JP6725221B2 - Thin film solar cell - Google Patents
Thin film solar cell Download PDFInfo
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- JP6725221B2 JP6725221B2 JP2015152799A JP2015152799A JP6725221B2 JP 6725221 B2 JP6725221 B2 JP 6725221B2 JP 2015152799 A JP2015152799 A JP 2015152799A JP 2015152799 A JP2015152799 A JP 2015152799A JP 6725221 B2 JP6725221 B2 JP 6725221B2
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- Prior art keywords
- transport layer
- photoelectric conversion
- organic
- layer
- electron transport
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 150000001875 compounds Chemical class 0.000 claims description 42
- 230000005525 hole transport Effects 0.000 claims description 33
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- 239000002184 metal Substances 0.000 claims description 13
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- 239000010408 film Substances 0.000 description 16
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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Description
本発明は、光を照射し続けることによる光電変換効率の低下（光劣化）が抑制された薄膜太陽電池に関する。 The present invention relates to a thin film solar cell in which a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light is suppressed.
従来から、対向する電極間にＮ型半導体層とＰ型半導体層とを配置した積層体を備えた光電変換素子が開発されている。このような光電変換素子では、光励起により光キャリアが生成し、電子がＮ型半導体を、ホールがＰ型半導体を移動することで、電界が生じる。 BACKGROUND ART Conventionally, a photoelectric conversion element including a laminated body in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between opposing electrodes has been developed. In such a photoelectric conversion element, photocarriers are generated by photoexcitation, electrons move in the N-type semiconductor, and holes move in the P-type semiconductor, thereby generating an electric field.
現在、実用化されている光電変換素子の多くは、シリコン等の無機半導体を用いて製造される無機太陽電池である。しかしながら、無機太陽電池は製造にコストがかかるうえ大型化が困難であり、利用範囲が限られてしまうことから、無機半導体の代わりに有機半導体を用いて製造される有機太陽電池が注目されている。 Most of the photoelectric conversion elements currently in practical use are inorganic solar cells manufactured using an inorganic semiconductor such as silicon. However, since inorganic solar cells are expensive to manufacture and difficult to increase in size, and the range of use is limited, organic solar cells manufactured using organic semiconductors instead of inorganic semiconductors are receiving attention. ..
有機太陽電池においては、ほとんどの場合フラーレンが用いられている。フラーレンは、主にＮ型半導体として働くことが知られている。例えば、特許文献１には、Ｐ型半導体となる有機化合物とフラーレン類とを用いて形成された半導体ヘテロ接合膜が記載されている。しかしながら、フラーレンを用いて製造される有機太陽電池において、その劣化の原因はフラーレンであることが知られており（例えば、非特許文献１参照）、フラーレンに代わる材料が求められている。 In most of the organic solar cells, fullerenes are used. Fullerenes are known to act mainly as N-type semiconductors. For example, Patent Document 1 describes a semiconductor heterojunction film formed using an organic compound that becomes a P-type semiconductor and fullerenes. However, in organic solar cells manufactured using fullerenes, it is known that the cause of deterioration is fullerenes (for example, refer to Non-Patent Document 1), and a material replacing fullerenes is required.
そこで近年、有機無機ハイブリッド半導体と呼ばれる、中心金属に鉛、スズ等を用いたペロブスカイト構造を有する光電変換材料が発見され、高い光電変換効率を有することが示された（例えば、非特許文献２）。 Therefore, in recent years, a photoelectric conversion material having a perovskite structure using lead, tin, or the like as a central metal, which is called an organic-inorganic hybrid semiconductor, was discovered and shown to have high photoelectric conversion efficiency (for example, Non-Patent Document 2). ..
本発明者らは、陰極、電子輸送層、光電変換層、ホール輸送層及び陽極がこの順に積層された構造を有する薄膜太陽電池において、光電変換層に有機無機ペロブスカイト化合物を用いることを検討した。有機無機ペロブスカイト化合物を用いることにより、薄膜太陽電池の光電変換効率の向上が期待できる。
しかしながら、光電変換層が有機無機ペロブスカイト化合物を含む薄膜太陽電池は、光照射を開始した直後は高い光電変換効率を示すものの、光を照射し続けると光電変換効率が低下していくことが新たに明らかとなった（光劣化）。
The present inventors examined the use of an organic-inorganic perovskite compound for the photoelectric conversion layer in a thin film solar cell having a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and an anode are laminated in this order. By using the organic-inorganic perovskite compound, improvement in photoelectric conversion efficiency of the thin film solar cell can be expected.
However, a thin-film solar cell in which the photoelectric conversion layer contains an organic-inorganic perovskite compound shows high photoelectric conversion efficiency immediately after the start of light irradiation, but the photoelectric conversion efficiency decreases anew when light irradiation is continued. It became clear (light deterioration).
本発明は、上記現状に鑑み、光を照射し続けることによる光電変換効率の低下（光劣化）が抑制された薄膜太陽電池を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a thin-film solar cell in which a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light is suppressed.
本発明は、陰極、電子輸送層、光電変換層、ホール輸送層及び陽極がこの順に積層された構造を有する薄膜太陽電池であって、前記電子輸送層は薄膜状の電子輸送層と、多孔質状の電子輸送層とを有し、前記光電変換層は、一般式Ｒ−Ｍ−Ｘ３（但し、Ｒは有機分子、Ｍは金属原子、Ｘはハロゲン原子又はカルコゲン原子である。）で表される有機無機ペロブスカイト化合物を含み、前記薄膜状の電子輸送層の厚みが１００ｎｍ以上、前記ホール輸送層の厚みが１００ｎｍ以上であり、かつ、前記光電変換層の前記電子輸送層又は前記ホール輸送層に接する側の少なくとも一方の表面の算術平均粗さＲａが５０ｎｍ以下である薄膜太陽電池である。
以下に本発明を詳述する。
The present invention is a thin-film solar cell having a structure in which a cathode, an electron-transporting layer, a photoelectric conversion layer, a hole-transporting layer, and an anode are laminated in this order, wherein the electron-transporting layer is a thin-film electron-transporting layer and is porous. and a Jo electron transporting layer, the photoelectric conversion layer has the general formula R-M-X 3 (where, R represents an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom.) Table A thin film electron transport layer having a thickness of 100 nm or more, the hole transport layer having a thickness of 100 nm or more, and the electron transport layer or the hole transport layer of the photoelectric conversion layer. The thin-film solar cell has an arithmetic average roughness Ra of 50 nm or less on at least one surface in contact with.
The present invention will be described in detail below.
本発明者らは、陰極、電子輸送層、有機無機ペロブスカイト化合物を含む光電変換層、ホール輸送層及び陽極がこの順に積層された構造を有する薄膜太陽電池において、該電子輸送層が薄膜状の電子輸送層と多孔質状の電子輸送層とを有する場合、上記電子輸送層及びホール輸送層の厚みを一定の厚さとするとともに、光電変換層の電子輸送層又はホール輸送層に接する側の少なくとも一方の表面の算術平均粗さＲａを一定以下とすることにより、光を照射し続けることによる光電変換効率の低下（光劣化）を抑制できることを見出し、本発明を完成させるに至った。 The inventors have prepared a thin film solar cell having a structure in which a cathode, an electron transport layer, a photoelectric conversion layer containing an organic-inorganic perovskite compound, a hole transport layer, and an anode are laminated in this order, and the electron transport layer is a thin film electron. When having a transporting layer and a porous electron transporting layer, the thickness of the electron transporting layer and the hole transporting layer is set to a constant thickness, and at least one of the sides of the photoelectric conversion layer in contact with the electron transporting layer or the hole transporting layer. It was found that the reduction of the photoelectric conversion efficiency (photodegradation) due to the continuous irradiation of light can be suppressed by setting the arithmetic average roughness Ra of the surface to a certain level or less, and the present invention has been completed.
本発明の薄膜太陽電池は、陰極、電子輸送層、光電変換層、ホール輸送層及び陽極がこの順に積層された構造を有する。
なお、本明細書中、「層」とは、明確な境界を有する層だけではなく、含有元素が徐々に変化する濃度勾配のある層をも意味する。なお、層の元素分析は、例えば、薄膜太陽電池の断面のＦＥ−ＴＥＭ／ＥＤＳ線分析測定を行い、特定元素の元素分布を確認する等によって行うことができる。また、本明細書中、層とは、平坦な薄膜状の層だけではなく、他の層と一緒になって複雑に入り組んだ構造を形成しうる層をも意味する。
The thin film solar cell of the present invention has a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, a hole transport layer, and an anode are laminated in this order.
In the present specification, the term “layer” means not only a layer having a clear boundary but also a layer having a concentration gradient in which the contained element gradually changes. The elemental analysis of the layer can be performed by, for example, performing FE-TEM/EDS line analysis measurement of the cross section of the thin film solar cell and confirming the elemental distribution of the specific element. Further, in the present specification, the layer means not only a flat thin film-like layer but also a layer capable of forming a complicated and complicated structure together with other layers.
上記光電変換層は、一般式Ｒ−Ｍ−Ｘ３（但し、Ｒは有機分子、Ｍは金属原子、Ｘはハロゲン原子又はカルコゲン原子である。）で表される有機無機ペロブスカイト化合物を含む。
上記光電変換層に上記有機無機ペロブスカイト化合物を用いることにより、薄膜太陽電池の光電変換効率を向上させることができる。
The photoelectric conversion layer has the general formula R-M-X 3 (where, R represents an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom.) Containing an organic-inorganic perovskite compound represented by.
By using the organic-inorganic perovskite compound in the photoelectric conversion layer, the photoelectric conversion efficiency of the thin film solar cell can be improved.
上記Ｒは有機分子であり、ＣｌＮｍＨｎ（ｌ、ｍ、ｎはいずれも正の整数）で示されることが好ましい。
上記Ｒは、具体的には例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、エチルメチルアミン、メチルプロピルアミン、ブチルメチルアミン、メチルペンチルアミン、ヘキシルメチルアミン、エチルプロピルアミン、エチルブチルアミン、イミダゾール、アゾール、ピロール、アジリジン、アジリン、アゼチジン、アゼト、イミダゾリン、カルバゾール、メチルカルボキシアミン、エチルカルボキシアミン、プロピルカルボキシアミン、ブチルカルボキシアミン、ペンチルカルボキシアミン、ヘキシルカルボキシアミン、ホルムアミジニウム、グアニジン、アニリン、ピリジン及びこれらのイオン（例えば、メチルアンモニウム（ＣＨ３ＮＨ３）等）やフェネチルアンモニウム等が挙げられる。なかでも、メチルアミン、エチルアミン、プロピルアミン、プロピルカルボキシアミン、ブチルカルボキシアミン、ペンチルカルボキシアミン、ホルムアミジニウム、グアニジン及びこれらのイオンが好ましく、メチルアミン、エチルアミン、ペンチルカルボキシアミン、ホルムアミジニウム、グアニジン及びこれらのイオンがより好ましい。中でも高い光電変換効率が得られることから、メチルアミン、ホルムアミニジウム及びこれらのイオンが更に好ましい。
The above R is an organic molecule and is preferably represented by C 1 N m H n (where l, m and n are all positive integers).
Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl. Amine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, Azetidine, azeto, imidazoline, carbazole, methylcarboxyamine, ethylcarboxyamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, hexylcarboxyamine, formamidinium, guanidine, aniline, pyridine and their ions (for example, methyl ammonium). (CH 3 NH 3 ), etc. and phenethyl ammonium. Among them, methylamine, ethylamine, propylamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, guanidine and these ions are preferable, and methylamine, ethylamine, pentylcarboxyamine, formamidinium, guanidine and These ions are more preferable. Among them, methylamine, formamidinium and these ions are more preferable because they can obtain high photoelectric conversion efficiency.
上記Ｍは金属原子であり、例えば、鉛、スズ、亜鉛、チタン、アンチモン、ビスマス、ニッケル、鉄、コバルト、銀、銅、ガリウム、ゲルマニウム、マグネシウム、カルシウム、インジウム、アルミニウム、マンガン、クロム、モリブデン、ユーロピウム等が挙げられる。なかでも、電子軌道の重なりの観点から、鉛又はスズが好ましい。これらの金属原子は単独で用いられてもよく、２種以上が併用されてもよい。 The M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, Examples include europium. Among them, lead or tin is preferable from the viewpoint of overlapping electron orbits. These metal atoms may be used alone or in combination of two or more.
上記Ｘはハロゲン原子又はカルコゲン原子であり、例えば、塩素、臭素、ヨウ素、硫黄、セレン等が挙げられる。これらのハロゲン原子又はカルコゲン原子は単独で用いられてもよく、２種以上が併用されてもよい。なかでも、構造中にハロゲンを含有することで、上記有機無機ペロブスカイト化合物が有機溶媒に可溶になり、安価な印刷法等への適用が可能になることから、ハロゲン原子が好ましい。更に、上記有機無機ペロブスカイト化合物のエネルギーバンドギャップが狭くなることから、ヨウ素がより好ましい。 The above X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among them, the halogen atom is preferable since the organic-inorganic perovskite compound becomes soluble in the organic solvent by containing halogen in the structure, and the application to an inexpensive printing method or the like becomes possible. Furthermore, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound is narrowed.
上記有機無機ペロブスカイト化合物は、体心に金属原子Ｍ、各頂点に有機分子Ｒ、面心にハロゲン原子又はカルコゲン原子Ｘが配置された立方晶系の構造を有することが好ましい。
図１は、体心に金属原子Ｍ、各頂点に有機分子Ｒ、面心にハロゲン原子又はカルコゲン原子Ｘが配置された立方晶系の構造である、有機無機ペロブスカイト化合物の結晶構造の一例を示す模式図である。詳細は明らかではないが、上記構造を有することにより、結晶格子内の八面体の向きが容易に変わることができるため、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、薄膜太陽電池の光電変換効率が向上すると推定される。
The organic-inorganic perovskite compound preferably has a cubic structure in which a metal atom M is arranged in the body center, an organic molecule R is arranged in each vertex, and a halogen atom or a chalcogen atom X is arranged in the face center.
FIG. 1 shows an example of a crystal structure of an organic-inorganic perovskite compound having a cubic structure in which a metal atom M is arranged in the body center, an organic molecule R is arranged at each vertex, and a halogen atom or a chalcogen atom X is arranged in the face center. It is a schematic diagram. Although details are not clear, since the orientation of the octahedron in the crystal lattice can be easily changed by having the above structure, the mobility of electrons in the organic-inorganic perovskite compound becomes high, and thus the thin film solar cell It is estimated that the photoelectric conversion efficiency is improved.
上記有機無機ペロブスカイト化合物は、結晶性半導体であることが好ましい。結晶性半導体とは、Ｘ線散乱強度分布を測定し、散乱ピークが検出できる半導体を意味している。
上記有機無機ペロブスカイト化合物が結晶性半導体であれば、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、薄膜太陽電池の光電変換効率が向上する。また、上記有機無機ペロブスカイト化合物が結晶性半導体であれば、薄膜太陽電池に光を照射し続けることによる光電変換効率の低下（光劣化）、特に短絡電流の低下に起因する光劣化が抑制されやすくなる。
The organic-inorganic perovskite compound is preferably a crystalline semiconductor. The crystalline semiconductor means a semiconductor whose X-ray scattering intensity distribution can be measured and whose scattering peak can be detected.
When the organic-inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound is high, and the photoelectric conversion efficiency of the thin-film solar cell is improved. Further, if the organic-inorganic perovskite compound is a crystalline semiconductor, the photoelectric conversion efficiency reduction (photodegradation) due to continuous irradiation of light to the thin-film solar cell (photodegradation), particularly the photodegradation resulting from the reduction of the short-circuit current, is easily suppressed. Become.
また、結晶化の指標として結晶化度を評価することもできる。結晶化度は、Ｘ線散乱強度分布測定により検出された結晶質由来の散乱ピークと非晶質部由来のハローとをフィッティングにより分離し、それぞれの強度積分を求めて、全体のうちの結晶部分の比を算出することにより求めることができる。
上記有機無機ペロブスカイト化合物の結晶化度の好ましい下限は３０％である。上記結晶化度が３０％以上であれば、上記有機無機ペロブスカイト化合物中の電子の移動度が高くなり、薄膜太陽電池の光電変換効率が向上する。また、上記結晶化度が３０％以上であれば、薄膜太陽電池に光を照射し続けることによる光電変換効率の低下（光劣化）、特に短絡電流の低下に起因する光劣化が抑制されやすくなる。上記結晶化度のより好ましい下限は５０％、更に好ましい下限は７０％である。
また、上記有機無機ペロブスカイト化合物の結晶化度を上げる方法として、例えば、熱アニール（加熱処理）、レーザー等の強度の強い光の照射、プラズマ照射等が挙げられる。
Also, the crystallinity can be evaluated as an index of crystallization. The degree of crystallinity is determined by separating the scattering peak derived from a crystalline material detected by X-ray scattering intensity distribution measurement and the halo derived from an amorphous portion by fitting, and calculating the respective intensity integrals to determine the crystalline portion of the whole. It can be determined by calculating the ratio.
A preferable lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. When the crystallinity is 30% or more, the mobility of electrons in the organic-inorganic perovskite compound is high, and the photoelectric conversion efficiency of the thin film solar cell is improved. Further, when the crystallinity is 30% or more, it is easy to suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light to the thin-film solar cell (photodegradation), particularly a photodegradation resulting from a reduction in short-circuit current. .. The more preferable lower limit of the crystallinity is 50%, and the still more preferable lower limit thereof is 70%.
Examples of methods for increasing the crystallinity of the organic-inorganic perovskite compound include thermal annealing (heat treatment), irradiation with intense light such as laser, and plasma irradiation.
上記光電変換層には、上記有機無機ペロブスカイト化合物に加え、周期表２族元素、周期表１１族元素、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタンからなる群より選択される少なくとも１種の元素を更に含むことが好ましい。
上記光電変換層が有機無機ペロブスカイト化合物と、上記の元素とを含むことにより、薄膜太陽電池に光を照射し続けることによるより光電変換効率の低下（光劣化）、特に短絡電流とフィルファクターの低下に起因する光劣化が抑制される。
上記周期表２族元素、周期表１１族元素、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタンからなる群より選択される少なくとも１種の元素として、具体的には例えば、カルシウム、ストロンチウム、銀、銅、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタン等が挙げられる。なかでも、カルシウム、ストロンチウム、銀、銅、ネオジム、イリジウムが好ましい。また初期変換効率も高くなるという観点からは、カルシウム、ストロンチウム、銀、銅、マンガン、ランタンがより好ましく、カルシウム、ストロンチウム、銀、銅が特に好ましい。
In the photoelectric conversion layer, in addition to the organic-inorganic perovskite compound, at least one element selected from the group consisting of elements of
When the photoelectric conversion layer contains an organic-inorganic perovskite compound and the above-mentioned element, the photoelectric conversion efficiency is further reduced (photodegradation) by continuing to irradiate the thin-film solar cell with light, especially the short-circuit current and the fill factor are reduced. The photodegradation due to is suppressed.
As the at least one element selected from the group consisting of the elements of
上記周期表２族元素、周期表１１族元素、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタンからなる群より選択される少なくとも１種の元素の含有量の割合（モル％）は特に限定されないが、上記有機無機ペロブスカイト化合物中の金属元素（Ｒ−Ｍ−Ｘ３で表されるＭ）１００に対する好ましい下限が０．０１、好ましい上限が２０である。上記含有量の割合（モル％）が０．０１以上であれば、薄膜太陽電池に光を照射し続けることによる光電変換効率の低下（光劣化）、特に短絡電流密度、フィルファクターの低下に起因する光劣化が抑制される。上記含有量の割合（モル％）が２０以下であれば、上記元素の存在による初期変換効率低下を抑制することができる。上記含有量の割合（モル％）のより好ましい下限は０．１、より好ましい上限は１０である。
The proportion (mol %) of the content of at least one element selected from the group consisting of the elements of
上記有機無機ペロブスカイト化合物に上記周期表２族元素、周期表１１族元素、アンチモン、マンガン、ネオジム、イリジウム、チタン及びランタンからなる群より選択される少なくとも１種の元素を含有させる方法は特に限定されず、例えば、有機無機ペロブスカイト化合物の層を成膜する際に使用する溶液に上記元素のハロゲン化物を混合しておく方法等が挙げられる。
The method of incorporating the above-mentioned organic-inorganic perovskite compound with at least one element selected from the group consisting of elements of
上記光電変換層は、本発明の効果を損なわない範囲内であれば、上記有機無機ペロブスカイト化合物に加えて、更に、有機半導体又は無機半導体を含んでいてもよい。
上記有機半導体として、例えば、ポリ（３−アルキルチオフェン）等のチオフェン骨格を有する化合物等が挙げられる。また、例えば、ポリパラフェニレンビニレン骨格、ポリビニルカルバゾール骨格、ポリアニリン骨格、ポリアセチレン骨格等を有する導電性高分子等も挙げられる。更に、例えば、フタロシアニン骨格、ナフタロシアニン骨格、ペンタセン骨格、ベンゾポルフィリン骨格等のポルフィリン骨格、スピロビフルオレン骨格等を有する化合物や、表面修飾されていてもよいカーボンナノチューブ、グラフェン、フラーレン等のカーボン含有材料も挙げられる。
The photoelectric conversion layer may further contain an organic semiconductor or an inorganic semiconductor in addition to the organic-inorganic perovskite compound as long as the effect of the present invention is not impaired.
Examples of the organic semiconductor include compounds having a thiophene skeleton such as poly(3-alkylthiophene). Further, for example, a conductive polymer having a polyparaphenylenevinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, or the like can be given. Furthermore, for example, a compound having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, or a spirobifluorene skeleton, or a carbon nanotube that may be surface-modified, graphene, a carbon-containing material such as fullerene Can also be mentioned.
上記無機半導体として、例えば、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛、ＣｕＳＣＮ、Ｃｕ２Ｏ、ＣｕＩ、ＭｏＯ３、Ｖ２Ｏ５、ＷＯ３、ＭｏＳ２、ＭｏＳｅ２、Ｃｕ２Ｓ等が挙げられる。 Examples of the inorganic semiconductor include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI, MoO 3 , V 2 O 5 , WO 3 , MoS 2, MoSe 2, Cu 2 S , and the like.
上記光電変換層は、上記有機無機ペロブスカイト化合物と上記有機半導体又は上記無機半導体とを含む場合、薄膜状の有機半導体又は無機半導体部位と薄膜状の有機無機ペロブスカイト化合物部位とを積層した積層体であってもよいし、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜であってもよい。製法が簡便である点では積層体が好ましく、上記有機半導体又は上記無機半導体中の電荷分離効率を向上させることができる点では複合膜が好ましい。 When the photoelectric conversion layer contains the organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor, it is a laminated body in which a thin-film organic semiconductor or an inorganic semiconductor part and a thin-film organic-inorganic perovskite compound part are laminated. It may be a composite film in which an organic semiconductor or an inorganic semiconductor part and an organic-inorganic perovskite compound part are combined. A laminated body is preferable in that the manufacturing method is simple, and a composite film is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
上記薄膜状の有機無機ペロブスカイト化合物部位の厚みは、好ましい下限が５ｎｍ、好ましい上限が５０００ｎｍである。上記厚みが５ｎｍ以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが５０００ｎｍ以下であれば、電荷分離できない領域が発生することを抑制できるため、光電変換効率の向上につながる。上記厚みのより好ましい下限は１０ｎｍ、より好ましい上限は１０００ｎｍであり、更に好ましい下限は２０ｎｍ、更に好ましい上限は５００ｎｍである。 The lower limit of the thickness of the thin-film organic-inorganic perovskite compound moiety is preferably 5 nm, and the preferable upper limit thereof is 5000 nm. When the thickness is 5 nm or more, it becomes possible to absorb light sufficiently and the photoelectric conversion efficiency becomes high. When the thickness is 5000 nm or less, it is possible to suppress the generation of a region where charge cannot be separated, which leads to an improvement in photoelectric conversion efficiency. The more preferable lower limit of the thickness is 10 nm, the more preferable upper limit thereof is 1000 nm, the still more preferable lower limit thereof is 20 nm, and the still more preferable upper limit thereof is 500 nm.
上記光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、上記複合膜の厚みの好ましい下限は３０ｎｍ、好ましい上限は３０００ｎｍである。上記厚みが３０ｎｍ以上であれば、充分に光を吸収することができるようになり、光電変換効率が高くなる。上記厚みが３０００ｎｍ以下であれば、電荷が電極に到達しやすくなるため、光電変換効率が高くなる。上記厚みのより好ましい下限は４０ｎｍ、より好ましい上限は２０００ｎｍであり、更に好ましい下限は５０ｎｍ、更に好ましい上限は１０００ｎｍである。 When the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor part and an organic-inorganic perovskite compound part are combined, a preferable lower limit of the thickness of the composite film is 30 nm and a preferable upper limit thereof is 3000 nm. When the thickness is 30 nm or more, it becomes possible to absorb light sufficiently and the photoelectric conversion efficiency becomes high. When the thickness is 3000 nm or less, the electric charge easily reaches the electrode, and the photoelectric conversion efficiency is increased. A more preferable lower limit of the thickness is 40 nm, a more preferable upper limit thereof is 2000 nm, a still more preferable lower limit thereof is 50 nm, and a still more preferable upper limit thereof is 1000 nm.
上記光電変換層は、電子輸送層又はホール輸送層に接する側の少なくとも一方の表面の算術平均粗さＲａが５０ｎｍ以下である。上記電子輸送層及びホール輸送層の厚みを一定の厚さとするとともに、光電変換層の電子輸送層又はホール輸送層に接する側の少なくとも一方の表面の算術平均粗さＲａを５０ｎｍ以下とすることにより、光を照射し続けることによる光電変換効率の低下（光劣化）を抑制することができる。上記表面の算術平均粗さＲａは３０ｎｍ以下であることが好ましく、１０ｎｍ以下であることがより好ましい。下限は特に限定されないが、製造上の都合からは、１ｎｍ以上であってもよい。
なお、本明細書において算術平均粗さＲａは、ＪＩＳ Ｂ ０６０１：２０１３に規定される算術平均粗さを意味する。
また、光電変換層の表面の算術平均粗さＲａは、原子間力顕微鏡による表面形状の計測や透過型電子顕微鏡による断面測定により測定することができる。
The photoelectric conversion layer has an arithmetic average roughness Ra of 50 nm or less on at least one surface on the side in contact with the electron transport layer or the hole transport layer. By making the thicknesses of the electron transporting layer and the hole transporting layer constant and setting the arithmetic average roughness Ra of at least one surface of the photoelectric conversion layer on the side in contact with the electron transporting layer or the hole transporting layer to 50 nm or less. Therefore, it is possible to suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light. The arithmetic average roughness Ra of the surface is preferably 30 nm or less, and more preferably 10 nm or less. The lower limit is not particularly limited, but may be 1 nm or more for manufacturing convenience.
In this specification, the arithmetic mean roughness Ra means the arithmetic mean roughness defined in JIS B 0601:2013.
The arithmetic mean roughness Ra of the surface of the photoelectric conversion layer can be measured by measuring the surface shape with an atomic force microscope or by measuring the cross section with a transmission electron microscope.
上記光電変換層の電子輸送層又はホール輸送層に接する側の少なくとも一方の表面の算術平均粗さＲａを５０ｎｍ以下とする方法は特に限定されないが、例えば、原料となる金属ハロゲン化物をジメチルスルホキシド（ＤＭＳＯ）等のスルホキシド化合物と反応させて金属ハロゲン化物−スルホキシド複合体を調製し、該金属ハロゲン化物−スルホキシド複合体をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等の適当な溶媒に溶解して塗工液を調製し、該塗工液をスピンコート法等の塗工方法によって塗工して成膜し、次いで有機ハロゲン化物をイソプロパノール（ＩＰＡ）等の適当な溶媒に溶解して調整した塗工液をスピンコート法等によって塗工する方法により光電変換層を形成することが挙げられる。いったん金属ハロゲン化物−スルホキシド複合体を製膜してから有機ハロゲン化物と反応させることにより、きわめて均一なペロブスカイト構造を作製することができ、表面の算術平均粗さＲａを５０ｎｍ以下である光電変換層を得ることができる。 The method for setting the arithmetic average roughness Ra of at least one surface of the photoelectric conversion layer on the side in contact with the electron transport layer or the hole transport layer to 50 nm or less is not particularly limited, but, for example, a metal halide as a raw material may be dimethyl sulfoxide ( (DMSO) and the like to react with a sulfoxide compound to prepare a metal halide-sulfoxide complex, and the metal halide-sulfoxide complex is dissolved in an appropriate solvent such as N,N-dimethylformamide (DMF) and applied. A coating solution prepared by preparing a solution, applying the coating solution by a coating method such as a spin coating method to form a film, and then dissolving an organic halide in a suitable solvent such as isopropanol (IPA) to prepare a coating solution. The photoelectric conversion layer may be formed by a method of coating with a spin coating method or the like. A highly uniform perovskite structure can be produced by once forming a film of a metal halide-sulfoxide complex and then reacting it with an organic halide, and a photoelectric conversion layer having a surface arithmetic average roughness Ra of 50 nm or less. Can be obtained.
より具体的には、例えば、本発明の薄膜太陽電池を、基板上に陰極、薄膜状の電子輸送層、多孔質状の電子輸送層、光電変換層、ホール輸送層及び陽極をこの順で形成する場合に、上記電子輸送層上に上記塗工液を塗工して光電変換層を形成すれば、光電変換層のホール輸送層に接する側の表面の算術平均粗さＲａを５０ｎｍ以下とすることができる。
また、例えば、本発明の薄膜太陽電池を、基板上に陽極、ホール輸送層、光電変換層、多孔質状の電子輸送層、薄膜状の電子輸送層及び陰極をこの順で形成する場合に、上記ホール輸送層上に上記塗工液を塗工して光電変換層を形成すれば、光電変換層の多孔質状の電子輸送層に接する側の表面の算術平均粗さＲａを５０ｎｍ以下とすることができる。
More specifically, for example, the thin-film solar cell of the present invention, a cathode, a thin-film electron transport layer, a porous electron transport layer, a photoelectric conversion layer, a hole transport layer and an anode are formed in this order on a substrate. In this case, when the photoelectric conversion layer is formed by applying the coating liquid on the electron transport layer, the arithmetic average roughness Ra of the surface of the photoelectric conversion layer on the side in contact with the hole transport layer is set to 50 nm or less. be able to.
Further, for example, in the case of forming a thin film solar cell of the present invention on a substrate, an anode, a hole transport layer, a photoelectric conversion layer, a porous electron transport layer, a thin film electron transport layer and a cathode in this order, When the photoelectric conversion layer is formed by applying the coating liquid on the hole transport layer, the arithmetic mean roughness Ra of the surface of the photoelectric conversion layer on the side in contact with the porous electron transport layer is set to 50 nm or less. be able to.
上記光電変換層は、光電変換層形成後に熱アニール（加熱処理）が施されてもよい。熱アニール（加熱処理）を施すことにより、光電変換層中の有機無機ペロブスカイト化合物の結晶化度を充分に上げることができ、光を照射し続けることによる光電変換効率の低下（光劣化）をより抑制することができる。
上記熱アニール（加熱処理）を行う場合、上記光電変換層を加熱する温度は特に限定されないが、１００℃以上、２００℃未満であることが好ましい。上記加熱温度が１００℃以上であれば、上記有機無機ペロブスカイト化合物の結晶化度を充分に上げることができる。上記加熱温度が２００℃未満であれば、上記有機無機ペロブスカイト化合物を熱劣化させることなく加熱処理を行うことができる。より好ましい加熱温度は、１２０℃以上、１７０℃以下である。また、加熱時間も特に限定されないが、３分以上、２時間以内であることが好ましい。上記加熱時間が３分以上であれば、上記有機無機ペロブスカイト化合物の結晶化度を充分に上げることができる。上記加熱時間が２時間以内であれば、上記有機無機ペロブスカイト化合物を熱劣化させることなく加熱処理を行うことができる。
これらの加熱操作は真空又は不活性ガス下で行われることが好ましく、露点温度は１０℃以下が好ましく、７．５℃以下がより好ましく、５℃以下が更に好ましい。
The photoelectric conversion layer may be subjected to thermal annealing (heat treatment) after the photoelectric conversion layer is formed. By performing thermal annealing (heat treatment), the crystallinity of the organic-inorganic perovskite compound in the photoelectric conversion layer can be sufficiently increased, and the decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light can be further suppressed. Can be suppressed.
When performing the thermal annealing (heat treatment), the temperature for heating the photoelectric conversion layer is not particularly limited, but is preferably 100° C. or higher and lower than 200° C. When the heating temperature is 100° C. or higher, the crystallinity of the organic-inorganic perovskite compound can be sufficiently increased. When the heating temperature is lower than 200° C., the heat treatment can be performed without thermally deteriorating the organic/inorganic perovskite compound. A more preferable heating temperature is 120° C. or higher and 170° C. or lower. The heating time is not particularly limited, but is preferably 3 minutes or more and 2 hours or less. When the heating time is 3 minutes or more, the crystallinity of the organic-inorganic perovskite compound can be sufficiently increased. When the heating time is within 2 hours, the heat treatment can be performed without thermally deteriorating the organic-inorganic perovskite compound.
These heating operations are preferably performed in vacuum or under an inert gas, and the dew point temperature is preferably 10° C. or lower, more preferably 7.5° C. or lower, still more preferably 5° C. or lower.
上記陰極及び陽極の材料は特に限定されず、従来公知の材料を用いることができる。なお、上記陰極及び陽極は、パターニングされた電極であることが多い。
電極材料として、例えば、ＦＴＯ（フッ素ドープ酸化スズ）、金、銀、チタン、ナトリウム、ナトリウム−カリウム合金、リチウム、マグネシウム、アルミニウム、マグネシウム−銀混合物、マグネシウム−インジウム混合物、アルミニウム−リチウム合金、Ａｌ／Ａｌ２Ｏ３混合物、Ａｌ／ＬｉＦ混合物等が挙げられる。対向電極材料として、例えば、金等の金属、ＣｕＩ、ＩＴＯ（インジウムスズ酸化物）、ＳｎＯ２、ＡＺＯ（アルミニウム亜鉛酸化物）、ＩＺＯ（インジウム亜鉛酸化物）、ＧＺＯ（ガリウム亜鉛酸化物）、ＡＴＯ（アンチモンドープ酸化スズ）等の導電性透明材料、導電性透明ポリマー等が挙げられる。これらの材料は単独で用いられてもよく、２種以上が併用されてもよい。
The materials for the cathode and the anode are not particularly limited, and conventionally known materials can be used. The cathode and the anode are often patterned electrodes.
Examples of the electrode material include FTO (fluorine-doped tin oxide), gold, silver, titanium, sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al/ Examples include Al 2 O 3 mixture and Al/LiF mixture. Examples of the counter electrode material include metals such as gold, CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), and ATO. Examples thereof include conductive transparent materials such as (antimony-doped tin oxide) and conductive transparent polymers. These materials may be used alone or in combination of two or more.
上記電子輸送層の材料は特に限定されず、例えば、Ｎ型導電性高分子、Ｎ型低分子有機半導体、Ｎ型金属酸化物、Ｎ型金属硫化物、ハロゲン化アルカリ金属、アルカリ金属、界面活性剤等が挙げられ、具体的には例えば、シアノ基含有ポリフェニレンビニレン、ホウ素含有ポリマー、バソキュプロイン、バソフェナントレン、ヒドロキシキノリナトアルミニウム、オキサジアゾール化合物、ベンゾイミダゾール化合物、ナフタレンテトラカルボン酸化合物、ペリレン誘導体、ホスフィンオキサイド化合物、ホスフィンスルフィド化合物、フルオロ基含有フタロシアニン、酸化チタン、酸化亜鉛、酸化インジウム、酸化スズ、酸化ガリウム、硫化スズ、硫化インジウム、硫化亜鉛等が挙げられる。 The material of the electron transport layer is not particularly limited, and examples thereof include N-type conductive polymers, N-type low molecular weight organic semiconductors, N-type metal oxides, N-type metal sulfides, alkali metal halides, alkali metals, surface active agents. Agents and the like, specifically, for example, cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, benzimidazole compound, naphthalenetetracarboxylic acid compound, perylene derivative, Examples thereof include phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide and zinc sulfide.
上記電子輸送層は、薄膜状の電子輸送層と、多孔質状の電子輸送層とを含む。特に、上記光電変換層が、有機半導体又は無機半導体部位と有機無機ペロブスカイト化合物部位とを複合化した複合膜である場合、より複雑な複合膜（より複雑に入り組んだ構造）が得られ、光電変換効率が高くなることから、多孔質状の電子輸送層上に複合膜が製膜されていることが好ましい。 The electron transport layer includes a thin film electron transport layer and a porous electron transport layer. In particular, when the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor part and an organic-inorganic perovskite compound part are combined, a more complicated composite film (more complicated intricate structure) is obtained, and photoelectric conversion is performed. It is preferable that the composite film is formed on the porous electron transport layer because the efficiency is high.
上記薄膜状の電子輸送層の厚みの下限は１００ｎｍである。上記薄膜状の電子輸送層の厚みを上記下限以上とすることにより、光を照射し続けることによる光電変換効率の低下（光劣化）を抑制できる。上記薄膜状の電子輸送層の厚みの上限は特に限定されないが、５００ｎｍであることが好ましい。上記薄膜状の電子輸送層の厚みが上記上限以下であると、クラックの発生を抑制しやすくなる。上記薄膜状の電子輸送層の厚みの好ましい下限は１５０ｎｍ、より好ましい上限は４００ｎｍであり、より好ましい下限は２００ｎｍ、更に好ましい上限は３００ｎｍである。なお、本明細書において上記薄膜状の電子輸送層の厚みは電極から多孔質状の電子輸送層までの距離の平均値を意味し、透過型電子顕微鏡による断面観察により測定することができる。 The lower limit of the thickness of the thin-film electron transport layer is 100 nm. By setting the thickness of the thin-film electron transport layer to the above lower limit or more, it is possible to suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light. The upper limit of the thickness of the thin film electron transport layer is not particularly limited, but is preferably 500 nm. When the thickness of the thin film electron transport layer is equal to or less than the upper limit, it becomes easy to suppress the occurrence of cracks. The preferable lower limit of the thickness of the thin-film electron transport layer is 150 nm, the more preferable upper limit is 400 nm, the more preferable lower limit is 200 nm, and the still more preferable upper limit is 300 nm. In the present specification, the thickness of the thin film electron transport layer means the average value of the distance from the electrode to the porous electron transport layer, and can be measured by observing a cross section with a transmission electron microscope.
上記ホール輸送層の材料は特に限定されず、例えば、Ｐ型導電性高分子、Ｐ型低分子有機半導体、Ｐ型金属酸化物、Ｐ型金属硫化物、界面活性剤等が挙げられ、具体的には例えば、ポリエチレンジオキシチオフェンのポリスチレンスルホン酸付加物、カルボキシル基含有ポリチオフェン、フタロシアニン、ポルフィリン、酸化モリブデン、酸化バナジウム、酸化タングステン、酸化ニッケル、酸化銅、酸化スズ、硫化モリブデン、硫化タングステン、硫化銅、硫化スズ等、フルオロ基含有ホスホン酸、カルボニル基含有ホスホン酸、ＣｕＳＣＮ、ＣｕＩ等の銅化合物、表面修飾されていてもよいカーボンナノチューブ、グラフェン等のカーボン含有材料等が挙げられる。 The material of the hole transport layer is not particularly limited, and examples thereof include P-type conductive polymers, P-type low molecular weight organic semiconductors, P-type metal oxides, P-type metal sulfides, and surfactants. Examples thereof include polystyrene sulfonic acid adduct of polyethylenedioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Tin sulfide and the like, fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI, carbon nanotubes which may be surface-modified, and carbon-containing materials such as graphene.
上記ホール輸送層の厚みの下限は１００ｎｍである。上記ホール輸送層の厚みを上記下限以上とすることにより、光を照射し続けることによる光電変換効率の低下（光劣化）を抑制できる。上記ホール輸送層の厚みの上限は特に限定されないが、５００ｎｍであることが好ましい。上記ホール輸送層の厚みが上記上限以下であると、クラックの発生を抑制しやすくなる。上記ホール輸送層の厚みの好ましい下限は２００ｎｍ、より好ましい上限は４００ｎｍであり、より好ましい下限は３００ｎｍ、更に好ましい上限は４００ｎｍである。なお、本明細書において上記ホール輸送層の厚みは光電変換層から電極までの距離の平均値を意味し、透過型電子顕微鏡による断面観察により測定することができる。 The lower limit of the thickness of the hole transport layer is 100 nm. By setting the thickness of the hole transport layer to the above lower limit or more, it is possible to suppress a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light. The upper limit of the thickness of the hole transport layer is not particularly limited, but is preferably 500 nm. When the thickness of the hole transport layer is equal to or less than the upper limit, it becomes easy to suppress the generation of cracks. The preferable lower limit of the thickness of the hole transport layer is 200 nm, the more preferable upper limit thereof is 400 nm, the more preferable lower limit thereof is 300 nm, and the still more preferable upper limit thereof is 400 nm. In the present specification, the thickness of the hole transport layer means the average value of the distance from the photoelectric conversion layer to the electrode, and can be measured by observing a cross section with a transmission electron microscope.
本発明の薄膜太陽電池は、更に、基板等を有していてもよい。上記基板は特に限定されず、例えば、ソーダライムガラス、無アルカリガラス等の透明ガラス基板、セラミック基板、透明プラスチック基板等が挙げられる。 The thin film solar cell of the present invention may further have a substrate and the like. The substrate is not particularly limited, and examples thereof include a transparent glass substrate such as soda lime glass and non-alkali glass, a ceramic substrate, and a transparent plastic substrate.
図２は、本発明の薄膜太陽電池の一例を模式的に示す断面図である。
図２に示す薄膜太陽電池１は、基板７上に陰極２、電子輸送層３（薄膜状の電子輸送層３１と多孔質状の電子輸送層３２）、有機無機ペロブスカイト化合物を含む光電変換層４、ホール輸送層５及び陽極６がこの順に積層されたものである。なお、図２に示す薄膜太陽電池１において、陽極６はパターニングされた電極である。
FIG. 2 is a sectional view schematically showing an example of the thin film solar cell of the present invention.
The thin film solar cell 1 shown in FIG. 2 has a
本発明によれば、光を照射し続けることによる光電変換効率の低下（光劣化）が抑制された薄膜太陽電池を提供することができる。 According to the present invention, it is possible to provide a thin-film solar cell in which a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light is suppressed.
以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, the embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
ガラス基板上に、陰極として厚み１０００ｎｍのＦＴＯ膜を形成し、純水、アセトン、メタノールをこの順に用いて各１０分間超音波洗浄した後、乾燥させた。
ＦＴＯ膜の表面上に、２％に調整したチタンイソプロポキシドエタノール溶液をスピンコート法により塗布した後、４００℃で１０分間焼成し、薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、有機バインダとしてのポリイソブチルメタクリレートと酸化チタン（平均粒子径１０ｎｍと３０ｎｍとの混合物）とを含有する酸化チタンペーストをスピンコート法により塗布した後、５００℃で１０分間焼成し、多孔質状の電子輸送層を形成した。
(Example 1)
An FTO film having a thickness of 1000 nm was formed as a cathode on a glass substrate, ultrasonically washed with pure water, acetone, and methanol in this order for 10 minutes each, and then dried.
A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, and then baked at 400° C. for 10 minutes to form a thin film electron transport layer. Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of average particle diameters of 10 nm and 30 nm) was applied on the thin film electron transport layer by spin coating, and then 500° C. And baked for 10 minutes to form a porous electron transport layer.
一方、予めヨウ化鉛をジメチルスルホキシド（ＤＭＳＯ）と反応させてヨウ化鉛−ジメチルスルホキシド複合体を調製し、該ヨウ化鉛−ジメチルスルホキシド複合体をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に溶解して８０％の塗工液を得た。上記電子輸送層上に、得られた塗工液をスピンコート法によって２００ｎｍの厚みに積層し、更にその上から８％に調整したヨウ化ホルムアミジン（ＣＨ４Ｎ２Ｉ）のイソプロパノール溶液をスピンコート法によって積層することでヨウ化鉛と反応させ、有機無機ペロブスカイト化合物を含む光電変換層を形成した。 On the other hand, lead iodide is previously reacted with dimethylsulfoxide (DMSO) to prepare a lead iodide-dimethylsulfoxide complex, and the lead iodide-dimethylsulfoxide complex is dissolved in N,N-dimethylformamide (DMF). 80% coating solution was obtained. The obtained coating solution was laminated on the electron transport layer to a thickness of 200 nm by a spin coating method, and an isopropanol solution of formamidine iodide (CH 4 N 2 I) adjusted to 8% was spun on the layer. By laminating by a coating method, it was reacted with lead iodide to form a photoelectric conversion layer containing an organic-inorganic perovskite compound.
次いで、クロロベンゼン２５μＬにＳｐｉｒｏ−ＯＭｅＴＡＤ（スピロビフルオレン骨格を有する）を６８ｍＭ、ｔ−ブチルピリジンを５５ｍＭ、ビス（トリフルオロメチルスルホニル）イミド・リチウム塩を９ｍＭ溶解させた溶液をスピンコート法により塗布して、
ール輸送層を形成した。
Then, a solution in which 25 mM of chlorobenzene was dissolved in 68 mM of Spiro-OMeTAD (having a spirobifluorene skeleton), 55 mM of t-butylpyridine, and 9 mM of bis(trifluoromethylsulfonyl)imide lithium salt was applied by spin coating. hand,
A layer transport layer was formed.
得られたホール輸送層上に、陽極として真空蒸着により厚み１００ｎｍのＩＴＯ膜を形成し、陰極／電子輸送層／光電変換層／ホール輸送層／陽極が積層された薄膜太陽電池を得た。 An ITO film having a thickness of 100 nm was formed as an anode on the obtained hole transport layer by vacuum vapor deposition to obtain a thin film solar cell in which a cathode/electron transport layer/photoelectric conversion layer/hole transport layer/anode were laminated.
得られた薄膜太陽電池について透過型電子顕微鏡による断面観察により、光電変換層のホール輸送層に接する側の表面の算術平均粗さＲａを測定したところ、３０ｎｍであった。また、電子輸送層の厚みは１５０ｎｍ、ホール輸送層の厚みは３００ｎｍであった。 The arithmetic average roughness Ra of the surface of the photoelectric conversion layer on the side in contact with the hole transport layer was measured by observing the cross section of the obtained thin film solar cell with a transmission electron microscope, and it was 30 nm. The thickness of the electron transport layer was 150 nm, and the thickness of the hole transport layer was 300 nm.
（実施例２〜３、比較例２〜４）
電子輸送層及びホール輸送層の厚みを表１に示したようにした以外は、実施例１と同様にして薄膜太陽電池を得た。
(Examples 2-3, Comparative Examples 2-4)
A thin film solar cell was obtained in the same manner as in Example 1 except that the thicknesses of the electron transport layer and the hole transport layer were as shown in Table 1.
（比較例１）
ガラス基板上に、陰極として厚み１０００ｎｍのＦＴＯ膜を形成し、純水、アセトン、メタノールをこの順に用いて各１０分間超音波洗浄した後、乾燥させた。
ＦＴＯ膜の表面上に、２％に調整したチタンイソプロポキシドエタノール溶液をスピンコート法により塗布した後、４００℃で１０分間焼成し、厚み２００ｎｍの薄膜状の電子輸送層を形成した。更に、薄膜状の電子輸送層上に、有機バインダとしてのポリイソブチルメタクリレートと酸化チタン（平均粒子径１０ｎｍと３０ｎｍとの混合物）とを含有する酸化チタンペーストをスピンコート法により塗布した後、５００℃で１０分間焼成し、厚み２００ｎｍの多孔質状の電子輸送層を形成した。
(Comparative Example 1)
An FTO film having a thickness of 1000 nm was formed as a cathode on a glass substrate, ultrasonically washed with pure water, acetone, and methanol in this order for 10 minutes each, and then dried.
A titanium isopropoxide ethanol solution adjusted to 2% was applied on the surface of the FTO film by a spin coating method, and then baked at 400° C. for 10 minutes to form a thin-film electron transport layer having a thickness of 200 nm. Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of average particle diameters of 10 nm and 30 nm) was applied on the thin film electron transport layer by spin coating, and then 500° C. And baked for 10 minutes to form a 200 nm-thick porous electron transport layer.
次いで、有機無機ペロブスカイト化合物形成用溶液として、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を溶媒としてヨウ化ホルムアミジンとヨウ化鉛をモル比３：１で溶かし、ヨウ化ホルムアミジンとヨウ化鉛の合計重量濃度を２０％に調整した。この溶液を電子輸送層上にスピンコート法によって積層して、厚み３００ｎｍの光電変換層を形成した。 Then, as a solution for forming an organic-inorganic perovskite compound, N,N-dimethylformamide (DMF) was used as a solvent and formamidine iodide and lead iodide were dissolved at a molar ratio of 3:1 to obtain a total of formamidine iodide and lead iodide. The weight concentration was adjusted to 20%. This solution was laminated on the electron transport layer by spin coating to form a photoelectric conversion layer having a thickness of 300 nm.
次いで、クロロベンゼン２５μＬにＳｐｉｒｏ−ＯＭｅＴＡＤ（スピロビフルオレン骨格を有する）を６８ｍＭ、ｔ−ブチルピリジンを５５ｍＭ、ビス（トリフルオロメチルスルホニル）イミド・リチウム塩を９ｍＭ溶解させた溶液をスピンコート法により塗布して厚み３５０ｎｍのホール輸送層を形成した。 Then, a solution in which 25 mM of chlorobenzene was dissolved in 68 mM of Spiro-OMeTAD (having a spirobifluorene skeleton), 55 mM of t-butylpyridine, and 9 mM of bis(trifluoromethylsulfonyl)imide lithium salt was applied by spin coating. As a result, a hole transport layer having a thickness of 350 nm was formed.
得られたホール輸送層上に、陽極として真空蒸着により厚み１００ｎｍのＩＴＯ膜を形成し、陰極／電子輸送層／光電変換層／ホール輸送層／陽極が積層された薄膜太陽電池を得た。 An ITO film having a thickness of 100 nm was formed as an anode on the obtained hole transport layer by vacuum vapor deposition to obtain a thin film solar cell in which a cathode/electron transport layer/photoelectric conversion layer/hole transport layer/anode were laminated.
得られた薄膜太陽電池について、透過型電子顕微鏡により、光電変換層のホール輸送層に接する側の表面の算術平均粗さＲａを測定したところ、１２０ｎｍであった。電子輸送層の厚みは２００ｎｍ、ホール輸送層の厚みは３５０ｎｍであった。 With respect to the obtained thin-film solar cell, the arithmetic average roughness Ra of the surface of the photoelectric conversion layer in contact with the hole transport layer was measured by a transmission electron microscope, and it was 120 nm. The electron transport layer had a thickness of 200 nm, and the hole transport layer had a thickness of 350 nm.
＜評価＞
実施例及び比較例で得られた薄膜太陽電池について、以下の評価を行った。結果を表１に示した。
<Evaluation>
The thin film solar cells obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 1.
（光劣化試験）
太陽電池の電極間に電源（ＫＥＩＴＨＬＥＹ社製、２３６モデル）を接続し、ソーラーシミュレーション（山下電装社製）を用いて強度１００ｍＷ／ｃｍ２の光を照射した。光照射を開始した直後の光電変換効率と光照射を１時間続けた後の光電変換効率とをそれぞれ測定した。光照射を１時間続けた後の光電変換効率／光照射を開始した直後の光電変換効率の値を求め、その値が０．９以上であった場合を○○、０．８以上、０．９未満であった場合を○、０．８未満であった場合を×とした。
(Light deterioration test)
A power source (236 model, manufactured by KEITHLEY) was connected between the electrodes of the solar cell, and light having an intensity of 100 mW/cm 2 was irradiated using a solar simulation (manufactured by Yamashita Denso Co., Ltd.). The photoelectric conversion efficiency immediately after the light irradiation was started and the photoelectric conversion efficiency after the light irradiation was continued for 1 hour were measured. The value of the photoelectric conversion efficiency after the light irradiation was continued for 1 hour/the value of the photoelectric conversion efficiency immediately after the start of the light irradiation was obtained, and when the value was 0.9 or more, ◯, 0.8 or more, 0. When it was less than 9, it was evaluated as ◯, and when it was less than 0.8, it was evaluated as x.
本発明によれば、光を照射し続けることによる光電変換効率の低下（光劣化）が抑制された薄膜太陽電池を提供することができる。 According to the present invention, it is possible to provide a thin-film solar cell in which a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of light is suppressed.
１ 薄膜太陽電池
２ 陰極
３ 電子輸送層
３１ 薄膜状の電子輸送層
３２ 多孔質状の電子輸送層
４ 有機無機ペロブスカイト化合物を含む光電変換層
５ ホール輸送層
６ 陽極（パターニングされた電極）
７ 基板
DESCRIPTION OF SYMBOLS 1 thin film
7 substrate
Claims (1)
前記電子輸送層は薄膜状の電子輸送層と、多孔質状の電子輸送層とをこの順番に有し、
前記光電変換層は、一般式Ｒ−Ｍ−Ｘ３（但し、Ｒは有機分子、Ｍは金属原子、Ｘはハロゲン原子又はカルコゲン原子である。）で表される有機無機ペロブスカイト化合物を含み、
前記薄膜状の電子輸送層の厚みが１００ｎｍ以上３００ｎｍ以下、前記ホール輸送層の厚みが１００ｎｍ以上３００ｎｍ以下であり、かつ、前記光電変換層の前記ホール輸送層に接する側の表面の算術平均粗さＲａが５０ｎｍ以下である
ことを特徴とする薄膜太陽電池。 A thin film solar cell having a structure in which a cathode, an electron transport layer, a photoelectric conversion layer, a hole transport layer and an anode are laminated in this order,
The electron transport layer has a thin film electron transport layer and a porous electron transport layer in this order ,
The photoelectric conversion layer has the general formula R-M-X 3 (where, R represents an organic molecule, M is a metal atom, X is a halogen atom or a chalcogen atom.) An organic-inorganic perovskite compound represented by,
Hereinafter 300nm thickness 100nm or more of the thin film of the electron transport layer, the thickness of the hole transport layer is not less 100nm or 300nm or less, the arithmetic mean of the front surface of the side in contact with the front Symbol hole transport layer of the photoelectric conversion layer A thin film solar cell having a roughness Ra of 50 nm or less.
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