is an integer from 0 to 3. In one embodiment,

In the above general formulas (1) and (2), eight is preferably an organic group. This is because the vapor deposition layer can be formed well.

In one embodiment, in the above general formulas (1) and (2), 8 is the following general formula (3):

[Chemical 7]

(In the formula, 8'represents a divalent aromatic hydrocarbon group, n represents 0 or 1,

Are the same or different and represent a substituent,

Represents the integer, and 111 3 represents the integer from 0 to 4. )

Or a general formula (4): 〇 2020/174972 16 卩(：171? 2020/002820

[Chemical 8]

Are the same or different and each represents a substituent, 111 4 represents an integer from 0 to 4, 11 15 represents an integer from 0 to 3, and 11 16 represents an integer from 0 to 3. )

Is a group represented by.

[0054] In the above general formulas (3) and (4),

The above is as described above.

In the above general formulas (3) and (4), “represents a divalent aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a monocyclic aromatic hydrocarbon group and a polycyclic aromatic group. And a condensed polycyclic aromatic hydrocarbon group.

[Chemical 9]

Is. \¥0 2020/174972 17 卩(: 17 2020/002820

[0056] In one embodiment, in the general formulas (1) and (2), 8 is a nitrogen-containing group. As a specific example,

[Chemical 10]

, The following general formula (5)

[Chemical 1 1]

(In the formula,

Are the same or different and represent a substituent,

Are the same or different and each represents a substituent, 111 7 represents an integer from 0 to 5, and 0! 8 represents an integer from 0 to 5. And a group represented by:

The details of the substituent of the general formula (5) are as described above.

[0058] The molecular weight of the organic material contained in the hole transport layer 50 is preferably 270 or more, more preferably 300 or more, and particularly preferably 400 or more. On the other hand, the molecular weight of the organic material contained in the pore transport layer 50 is preferably 200 or less, more preferably 180 or less, and particularly preferably 150 or less. By having a molecular weight in such a range, a vapor deposition layer can be formed well. Specifically, materials with a low molecular weight tend to sublime, making it difficult to control the deposition amount. Materials with high molecular weight have a high sublimation temperature and tend to decompose before vapor deposition. Further, if the sublimation temperature is high, the light absorption layer 40 may be damaged when the hole transport layer 50 is formed.

As a method of forming the hole transport layer 50, for example, a vapor deposition material containing an organic material is used. A method of vapor deposition by any appropriate vapor deposition method is used. Examples of the vapor deposition method include a physical vapor deposition method and a chemical vapor deposition method. Examples of the physical vapor deposition method include vacuum vapor deposition method, sputtering, and ion plating. Examples of the chemical vapor deposition (CV D) method include a thermal CV D method, a plasma CV D method, and an optical CV D method. Among these, the vacuum deposition method is preferably used. For example, the hole transport layer 50 is formed after forming the light absorption layer 40. In this case, for example, from the viewpoint of suppressing damage to the light absorption layer, it is preferable to form the film at a low film formation rate by the vacuum evaporation method.

[0060] The hole transport layer 50 (vapor deposition material) contains an organic material as a main component. The content of the organic material in the hole transport layer 50 is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more, further preferably 99% by weight or more, particularly preferably 99. It is at least 5% by weight, most preferably 100% by weight.

[0061] The hole transport layer 50 (vapor deposition material) may contain an additive. Specific examples of the additive include metal salts such as lithium and cobalt (for example, bis (trif I u 〇 romethylsu IT onyl; imide lithium, C oba It (III) tris [bis (trif I uoromethylsu I fonyl) imide]), an acceptor material (eg, tetrafluorotetracyanoquinodimethane (F4 TC NQ)), etc. Another specific example of the additive is 4-tert-buthylpyridien. The hole transport layer 50 (vapor deposition material) contains substantially no dopant.Specifically, the content of the dopant in the hole transport layer (vapor deposition material) is 10% by weight or less. It is more preferably 5% by weight or less, still more preferably 1% by weight or less, particularly preferably 0.5% by weight or less, and most preferably 0% by weight. The performance (conductivity) can be maintained even if the dopant is not substantially contained, and the performance (conductivity) can be maintained even if the dopant is not substantially contained by using the above predetermined organic material. Rate) can be retained. \¥0 2020/174972 19 卩 (: 17 2020 /002820

By forming a vapor-deposited layer, the use of dopant can be suppressed very well.

[0062] Examples of the material for forming the buffer layer (eg, hole injection layer) arranged between the hole transport layer 50 and the second electrode layer 22 include molybdenum oxide (1\/1 〇〇 ₃ )

, Tungsten oxide (\ ^ / 〇 _3), nickel oxide (1 \ 1丨〇), copper oxide (〇 Li 〇)

Examples thereof include metal oxides such as tin oxide (s _n 〇) and halides such as lithium fluoride (preferably fluorides). Among these, it is preferable to include a metal oxide (in particular, molybdenum oxide, nickel oxide). The thickness of the buffer layer is, for example,

Preferably

Is. Examples of the method for forming the buffer layer include a vacuum vapor deposition method.

[0063] The material for forming the anti-reflection layer, for example, 1 \ / 1 _{9 2,} 1_丨, 3 I 0,, include the low refractive index material such as eight I ₂ 〇 _3. The thickness of the antireflection layer is, for example, 5

Is. Any appropriate method can be adopted as a method of forming the antireflection layer. Specifically, when using a IV! 9 ₂ as the material, if example embodiment, an electron beam deposition method is employed.

[0064] Fig. 2 is a schematic cross-sectional view of a photoelectric conversion element in another embodiment of the present invention. The photoelectric conversion element 200 includes a transparent substrate 10, a transparent electrode layer 20, a hole transport layer 50, a light absorbing layer 40 containing a perovskite compound, an electron transport layer 30 and a metal electrode layer 60. In this order. In the illustrated example, as shown by the arrow in the figure, light is incident on the light absorption layer 40 from the side where the transparent electrode layer 20 (transparent substrate 10) is arranged. The transparent substrate 10, the transparent electrode layer 20, the electron transporting layer 30, the light absorbing layer 40 containing the belovskite compound, and the hole transporting layer 50 are as described above.

[0065] Examples of the material for forming the metal electrode layer 60 include metals such as gold, silver, and aluminum. The thickness of the metal electrode layer 60 is typically 100 nm to 50 nm.

The metal electrode layer 60 may be formed by, for example, a grasshopper method, an ion plating method, or the like. 〇 2020/174972 20 卩 (：171? 2020 /002820

A known technique such as the 0 method or resistance heating may be used, and the sputtering method is preferably used from the viewpoint of productivity.

[0066] The photoelectric conversion element 200 is typically manufactured by sequentially laminating each layer on the substrate 10. As shown in FIG. 2, in the form in which the hole transport layer 50 is arranged on the substrate 10 side of the light absorption layer 40, the light absorption layer 40 is formed after the hole transport layer 50 is formed. Can be done. According to such an order, the hole transport layer 50 can be formed without considering the influence (damage or the like) on the light absorption layer 40.

[0067] Fig. 3 is a schematic cross-sectional view of a stacked photoelectric conversion element according to an embodiment of the present invention. The photoelectric conversion element 300 has a first photoelectric conversion unit (top cell) 3 01 and a second photoelectric conversion unit (bottom cell) 30 2 in this order. In the illustrated example, as shown by the arrow in the figure, light is incident from the side where the first photoelectric conversion unit 301 is arranged.

[0068] As one of the photoelectric conversion units constituting the laminated photoelectric conversion element, a perovskite type photoelectric conversion unit having a light absorbing layer containing the above perovskite compound is adopted. In the illustrated example, a perovskite type photoelectric conversion unit is adopted as the first photoelectric conversion unit 301. The first photoelectric conversion unit 301 is arranged on one side of the light absorption layer 40 containing the perovskite compound and the light absorption layer 40, and on the other side of the electron transport layer 30 and the light absorption layer 40. And the hole transport layer 50 is formed. In the illustrated example, the hole transport layer (vapor deposition layer) 50 is disposed on the light incident side of the light absorption layer 40. The electron transport layer 30 includes a blocking layer 31 and a porous carrier layer 32. The details of each layer are as described above.

[0069] Any appropriate photoelectric conversion unit may be adopted as the photoelectric conversion unit (the second photoelectric conversion unit 302 in the illustrated example) combined with the above-mentioned perovskite photoelectric conversion unit. .. Preferably, a photoelectric conversion unit having a bandgap narrower than that of the perovskite type photoelectric conversion unit is used. For example, higher efficiency is expected. A photoelectric conversion unit having a band gap narrower than that of a belovskite type photoelectric conversion unit is, for example, a silicon-based photoelectric conversion unit. 〇 2020/174972 21 卩(：171? 2020/002820

A conversion unit (typically a crystalline silicon-based photoelectric conversion unit) can be mentioned. A crystalline silicon photoelectric conversion unit is typically composed of a crystalline silicon substrate, a first conductive layer arranged on one side of the crystalline silicon substrate, and a second conductive layer arranged on the other side of the crystalline silicon substrate. Have and. The conductivity type of the crystalline silicon substrate may be n-type or n-type. The conductivity type of the first conductive layer and the conductivity type of the second conductive layer are different. Specifically, one is a mold and the other is a door.

[0070] The first conductive layer 71 disposed on the light incident side of the substrate (crystalline silicon substrate) 70 of the second photoelectric conversion unit 302 is the first photoelectric conversion unit 300 Of the second photoelectric conversion unit 302, which has the same conductivity type as the conductive layer (hole transport layer 50) arranged on the light incident side of the second photoelectric conversion unit 302. The conductive layer 72 has the same conductivity type as the conductive layer (electron transport layer 30) arranged on the back side of the first photoelectric conversion unit 30 1. Specifically, the first conductive layer 71 is a type and the second conductive layer 72 is an n type. Therefore, the first photoelectric conversion unit 3001 and the second photoelectric conversion unit 3002 are connected in series, and both have rectifying properties in the same direction.

[0071] Specific examples of the crystalline silicon-based photoelectric conversion unit include a diffusion-type silicon photoelectric conversion unit and a heterojunction silicon photoelectric conversion unit. The diffusion type silicon photoelectric conversion unit is obtained, for example, by diffusing a doping impurity such as boron or phosphorus on the surface of a crystalline silicon substrate to form a conductive layer (conductive type silicon-based semiconductor layer). The heterojunction silicon photoelectric conversion unit is obtained, for example, by forming a non-single crystal silicon thin film such as amorphous silicon or microcrystalline silicon on a single crystal silicon substrate to form a conductive layer. Here, a heterojunction is formed between the single crystal silicon substrate and the non-single crystal silicon thin film. The heterojunction silicon photoelectric conversion unit preferably has an intrinsic silicon based thin film between the single crystal silicon substrate and the conductivity type silicon based thin film. Having an intrinsic silicon thin film enables effective surface passivation while suppressing diffusion of impurities into the single crystal silicon substrate. \¥0 2020/174972 22 卩 (: 17 2020 /002820

It

As the second photoelectric conversion unit (crystalline silicon photoelectric conversion unit) 302, for example, the above heterojunction silicon photoelectric conversion unit is adopted. As the substrate 70, for example, an n-type single crystal silicon substrate is used. Although not shown, the substrate 70 may have a textured structure formed on its surface from the viewpoint of light confinement or the like.

On the light-incident side of the n-type single crystal silicon substrate 70, a type silicon-based thin film (first conductive layer 71) is formed via an intrinsic silicon-based thin film (not shown). On the back side of the single crystal silicon substrate 70 of the mold, a gate type silicon thin film (second conductive layer 72) is formed via an intrinsic silicon thin film (not shown). Here, the intrinsic silicon-based thin film is formed by forming an intrinsic amorphous silicon thin film on the surface of the substrate 70 by any appropriate method from the viewpoint of more effectively performing the above-mentioned surface passivation. It is preferably formed. The thickness of the intrinsic silicon thin film is preferably

Is.

[0074] Examples of the material for forming the conductive type silicon-based thin film (conductive layers 7 1 and 7 2) include amorphous silicon, microcrystalline silicon (a material containing amorphous silicon and crystalline silicon), Amorphous silicon alloy, microcrystalline silicon alloy, etc. are used. Examples of silicon alloys include silicon oxide, silicon carbide, silicon nitride, and silicon germanium. Among these, the conductive silicon-based thin film is preferably an amorphous silicon thin film. The film thickness of the conductive type silicon-based thin film (conductive layers 71, 72) is preferably 3 n 0 1 to 300 0!.

As the photoelectric conversion element 300, for example, a second photoelectric conversion unit 300 2 is prepared in advance, and the second photoelectric conversion unit 300 2 is provided with the first photoelectric conversion unit 300. It is produced by sequentially forming the respective layers constituting 1. In one embodiment, between the first photoelectric conversion unit 30 1 (top cell) and the second photoelectric conversion unit 30 2 (bottom cell), for example, both units are connected. For the purpose of electrical connection and adjustment of the amount of incident light for current matching, the intermediate layer (Fig. 〇 2020/174972 23 卩(：171? 2020/002820

(Not shown) may be provided. In another embodiment, the bottom layer of the top cell (the electron transport layer 30 in the illustrated example) and/or the top layer of the bottom cell (the first conductive layer 71 in the illustrated example) has one of the functions of the intermediate layer. You may have some or all.

[0076] The wavelength range of light absorbed by the light absorbing layer 40 containing the perovskite compound is typically determined by the band gap of the perovskite compound. The band gap of the light absorption layer 40 containing the perovskite compound is 1.556 to 1.756 V from the viewpoint of current matching (with the top cell and the bottom cell) with another photoelectric conversion unit to be combined. It is preferably, and more preferably 1.66 to 1.656 V. For example, the perovskite compound

In order to obtain a bandgap of 1.556 to 1.756 V, it is preferable to set so = 0 ~ 〇.85, and to obtain a bandgap of 1.606 to 1.656 V. = 〇.15 to 〇.

About 55 is preferable.

Although not shown, a transparent electrode layer is typically formed on the light incident surface of the first photoelectric conversion unit 301 arranged on the light incident side (upper side in the figure). From the viewpoint of improving the carrier extraction efficiency, for example, a patterned metal electrode may be further provided on the surface of the transparent electrode layer. A back electrode is provided on the side (back side) opposite to the light incident side of the second photoelectric conversion unit 302. For example, a transparent electrode layer is formed on the back surface of the second photoelectric conversion unit 302, and a back surface metal electrode is provided on this transparent electrode layer to form a back surface electrode.

[0078] Examples of materials for forming the transparent electrode layer include oxides such as zinc oxide (Z _n 〇), tin oxide (S _n 〇 ₂ ), indium oxide (丨门₂ 〇 ₃ ), and indium tin oxide (丨). A composite oxide such as that described above is preferably used. It may also be a material doped with W or Ding丨等to丨n ₂ 〇 ₃ and S N_〇 _2. Since such a transparent conductive oxide has transparency and low resistance, it can efficiently collect photoexcited carriers. The method for forming the transparent electrode layer is preferably the Svatta method or the 1\/100 method. In addition to transparent conductive oxides, fine metal wires such as 9 nanowires, and?巳 0 〇 _ 3 Organic materials such as S can also be used.

When a metal oxide such as To is used as the transparent electrode layer on the light incident side, the photoelectric conversion element preferably has an antireflection layer on the outermost surface thereof. By having the antireflection layer on the outermost surface, it is possible to reduce the difference in refractive index at the air interface, reduce the reflected light, and increase the amount of light taken into the photoelectric conversion element.

The back surface metal electrode may be patterned or planar.

For the back electrode, it is desirable to use a material having a high reflectance for long-wavelength light, high conductivity, and high chemical stability. Examples of materials that satisfy such characteristics include silver, copper, and aluminum. The back electrode is formed by, for example, a printing method, various physical vapor deposition methods, a plating method, or the like.

[0081] Practically, it is preferable that the stacked photoelectric conversion element is modularized. For example, a photoelectric conversion element is sealed between a substrate and a back sheet via a sealing material to form a module. A plurality of units may be connected in series or in parallel via the interconnector and then sealed.

Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The measuring method of each property is as follows unless otherwise specified.

1. Thickness

It was calculated by observing the cross section with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation).

2. Absorption rate

It was measured by an ultraviolet-visible spectrophotometer (L A M B D A manufactured by Perr k i n E I m er).

[0083] [Example 1]

A substrate (made by Pi Ikington, T EC 7) having a transparent conductive film (F TO) formed on a glass substrate was prepared. This substrate was ultrasonically cleaned with ultrapure water, ethanol, and acetone for 10 minutes each, and then dried. Then on the board, The surface was treated with UV ozone for 30 minutes.

[0084] Then, the transparent conductive film side of the substrate (surface processing side), was formed a compact Bok T i 〇 ₂ film having a thickness of 3 1 nm. Specifically, by spraying the solution of titanium diisopropoxide bis(acetylacetonate)/ethanol of 0.3/4.0 vol% on the substrate surface heated to 500 ^° C by the spray pyrolysis method. The film was formed.

[0085] Subsequently, the compact T i 〇 ₂ film side of the substrate, the thickness 350 nm of the mesoporous

It was formed a T i 〇 ₂ film. Specifically, titania best (product name: 18 NR—T, manufactured by T ransparent T itania Paste D yesol) and ethanol were mixed in a volume ratio of 0.7:0.3 and ultrasonic wave was added. Treatment was performed to obtain a dispersion. The dispersion thus obtained is dropped onto a substrate using a micropipette, spin-coated at a speed of 5000 rpm for 30 seconds, and then the substrate is baked in an electric furnace at 500°C for 30 minutes. in was formed mesoporous T i 〇 ₂ film.

[0086] Subsequently, the compact T i 〇 ₂ film (mesoporous T i 〇 ₂ film) side of the substrate, C

_{_{H 3 NH 3 P b I a}} (MAP b I 3) layer was formed with 1 86 nm to 267 nm thickness. Specifically, 1.1 M0MA P bl ₃ /DMS 〇 solution was dropped onto the substrate using a micropipette, and spin coating was performed for 70 seconds at a speed of 1 000 rpm. .. Then, while rotating at a speed of 5000 rpm for 20 seconds, 0.5 m of toluene is dropped using a dropper, and then the substrate is baked at a substrate temperature of 100 ^° C for 10 minutes. As a result, _three black MA P b layers were formed.

[0087] Next, on the MAP b layer ₃ side of the substrate, the following compound (layer) with a thickness of 15 nm: 〇 2020/174972 26 卩 (：171? 2020 /002820

[Chemical 12]

(1 ^~ 1○1\/1○: -5.26V)

An organic material film consisting of was formed by a vacuum deposition method. Specifically, the alumina crucible containing the compound (I) is heated by heating a tungsten wire to sublimate the compound (丨), and the organic material film (absorption peak wavelength:

397 _n , absorption edge wavelength: 440 _n ) was formed into a film.

[0088] Thereafter, the organic material film side of the substrate, the thickness 1 thousand! 1 \ / 1_Rei_0 _three layers of more formed in the vacuum deposition method, and then, the thickness 8 0

I layer was formed by sputtering method. Thus, a photoelectric conversion element (solar cell) was produced.

[Example 2]

Compound (II) instead of compound (丨):

〇 2020/174972 27 卩(: 171-1?2020/002820

[Chemical 13]

(1 ^~ 1 ○ 1\ / 1 :: ^- 5.376 V)

A solar cell was produced in the same manner as in Example 1 except that the organic material film was formed using.

[0090] [Example 3]

Compound (I I I ): instead of compound (丨):

[Chemical 14]

A solar cell was produced in the same manner as in Example 1 except that the organic material film was formed using. \¥0 2020/174972 28 卩(: 17 2020/002820

[0091] [Example 4]

Compound (丨 V) instead of Compound (丨)

[Chemical 15]

(1 ^~ 1 ○ 1\/ 1 :: ^- 5.04 6 V)

After the formation of the organic material film, a residue was confirmed on the evaporation boat.

[0092] [Comparative Example 1]

Instead of compound (丨) when forming organic material film

[Chemical 16]

S pir o-Me TAD (HOMO: -5.1 e V) represented by the following method is used. Furthermore, instead of the vapor deposition method, the organic material film is formed by the solution method (solution coating). A solar cell was produced in the same manner as in Example 1 except for the above. Specifically, chlorobenzene was added to S piro— OMe TAD, bis (trifluor ome thylsulfonyl) imide lithium, Co balt (

III) A solution was prepared by mixing tris [bis (trif i uor ome thylsu I fony I) imide] and 4 — tert- buthy I pyridien, and the resulting solution was spin-coated on the substrate to give MA P b ₃ layers. It was applied on the side and heated at 70 ^° C for 30 minutes to form an organic material film (absorption peak wavelength: 390 nm, absorption edge wavelength: 580 nm).

[0093] <Evaluation method>

Using the solar simulator, the solar cell characteristics of the solar cells obtained in each Example and Comparative Example (short circuit current density (J sc), open circuit voltage (V o c ), curvilinear factor (FF) and conversion efficiency (E ff .))) was measured. The measurement was performed for each of the case where light was incident from the TO layer side and the case where light was incident from the substrate side. The evaluation results are shown in Table 1. The bandgap (E 〇 2020/174972 30 卩(: 171? 2020/002820

9) is an optical bandgap of an organic material film calculated by a spectroscopic ellipsometry (IV! 2000, manufactured by J.A. Woollam Co., Ltd.) using the Tauc-Lorenz model.

[0094] [Table 1]

[0095] Excellent solar cell characteristics were confirmed in each example (for example, even when compared with the values on the substrate side of Comparative Example 1).

[0096] á Measurement of external quantum efficiency ñ

The external quantum efficiency of the solar cells obtained in Example 1 and Comparative Example 1 was measured using a photometric sensitivity measurement device. Figure 4 shows the measurement results.

[0097] An antireflection layer was formed on the surface of the solar cell obtained in Example 1. In concrete terms, it was formed with 1 \ / 1 _{9 2} film having a thickness of 1 1 5 _n by electron beam evaporation method. The external quantum efficiency was measured before and after the formation of the antireflection layer. Figure 5 shows the measurement results.

[0098] As shown in FIG.

A remarkable improvement in sensitivity was confirmed in the range of.

[0099] [Example 5-1]

Compound (V) instead of compound (丨): 〇 2020/174972 卩 (: 171-1? 2020 /002820

[Chemical 17]

(1 ^~ 1 ○ 1\/1 〇:-5.26 V)

Was used to form an organic material film, and instead of forming IV!○ ₃ layers and 丨〇 layers on the organic material film side of the substrate, a thickness of 100

A solar cell was prepared in the same manner as in Example 1 except that the eight layers were formed by resistance heating evaporation.

[0100] [Example 5 -2]

An organic material film with a thickness of 30 _n was formed, and

Except that by interposing a 1 \ / 1_Rei_rei _three layers of thickness 30 N_rei_1 in the same manner as in Example 5-1 between, to produce a solar cell.

[0101] [Example 5 -3]

Instead of forming an 8-layer on the organic material film side of the substrate, a 80-nm-thick layer was formed by the sputtering method, and then a 1001-thick-layer 89 layer was formed by a vacuum evaporation method. A solar cell was produced in the same manner as in Example 5_2 except for the above.

[0102] [Reference example 5 -4]

Similarly except that the film formation of the organic material film having a thickness of 1 1 0 _n m is as in Example 5 _ 1 \¥02020/174972 32 卩 (: 17 2020 /002820

Then, a solar cell was produced.

[0103] <Evaluation method>

Using a solar simulator, the solar cell characteristics (short-circuit current density (“30)), open-circuit voltage (V 〇, fill factor (), and conversion efficiency (day † I)) of the solar cells obtained in each example were measured. The measurement was performed with light incident from the substrate side, and the evaluation results are shown in Table 2.

[0104] [Table 2]

[0105] In Examples 5_1 to 5-4. The organic material film contains no dopant. Example 5_4, in which the thickness of the organic material film is large, is inferior to the other solar cell characteristics.

From the comparison between Example 5-2 and Example 5-3, it is considered that the combination of 1\/1 〇 ₃ layers / 丨〇 layer is preferable. Explanation of symbols

[0106] 1 ○. Substrate (transparent substrate)

20. Transparent electrode layer

2 1. Electrode layer

22. Electrode layer

30. Electron transport layer

3 1. Blocking layer

32. Porous carrier layer

40. Light absorption layer

50. Hole transport layer 4972 33 ?01/1?2020/002820

〇. Metal electrode layer

〇.Substrate

1. First conductive layer

2. Second conductive layer

0. Photoelectric conversion element

1. First photoelectric conversion unit

2. Second photoelectric conversion unit

Claims

\0 2020/174972 34 卩(: 17 2020/002820 Scope [Claim 1] A light absorbing layer containing a compound having a belovskite structure, and an electron transporting layer disposed on one side of the light absorbing layer. A hole transport layer disposed on the other side of the light absorption layer, wherein the hole transport layer contains an organic material, has a thickness of 50 nm or less, and has an absorption peak wavelength of 400 nm. The following vapor deposition layer, wherein the organic material is represented by the following general formula (1):

[Chemical 1]

(In the formula, 8 represents a hydrogen atom or an organic group,

² is the same or different and represents a substituent,

Are the same or different and represent a substituent consisting of an organic group containing no nitrogen, 01 1 represents an integer of 0 to 4, 0 12 represents an integer of 0 to 2, 111 3 represents an integer of 0 to 4. Represent ) And/or the general formula (2):

〇 2020/174972 35 2020/002820

[Chemical 2]

(In the formula, 8 represents a hydrogen atom or an organic group,

⁵ is the same or different and represents a substituent consisting of a nitrogen-free organic group,

Are the same or different and represent a substituent,

, 5 represents an integer of 0 to 3, and 0! 6 represents an integer of 0 to 3. ) Is a compound represented by

Light is incident on the light absorption layer from the side where the hole transport layer is arranged,

Photoelectric conversion element.

2. The photoelectric conversion element according to claim 1, wherein the hole transport layer has an absorption edge wavelength of 450 n or less.

[Claim 3] The photoelectric conversion element according to claim 1 or 2, wherein the organic material has a molecular weight of 270 or more and 200 or less.

4. The hole transport layer is substantially free of a dopant.

4. The photoelectric conversion element according to any one of 3.

5. The photoelectric conversion element according to claim 1, further comprising a transparent electrode arranged on a side of the hole transport layer opposite to a side on which the light absorption layer is arranged.

6. The photoelectric conversion element according to claim 5, further comprising a buffer layer arranged between the hole transport layer and the transparent electrode. 〇 2020/174972 36 卩 (：171? 2020 /002820

7. The photoelectric conversion element according to claim 1, further comprising a transparent electrode arranged on a side of the electron transport layer opposite to a side on which the light absorption layer is arranged.

[Claim 8] further comprising another photoelectric conversion unit for photoelectric conversion

7. The photoelectric conversion element according to any one of 7.

9. The photoelectric conversion element according to claim 8, wherein the other photoelectric conversion unit includes a crystalline silicon substrate.

10. A light absorption layer containing a compound having a belovskite structure is formed on one side of a substrate, and

Depositing a vapor deposition material containing an organic material on one side of the substrate to form a hole transport layer having a thickness of 50 or less and an absorption peak wavelength of 400 n or less;

The organic material has the following general formula (1):

[Chemical 3]

(In the formula, 8 represents a hydrogen atom or an organic group,

² is the same or different and represents a substituent,

, 2 represents an integer of 0 to 2, and 0! 3 represents an integer of 0 to 4. ) And/or the general formula (2): 〇 2020/174972 37 卩(：171? 2020/002820

[Chemical 4]

(In the formula, 8 represents a hydrogen atom or an organic group,

Are the same or different and represent a substituent,

Method for manufacturing photoelectric conversion element.

11. The method for manufacturing a photoelectric conversion element according to claim 10, further comprising forming a transparent electrode on a side of the hole transport layer opposite to a side on which the light absorption layer is arranged.