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CN-122029970-A - Photoelectric conversion element and solar cell module

CN122029970ACN 122029970 ACN122029970 ACN 122029970ACN-122029970-A

Abstract

The purpose of the present invention is to provide a photoelectric conversion element that exhibits excellent photoelectric conversion characteristics and that has little fluctuation. The photoelectric conversion element 10 according to an embodiment of the present invention has a structure in which a first electrode 12, a hole transport layer 13, a photoelectric conversion layer 14, an electron transport layer 15, and a second electrode 16 are stacked in this order. The photoelectric conversion layer 14 contains a perovskite compound. The hole transport layer 13 contains an insulating compound and a single molecule hole transport material. The hole transport material contains a compound represented by the following chemical formula (I). Ar 1 -(L 1 -X 1 ) n. (I) in the chemical formula (I), ar 1 is a structure including an aromatic ring, a heteroatom may be included in an atom constituting the aromatic ring, and Ar 1 may have a substituent other than-L 1 -X 1 . n is an integer of 1 or more, and when n is 2 or more, the structures represented by-L 1 -X 1 may be the same or different from each other. L 1 is a divalent linking group or a single bond that bonds Ar 1 to X 1 . X 1 is a group capable of forming a chemical bond or hydrogen bond with the p-type metal oxide semiconductor.

Inventors

  • KANEKO KOJI
  • NISHITANI KOICHI

Assignees

  • 株式会社安能科多科技

Dates

Publication Date
20260512
Application Date
20241121
Priority Date
20231122

Claims (12)

  1. 1. A photoelectric conversion element is characterized in that a first electrode, a hole transport layer, a photoelectric conversion layer and a second electrode are directly or indirectly laminated in this order, The photoelectric conversion layer contains a perovskite compound, The hole transport layer comprises an insulating compound contacting with the main surface of the first electrode on the side of the photoelectric conversion layer and a compound represented by the following chemical formula (I), Ar 1 -(L 1 -X 1 )n...(I) In the chemical formula (I), ar 1 is a structure including an aromatic ring, a hetero atom may be included in atoms constituting the aromatic ring, ar 1 may have a substituent other than-L 1 -X 1 , n is an integer of 1 or more, when n is 2 or more, the structures represented by-L 1 -X 1 may be the same or different from each other, L 1 is a divalent linking group or a single bond bonding Ar 1 and X 1 , and X 1 is a group capable of forming a chemical bond or a hydrogen bond with the first electrode.
  2. 2. The photoelectric conversion element according to claim 1, wherein the hole transport layer contains a compound represented by the following chemical formula (II), A 1 -L 2 -X 2 ...(II) A 1 is an atomic group containing one or more substituents or structures selected from the group consisting of alkoxy, hydroxy, carboxyl, dihydroxyphosphoryl, dialkylphosphoryl, hydroxysulfonyl, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, monoalkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonyloxy, alkoxycarbonyl, aminocarbonyl, aminocarbonylamino, alkylcarbonylamino, alkylsulfonylamino, aminosulfonyl, and nitrogen-containing heterocyclic group, L 2 is a divalent linking group or a single bond bonding A 1 to X 2 , and X 2 is a group capable of forming a chemical bond or a hydrogen bond with the first electrode.
  3. 3. The photoelectric conversion element according to claim 1 or 2, wherein the compound represented by the formula (I) forms a monolayer.
  4. 4. The photoelectric conversion element according to claim 1 or 2, wherein the insulating compound is at least one or more selected from a metal oxide, a metal asphyxiation compound, an insulating organic compound, and an organic-inorganic hybrid compound.
  5. 5. The photoelectric conversion element according to claim 4, wherein the insulating compound is in a particle shape.
  6. 6. The photoelectric conversion element according to claim 5, wherein an average particle diameter of the insulating compound is in a range of 1 nm to 200 nm.
  7. 7. The photoelectric conversion element according to claim 1 OR 2, wherein X 1 in the chemical formula (I) is selected from the group consisting of dihydroxyphosphoryl group (-p=o (OH) 2 ), carboxyl group (-COOH), sulfo group (-SO 3 H), boric acid group (-B (OH) 2 ), silane trihalide group (-SiX 3 , where X is a halo group), trialkoxysilane group (-Si (OR) 3 , where R is an alkyl group), trihydroxysilane group, dialkylphosphoryl group, respectively.
  8. 8. The photoelectric conversion element according to claim 2, wherein X 2 in the chemical formula (II) is each independently selected from the group consisting of dihydroxyphosphoryl (-p=o (OH) 2 ), carboxyl (-COOH), sulfo (-SO 3 H), boric acid (-B (OH) 2 ), silane trihalide (-SiX 3 , wherein X is a halo group), trialkoxysilane (-Si (OR) 3 , wherein R is an alkyl group), trihydroxysilane group, dialkylphosphoryl group.
  9. 9. The photoelectric conversion element according to claim 1 or 2, wherein the perovskite compound is an organic-inorganic perovskite compound.
  10. 10. The photoelectric conversion element according to claim 1 or 2, wherein a mass ratio of the mass (m 1) of the compound represented by the chemical formula (I) to the mass (m 2) of the insulating compound satisfies the following formula (A), m1/m2=1/10~1/20000 (A)。
  11. 11. The photoelectric conversion element according to claim 1 or 2, wherein an intermediate layer containing nickel oxide is formed between the first electrode and the hole transport layer.
  12. 12. A solar cell module comprising the photoelectric conversion element according to claim 1 or 2.

Description

Photoelectric conversion element and solar cell module Technical Field The present invention relates to a photoelectric conversion element and a solar cell module. Background In recent years, solar power generation has been attracting attention as a clean energy source, and development of solar cells has been advancing. As one of them, a solar cell using a perovskite material for a light absorbing layer is receiving rapid attention as a next-generation solar cell that can be manufactured at low cost. For example, non-patent document 1 reports a solution type solar cell in which a perovskite material is used for a light absorbing layer. In addition, non-patent document 2 reports that solid perovskite solar cells exhibit high efficiency. As a basic structure of a perovskite solar cell, a sequential structure in which an electron transport layer, a light absorption layer (perovskite layer), a hole transport layer (also referred to as an electron hole (hole) transport layer), and a back electrode are sequentially stacked on an electrode, and an inverted structure in which a hole transport layer, a light absorption layer, an electron transport layer, and a back electrode are sequentially stacked on an electrode are known. An electron transport layer comprising a porous shape is sometimes included between the electron transport layer and the perovskite layer. Among them, a hole transporting material of an organic semiconductor is generally used for the hole transporting layer (for example, non-patent document 3 to non-patent document 10). Prior art literature Non-patent literature Non-patent document 1, journal of THE AMERICAN CHEMICAL Society of chemistry, 2009,131,6050-6051. Non-patent document 2, science, 2012,388,643-647. Non-patent document 3, applied materials and Interfaces of American society of chemistry (ACS appl. Mater. Interfaces), 2017,9,24778-24787. Non-patent document 4, "Energy science (Sci.)," 2014,7,1454-1460. Non-patent document 5 J.Material chemistry (J. Mater. Chem.) A, 2014,2,6305-6309. Non-patent document 6 J.Material chemistry (J. Mater. Chem.) A, 2015,3,12139-12144. Non-patent document 7 J.Material chemistry (J. Mater. Chem.) A, 2018,6,7950-7958. Non-patent document 8, applied materials and Interfaces of American society of chemistry (ACS appl. Mater. Interfaces), 2015,7,11107-11116. Non-patent document 9, energy and environmental science (Environmental Science) 2014,7,2963-2967. Non-patent document 10, advanced Energy materials (adv. Energy mater.), "2018,8,1801892. Disclosure of Invention Problems to be solved by the invention However, the photoelectric conversion efficiency of the conventional perovskite solar cell cannot be said to be sufficient. In order to improve the photoelectric conversion efficiency of the solar cell, it is particularly important to improve the characteristics of the hole transport layer. As hole transporting materials for the hole transporting layer, for example, a trimeric indene (truxene) compound (non-patent document 3), a diketopyrrolopyrrole compound (non-patent document 4), a thiophene compound (non-patent document 5, non-patent document 6), a dithienopyrrole (non-patent document 7), and the like have been reported so far. However, few compounds capable of exhibiting photoelectric conversion efficiency sufficient for perovskite-type solar cells have been reported. Thus, there has been proposed [2,2', 7' -tetrakis (N, N-di-p-methoxyphenylamino) -9,9'-spirobifluorene ] ([ 2,2', 7'-tetrakis (N, N-di-p-methoxyphenylamino) -9,9' -spirobifluorene ], spira-ome tad) which has been developed as a hole transport material for dye-sensitized solar cells, but it is known that the heat resistance is low (non-patent document 8). In addition, it is known that a polymer material having a triphenylamine skeleton called PTAA (poly [ bis (4-phenyl) (2, 4, 6-TRIMETHYLPHENYL) amine ]) (poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]) is also low in light resistance. Further, when these materials are used as a hole transport material for a p-buffer layer, it is necessary to add lithium bis (trifluoromethanesulfonyl) imide (bis (trifluoromethanesulfonyl) imide lithium, liTFSI) salt as an additive to improve conductivity, which is considered to be one of the causes of element degradation (non-patent document 9). In addition, carbazole-type hole transport materials having phosphonic acid have been reported in recent years (non-patent document 10). The compound reacts with an Indium Tin Oxide (ITO) compound used as a transparent electrode to form a monolayer on the transparent electrode. As for such a hole transport compound forming a monolayer, a compound having a photoelectric conversion efficiency exceeding 20% and being extremely excellent has been reported, but in the case where the hole transport layer is insufficient in coating property on an electrode, the electrode comes into contact with the photoelectric conversion layer, which may cause deterioration of photoele