JP6730037B2 - Solar cells and organic semiconductor materials - Google Patents
Solar cells and organic semiconductor materials Download PDFInfo
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- JP6730037B2 JP6730037B2 JP2016013836A JP2016013836A JP6730037B2 JP 6730037 B2 JP6730037 B2 JP 6730037B2 JP 2016013836 A JP2016013836 A JP 2016013836A JP 2016013836 A JP2016013836 A JP 2016013836A JP 6730037 B2 JP6730037 B2 JP 6730037B2
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- photoelectric conversion
- solar cell
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- 229910052796 boron Inorganic materials 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
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- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
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- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 description 1
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- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
-
- 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、スパッタリング耐性があり、かつ光電変換効率が高く、高温高湿下においても耐えうる太陽電池、及び、有機半導体材料に関する。 The present invention relates to a solar cell that has sputtering resistance, high photoelectric conversion efficiency, and can withstand high temperature and high humidity, and an organic semiconductor material.
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, a photocarrier is generated by photoexcitation, and an electron moves in the N-type semiconductor and a hole moves 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.
本発明は、スパッタリング耐性があり、かつ光電変換効率が高く、高温高湿下においても耐えうる太陽電池及び、有機半導体材料を提供することを目的とする。 An object of the present invention is to provide a solar cell having high sputtering resistance, high photoelectric conversion efficiency, and withstanding high temperature and high humidity, and an organic semiconductor material.
本発明は、電極と、透明電極と、前記電極と前記透明電極との間に配置された光電変換層と、前記光電変換層と前記透明電極との間に配置されたホール輸送層とを有する太陽電池であって、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、前記ホール輸送層は、フタロシアニン骨格を有する化合物を含み、前記フタロシアニン骨格を有する化合物がアルキル基、アルコキシ基、ハロゲン基、及び芳香族基からなる群から選択される少なくとも1種の置換基を有する太陽電池である。
以下、本発明を詳述する。
The present invention has an electrode, a transparent electrode, a photoelectric conversion layer arranged between the electrode and the transparent electrode, and a hole transport layer arranged between the photoelectric conversion layer and the transparent electrode. a solar cell, 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.) the organic-inorganic represented by The hole transport layer contains a compound having a phthalocyanine skeleton, and the compound having a phthalocyanine skeleton contains at least one selected from the group consisting of an alkyl group, an alkoxy group, a halogen group, and an aromatic group. It is a solar cell having a substituent.
Hereinafter, the present invention will be described in detail.
本発明者らは、電極と、透明電極と、前記電極と前記透明電極との間に配置された光電変換層とを有する太陽電池において、光電変換層に特定の有機無機ペロブスカイト化合物を用い、更に前記光電変換層と前記透明電極との間にホール輸送層を配置することを検討した。有機無機ペロブスカイト化合物を用いることにより、太陽電池の光電変換効率の向上が期待できる。更に前記光電変換層と前記透明電極との間にホール輸送層を配置することで、光電変換効率の向上が期待できる。
一方、有機太陽電池においては、透明電極をスパッタリング法等により形成することが一般的である。しかしながら、本発明者らは、透明電極をスパッタリング法等により形成する際、例えばポリチオフェンのようなホール輸送層の材料の種類によってはホール輸送層が損傷し、太陽電池の劣化(初期劣化)の原因になり高い光電変換効率が得られないことを見出した。この問題に対して、本発明者らは、光電変換層に特定の有機無機ペロブスカイト化合物を用い、かつ、ホール輸送層に特定の材料を用いることにより、光電変換効率が高くなり、スパッタリング法等によってホール輸送層上に直接透明電極を形成してもホール輸送層が損傷しない(即ち、スパッタリング耐性がある)ことを見出した。更に本発明者らは、このような特定のホール輸送層を用いることにより、高温高湿下においても耐えうる耐久性をも向上できることを見出し、本発明を完成させるに至った。
The present inventors, in a solar cell having an electrode, a transparent electrode, and a photoelectric conversion layer arranged between the electrode and the transparent electrode, using a specific organic-inorganic perovskite compound for the photoelectric conversion layer, further It was examined to dispose a hole transport layer between the photoelectric conversion layer and the transparent electrode. By using the organic-inorganic perovskite compound, improvement in photoelectric conversion efficiency of the solar cell can be expected. Further, by disposing a hole transport layer between the photoelectric conversion layer and the transparent electrode, improvement in photoelectric conversion efficiency can be expected.
On the other hand, in an organic solar cell, it is common to form a transparent electrode by a sputtering method or the like. However, when the transparent electrode is formed by the sputtering method or the like, the inventors of the present invention damage the hole transport layer depending on the kind of the material of the hole transport layer such as polythiophene and cause deterioration of the solar cell (initial deterioration). Therefore, it was found that high photoelectric conversion efficiency cannot be obtained. With respect to this problem, the present inventors, by using a specific organic-inorganic perovskite compound for the photoelectric conversion layer, and by using a specific material for the hole transport layer, the photoelectric conversion efficiency is increased, and by a sputtering method or the like. It has been found that the hole transport layer is not damaged even if the transparent electrode is directly formed on the hole transport layer (that is, it has sputtering resistance). Furthermore, the present inventors have found that by using such a specific hole transport layer, the durability which can withstand even under high temperature and high humidity can be improved, and the present invention has been completed.
本発明の太陽電池は、電極と、透明電極と、上記電極と上記透明電極との間に配置された光電変換層とを有する。
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、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 solar cell of the present invention has an electrode, a transparent electrode, and a photoelectric conversion layer arranged between the electrode and the transparent electrode.
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 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.
上記電極及び上記透明電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。
電極材料として、例えば、金、銀、チタン、銅等の金属、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。透明電極材料として、例えば、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)、FTO(フッ素ドープ酸化スズ)、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。上記電極は、透明電極であってもよい。また、上記電極は陰極であっても陽極であってもよい。なお、上記透明電極は、パターニングされた電極であることが多い。
Materials for the electrodes and the transparent electrodes are not particularly limited, and conventionally known materials can be used.
Examples of the electrode material include metals such as gold, silver, titanium, and copper, sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al/Al 2 O. 3 mixtures, Al/LiF mixtures, etc. are mentioned. Examples of transparent electrode materials include CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), GZO (gallium zinc oxide), FTO (fluorine-doped tin oxide). ), conductive transparent materials such as ATO (antimony-doped tin oxide), conductive transparent polymers, and the like. These materials may be used alone or in combination of two or more. The electrode may be a transparent electrode. Further, the electrode may be a cathode or an anode. The transparent electrode is often a patterned electrode.
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、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 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、アニリン、ピリジン、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、ブチルアミン、ペンチルアミン、ヘキシルアミン、アニリン、ピリジン、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、グアニジンのイオンやフェネチルアンモニウムが好ましく、メチルアミン、エチルアミン、プロピルアミン、ペンチルカルボキシアミン、ホルムアミジニウム、グアニジンのイオンがより好ましい。
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, aniline, pyridine, methylcarboxyamine, ethylcarboxyamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, hexylcarboxyamine, formamidinium, guanidine ion (for example, methylammonium (CH 3 NH 3 ) etc.) and phenethyl ammonium. Among them, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, aniline, pyridine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, guanidine ion and phenethylammonium are preferable, and methylamine More preferred are ions of ethylamine, propylamine, pentylcarboxyamine, formamidinium and guanidine.
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、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, and 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. Of these, lead and tin are 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やすく、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 is likely to be soluble in the organic solvent by containing halogen in the structure, and it becomes possible to apply to an inexpensive printing method or the like. 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、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 electron mobility in the organic-inorganic perovskite compound becomes high, and the photoelectric conversion of the solar cell is increased. It is estimated that the conversion efficiency will be 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ることにより、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、太陽電池の光電変換効率が向上する。 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 increased and the photoelectric conversion efficiency of the solar cell is improved.
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値を求めて、全体のうちの結晶部分の比から百分率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。結晶化度が30%以上であると、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、太陽電池の光電変換効率が向上する。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、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 crystallinity is obtained by separating the scattering peaks derived from the crystalline material detected by X-ray scattering intensity distribution measurement and the halo derived from the amorphous portion by fitting, obtaining the respective intensity integral values, and measuring the crystal of the whole. It can be obtained by calculating the percentage from the ratio of the parts.
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 solar cell is improved. A more preferable lower limit of the crystallinity is 50%, and a still more preferable lower limit thereof is 70%.
Examples of methods for increasing the crystallinity of the organic-inorganic perovskite compound include thermal annealing, irradiation with intense light such as laser, and plasma irradiation.
上記光電変換層の厚みは、好ましい下限は5nm、好ましい上限は1000nmである。上記厚みが5nm以上であれば、光を充分に吸収することができる。上記厚みが1000nm以下であれば、生成した電荷を各電極に輸送させることができる。上記厚みのより好ましい下限は10nm、より好ましい上限は700nmであり、更に好ましい下限は15nm、更に好ましい上限は500nmである。 The preferable lower limit of the thickness of the photoelectric conversion layer is 5 nm, and the preferable upper limit thereof is 1000 nm. When the thickness is 5 nm or more, light can be sufficiently absorbed. When the thickness is 1000 nm or less, the generated charges can be transported to each electrode. A more preferable lower limit of the thickness is 10 nm, a more preferable upper limit thereof is 700 nm, a still more preferable lower limit thereof is 15 nm, and a still more preferable upper limit thereof is 500 nm.
本発明の太陽電池は、上記光電変換層と上記透明電極との間に配置されたホール輸送層を有する。
上記ホール輸送層は、フタロシアニン骨格を有する化合物を含む。一般的に、太陽電池がホール輸送層を有することで、光電変換層と透明電極との間の界面における光キャリアの再結合を抑制し、更に界面抵抗値を減少させることで光電変換効率を高めることができる。しかし、透明電極をスパッタリング法等により形成する際、例えばポリチオフェンのようなホール輸送層の材料の種類によってはホール輸送層が損傷し、太陽電池の劣化(初期劣化)の原因になり高い光電変換効率が得られない。これに対して、本発明の太陽電池においては、上記ホール輸送層がフタロシアニン骨格を有する化合物を含むので、スパッタリング法等によって上記ホール輸送層上に直接上記透明電極を形成しても(即ち、上記ホール輸送層と上記透明電極とが隣接していても)スパッタリング耐性を向上させることができる。更に、上記フタロシアニン骨格を有する化合物を含むことで、太陽電池の高温高湿下においても耐えうる耐久性をも向上させることもできる。
The solar cell of the present invention has a hole transport layer arranged between the photoelectric conversion layer and the transparent electrode.
The hole transport layer contains a compound having a phthalocyanine skeleton. Generally, a solar cell having a hole transport layer suppresses recombination of photocarriers at the interface between the photoelectric conversion layer and the transparent electrode, and further increases the photoelectric conversion efficiency by reducing the interface resistance value. be able to. However, when the transparent electrode is formed by the sputtering method or the like, the hole transport layer may be damaged depending on the kind of the material of the hole transport layer such as polythiophene, which may cause deterioration (initial deterioration) of the solar cell and high photoelectric conversion efficiency. Can't get On the other hand, in the solar cell of the present invention, since the hole transport layer contains a compound having a phthalocyanine skeleton, even if the transparent electrode is directly formed on the hole transport layer by a sputtering method or the like (that is, the above Sputtering resistance can be improved (even if the hole transport layer and the transparent electrode are adjacent to each other). Furthermore, by including the compound having the phthalocyanine skeleton, the durability of the solar cell, which can withstand even under high temperature and high humidity, can be improved.
上記フタロシアニン骨格を有する化合物は、アルキル基、アルコキシ基、ハロゲン基、及び芳香族基からなる群から選択される少なくとも1種の置換基を有する。上記フタロシアニン骨格を有する化合物が上記置換基を有することで、上記フタロシアニン骨格を有する化合物が上記有機無機ペロブスカイト化合物を溶かしだしにくくなる。また、上記フタロシアニン骨格を有する化合物が、有機溶媒に可溶となるため、安価で簡便な塗布法を用いて上記ホール輸送層を形成することができる。これらの置換基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。中でも、有機溶媒への可溶性を高める観点から、上記置換基はアルキル基又は芳香族基であることが好ましい。上記置換基の置換部位は特に限定されず、フタロシアニン骨格のα位であってもβ位であってもよい。上記置換基の置換数は特に限定されず、複数であってもよい。また、上記置換基として芳香族基を用いる場合、上記芳香族基は、一部が置換基で置換されていてもよい。 The compound having a phthalocyanine skeleton has at least one kind of substituent selected from the group consisting of an alkyl group, an alkoxy group, a halogen group, and an aromatic group. When the compound having the phthalocyanine skeleton has the substituent, it becomes difficult for the compound having the phthalocyanine skeleton to dissolve the organic-inorganic perovskite compound. Moreover, since the compound having the phthalocyanine skeleton becomes soluble in the organic solvent, the hole transport layer can be formed by an inexpensive and simple coating method. These substituents may be used alone or in combination of two or more. Above all, the substituent is preferably an alkyl group or an aromatic group from the viewpoint of increasing the solubility in an organic solvent. The substitution site of the above substituent is not particularly limited, and may be the α-position or the β-position of the phthalocyanine skeleton. The number of substitutions of the above-mentioned substituents is not particularly limited and may be plural. When an aromatic group is used as the above-mentioned substituent, a part of the above-mentioned aromatic group may be substituted with a substituent.
上記フタロシアニン骨格を有する化合物は、中心金属を有していてもよい。上記中心金属としては例えば、亜鉛、銅、ニッケル、マグネシウム、コバルト、鉄、チタン、鉛、インジウム、ベリリウム、モリブデン、パラジウム、ナトリウム、リチウム、銀、スズ、ガリウム、ゲルマニウム、アルミニウム、マンガン等が挙げられる。中でも、光電変換効率がより高くなることから、中心金属は亜鉛、ニッケル、又はパラジウムが好ましく、パラジウムがより好ましい。 The compound having a phthalocyanine skeleton may have a central metal. Examples of the central metal include zinc, copper, nickel, magnesium, cobalt, iron, titanium, lead, indium, beryllium, molybdenum, palladium, sodium, lithium, silver, tin, gallium, germanium, aluminum and manganese. .. Among them, the central metal is preferably zinc, nickel, or palladium, and more preferably palladium, because the photoelectric conversion efficiency becomes higher.
上記フタロシアニン骨格を有する化合物の具体例としては、例えば、無金属フタロシアニン、亜鉛フタロシアニン、t−ブチル基を有する亜鉛フタロシアニン、t−ブチル基を有するパラジウムフタロシアニン、フェニル基を有するパラジウムフタロシアニン等が挙げられる。 Specific examples of the compound having a phthalocyanine skeleton include metal-free phthalocyanine, zinc phthalocyanine, zinc phthalocyanine having a t-butyl group, palladium phthalocyanine having a t-butyl group, and palladium phthalocyanine having a phenyl group.
上記ホール輸送層は、上記フタロシアニン骨格を有する化合物に加えて、下記一般式(1)で表されるフタロシアニン化合物カチオンとフッ素含有化合物アニオンとが結合したイオン化合物を含有することが好ましい。このようなイオン化合物を含有することにより、本発明の太陽電池は、光電変換効率と耐久性を両立しやすくなる。
下記一般式(1)で表されるフタロシアニン化合物カチオンとフッ素含有化合物アニオンとが結合したイオン化合物からなる有機半導体用材料もまた、本発明の一つである。
The hole transport layer preferably contains, in addition to the compound having a phthalocyanine skeleton, an ionic compound in which a phthalocyanine compound cation represented by the following general formula (1) and a fluorine-containing compound anion are combined. By containing such an ionic compound, the solar cell of the present invention can easily achieve both photoelectric conversion efficiency and durability.
A material for an organic semiconductor, which comprises an ionic compound in which a phthalocyanine compound cation represented by the following general formula (1) and a fluorine-containing compound anion are combined, is also one aspect of the present invention.
上記フッ素含有アニオンは、上記一般式(1)で表されるフタロシアニン化合物カチオンと安定なイオン化合物を形成できるものであれば特に限定されない。なかでも、下記式(2−1)で表されるアニオン、下記式(2−2)で表されるアニオン、下記式(2−3)で表されるアニオン、下記式(2−4)で表されるアニオン、下記式(2−5)で表されるアニオン、又は、下記式(2−6)で表されるアニオンであることが好ましい。 The fluorine-containing anion is not particularly limited as long as it can form a stable ionic compound with the phthalocyanine compound cation represented by the general formula (1). Among them, an anion represented by the following formula (2-1), an anion represented by the following formula (2-2), an anion represented by the following formula (2-3), and a following formula (2-4) An anion represented by the following formula, an anion represented by the following formula (2-5), or an anion represented by the following formula (2-6) is preferable.
上記ホール輸送層は、上記フタロシアニン骨格を有する化合物に加えて、他のホール輸送材料を含有してもよい。上記他のホール輸送材料としては例えば、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、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、トリフェニルアミン骨格等を有する化合物等が挙げられる。上記ホール輸送層における上記フタロシアニン骨格を有する化合物の割合は、スパッタリング耐性及び耐久性を高める観点からは、上限は特に限定されないが、下限は70モル%以上が好ましく、80モル%以上がより好ましく、90モル%以上が更に好ましく、100モル%が特に好ましい。
また、上記ホール輸送層の製膜方法は特に限定されず、上記フタロシアニン骨格を有する化合物を含むホール輸送層材料を真空蒸着法等の乾式工程を用いて積層することもできるが、下層である上記光電変換層に対する形状追従の観点から、上記フタロシアニン骨格を有する化合物を含むホール輸送層材料を有機溶媒等に溶解させた溶液を塗布することによって積層する湿式工程が好ましい。
The hole transport layer may contain another hole transport material in addition to the compound having the phthalocyanine skeleton. Examples of the other hole transport material 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, compounds having a porphyrin skeleton such as a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, a triphenylamine skeleton, and the like can be given. The ratio of the compound having the phthalocyanine skeleton in the hole transport layer is not particularly limited in terms of increasing sputtering resistance and durability, but the lower limit is preferably 70 mol% or more, more preferably 80 mol% or more, 90 mol% or more is more preferable, and 100 mol% is particularly preferable.
Further, the method for forming the hole transport layer is not particularly limited, and the hole transport layer material containing the compound having the phthalocyanine skeleton may be laminated using a dry process such as a vacuum deposition method. From the viewpoint of conforming to the shape of the photoelectric conversion layer, a wet process of laminating by applying a solution in which the hole transport layer material containing the compound having a phthalocyanine skeleton is dissolved in an organic solvent or the like is preferable.
上記ホール輸送層の厚みは、好ましい下限は1nm、好ましい上限は2000nmである。上記厚みが1nm以上であれば、充分に電子をブロックできるようになる。上記厚みが2000nm以下であれば、ホール輸送の際の抵抗になり難く、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3nm、より好ましい上限は500nmであり、更に好ましい下限は5nm、更に好ましい上限は200nmである。 The preferable lower limit of the thickness of the hole transport layer is 1 nm, and the preferable upper limit thereof is 2000 nm. When the thickness is 1 nm or more, electrons can be sufficiently blocked. When the thickness is 2000 nm or less, resistance during hole transportation is less likely to occur, and photoelectric conversion efficiency increases. The more preferable lower limit of the thickness is 3 nm, the more preferable upper limit thereof is 500 nm, the still more preferable lower limit thereof is 5 nm, and the still more preferable upper limit thereof is 200 nm.
上記ホール輸送層は単層でも多層でもよく、多層の場合は、スパッタリング耐性をより高める観点からは、上記ホール輸送層の最外層に上記フタロシアニン骨格を有する化合物が配置されていることが好ましい。上記最外層の厚みの好ましい下限は1nm、好ましい上限は100nmであり、より好ましい下限は5nm、より好ましい上限は70nmである。上記最外層以外の層に含まれるホール輸送層材料としては、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、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等を有する化合物等が挙げられる。 The hole transport layer may be a single layer or multiple layers. In the case of a multilayer, it is preferable that the compound having the phthalocyanine skeleton is arranged in the outermost layer of the hole transport layer from the viewpoint of further improving the sputtering resistance. The preferred lower limit of the thickness of the outermost layer is 1 nm, the preferred upper limit is 100 nm, the more preferred lower limit is 5 nm, and the more preferred upper limit is 70 nm. Examples of the hole transport layer material included in the layers other than the outermost layer 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. Further, examples thereof include compounds having a porphyrin skeleton such as a naphthalocyanine skeleton, a pentacene skeleton, and a benzoporphyrin skeleton.
本発明の太陽電池においては、上記電極と上記光電変換層との間に、電子輸送層が配置されていてもよい。
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。
In the solar cell of the present invention, an electron transport layer may be arranged between the electrode and the photoelectric conversion layer.
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. Specific examples include agents such as cyano group-containing polyphenylene vinylene, boron-containing polymers, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compounds, benzimidazole compounds, naphthalenetetracarboxylic acid compounds, perylene derivatives, 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のみからなっていてもよいが、多孔質状の電子輸送層を含むことが好ましい。特に、上記光電変換層が、上記有機無機ペロブスカイト化合物を含む複合膜である場合、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 may be composed of only a thin film electron transport layer, but preferably includes a porous electron transport layer. In particular, when the photoelectric conversion layer is a composite film containing the organic-inorganic perovskite compound, a more complicated composite film (more complicated intricate structure) is obtained, and the photoelectric conversion efficiency is increased, so that the porous film is porous. It is preferable that the composite film is formed on the electron transporting layer.
上記電子輸送層の厚みは、好ましい下限が1nm、好ましい上限が2000nmである。上記厚みが1nm以上であれば、充分にホールをブロックできるようになる。上記厚みが2000nm以下であれば、電子輸送の際の抵抗になり難く、光電変換効率が高くなる。上記電子輸送層の厚みのより好ましい下限は3nm、より好ましい上限は1000nmであり、更に好ましい下限は5nm、更に好ましい上限は500nmである。 The preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit thereof is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. When the thickness is 2000 nm or less, resistance during electron transport is less likely to occur, and photoelectric conversion efficiency is increased. A more preferable lower limit of the thickness of the electron transport layer is 3 nm, a more preferable upper limit thereof is 1000 nm, a still more preferable lower limit thereof is 5 nm, and a still more preferable upper limit thereof is 500 nm.
本発明の太陽電池においては、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 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.
本発明の太陽電池は、上述したような、必要に応じて配置される上記基板上に上記電極、必要に応じて上記電子輸送層、上記光電変換層、上記ホール輸送層及び上記透明電極が形成された積層体が、封止材で封止されていてもよい。上記封止材としてはガスバリア性を有していれば特に限定されないが、熱硬化性樹脂及び熱可塑性樹脂並びに無機材料等が挙げられる。 In the solar cell of the present invention, as described above, the electrode is formed on the substrate arranged as necessary, the electron transport layer, the photoelectric conversion layer, the hole transport layer, and the transparent electrode are formed if necessary. The laminated body thus formed may be sealed with a sealing material. The sealing material is not particularly limited as long as it has a gas barrier property, and examples thereof include thermosetting resins, thermoplastic resins, and inorganic materials.
上記熱硬化性樹脂及び熱可塑性樹脂としては、エポキシ樹脂、アクリル樹脂、シリコン樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、ブチルゴム、ポリエステル、ポリウレタン、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリビニルアルコール、ポリ酢酸ビニル、ABS樹脂、ポリブタジエン、ポリアミド、ポリカーボネート、ポリイミド、ポリイソブチレン等が挙げられる。 Examples of the thermosetting resin and thermoplastic resin include epoxy resin, acrylic resin, silicon resin, phenol resin, melamine resin, urea resin, butyl rubber, polyester, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, poly Examples thereof include vinyl acetate, ABS resin, polybutadiene, polyamide, polycarbonate, polyimide and polyisobutylene.
上記無機材料としては、Si、Al、Zn、Sn、In、Ti、Mg、Zr、Ni、Ta、W、Cu若しくはこれらを2種以上含む合金の酸化物、窒化物又は酸窒化物が挙げられる。なかでも、上記封止材に水蒸気バリア性及び柔軟性を付与するために、Zn、Snの両金属元素を含む金属元素の酸化物、窒化物又は酸窒化物が好ましい。 Examples of the inorganic material include oxides, nitrides or oxynitrides of Si, Al, Zn, Sn, In, Ti, Mg, Zr, Ni, Ta, W, Cu or alloys containing two or more of these. .. Among them, oxides, nitrides or oxynitrides of metal elements containing both metal elements Zn and Sn are preferable in order to impart water vapor barrier properties and flexibility to the above-mentioned sealing material.
上記無機材料と、上記積層体との間には、上記積層体の最表面を平坦化させるために上記熱硬化性樹脂及び/又は熱可塑性樹脂が配置されていてもよい。 The thermosetting resin and/or the thermoplastic resin may be disposed between the inorganic material and the laminate to flatten the outermost surface of the laminate.
また、本発明の太陽電池においては、更に、上記封止材上を、例えばガラス板、樹脂フィルム、無機材料を被覆した樹脂フィルム、金属箔等のその他の材料が覆っていてもよい。即ち、本発明の太陽電池は、上記積層体と上記その他の材料との間を、上記封止材によって封止、充填又は接着している構成であってもよい。これにより、仮に上記封止材にピンホールがあった場合にも充分に水蒸気をブロックすることができ、太陽電池の耐久性をより向上させることができる。 Further, in the solar cell of the present invention, the sealing material may be covered with other materials such as a glass plate, a resin film, a resin film coated with an inorganic material, and a metal foil. That is, the solar cell of the present invention may have a configuration in which the layered product and the other materials are sealed, filled, or adhered with the sealing material. Thereby, even if there is a pinhole in the encapsulant, the water vapor can be sufficiently blocked, and the durability of the solar cell can be further improved.
本発明の太陽電池を製造する方法は特に限定されず、例えば、必要に応じて配置される上記基板上に上記電極、必要に応じて上記電子輸送層、上記光電変換層、上記ホール輸送層及び上記透明電極をこの順で形成して積層体を作製した後、上記封止材で上記積層体を封止する方法等が挙げられる。 The method for producing the solar cell of the present invention is not particularly limited, and, for example, the electrode on the substrate arranged as necessary, the electron transport layer if necessary, the photoelectric conversion layer, the hole transport layer and Examples include a method in which the transparent electrode is formed in this order to produce a laminated body, and then the laminated body is sealed with the sealing material.
上記光電変換層を形成する方法は特に限定されず、真空蒸着法、スパッタリング法、気相反応法(CVD)、電気化学沈積法、印刷法等が挙げられる。なかでも、印刷法を採用することで、高い光電変換効率を発揮できる太陽電池を大面積で簡易に形成することができる。印刷法として、例えば、スピンコート法、キャスト法等が挙げられ、印刷法を用いた方法としてロールtoロール法等が挙げられる。 The method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include a vacuum vapor deposition method, a sputtering method, a vapor phase reaction method (CVD), an electrochemical deposition method, and a printing method. Above all, by adopting the printing method, a solar cell capable of exhibiting high photoelectric conversion efficiency can be easily formed in a large area. Examples of the printing method include a spin coating method and a casting method, and examples of the printing method include a roll-to-roll method.
上記封止材のうち、上記熱硬化性樹脂及び熱可塑性樹脂で上記積層体を封止する方法は特に限定されず、例えば、シート状の封止材を用いて上記積層体をシールする方法、封止材を有機溶媒に溶解させた封止材溶液を上記積層体に塗布する方法、封止材となる液状モノマーを上記積層体に塗布した後、熱又はUV等で液状モノマーを架橋又は重合させる方法、封止材に熱をかけて融解させた後に冷却させる方法等が挙げられる。 Of the encapsulant, the method of sealing the laminate with the thermosetting resin and the thermoplastic resin is not particularly limited, for example, a method of sealing the laminate using a sheet-like encapsulant, A method of applying a sealing material solution in which an encapsulating material is dissolved in an organic solvent to the above-mentioned laminated body, and after applying a liquid monomer serving as an encapsulating material to the above-mentioned laminated body, crosslinking or polymerization of the liquid monomer by heat or UV. Examples of the method include a method of applying the heat, a method of applying heat to the encapsulating material to melt it, and then cooling it.
上記封止材のうち、上記無機材料で上記積層体を覆う方法として、真空蒸着法、スパッタリング法、気相反応法(CVD)、イオンプレーティング法が好ましい。なかでも、緻密な層を形成するためにはスパッタリング法が好ましく、スパッタリング法のなかでもDCマグネトロンスパッタリング法がより好ましい。
上記スパッタリング法においては、金属ターゲット、及び、酸素ガス又は窒素ガスを原料とし、上記積層体上に原料を堆積して製膜することにより、無機材料からなる無機層を形成することができる。
Among the encapsulating materials, as a method of covering the laminate with the inorganic material, a vacuum vapor deposition method, a sputtering method, a vapor phase reaction method (CVD), and an ion plating method are preferable. Among them, the sputtering method is preferable for forming a dense layer, and the DC magnetron sputtering method is more preferable among the sputtering methods.
In the above-mentioned sputtering method, an inorganic layer made of an inorganic material can be formed by using a metal target and oxygen gas or nitrogen gas as a raw material and depositing the raw material on the above-mentioned laminate to form a film.
本発明によれば、スパッタリング耐性があり、かつ光電変換効率が高く、高温高湿下においても耐えうる太陽電池、及び、有機半導体材料を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the solar cell which has sputtering resistance, has high photoelectric conversion efficiency, and can withstand high temperature and high humidity, and an organic-semiconductor material can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
(参考例1)
(太陽電池の作製)
チタン基板を純水、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。
チタン基板表面上に、2重量%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20nm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25nm)とエタノール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500nmの多孔質状の電子輸送層を形成した。
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を溶媒としてCH3NH3IとPbCl2をモル比1:1で溶かし、CH3NH3IとPbCl2の合計重量濃度を20%に調製した。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、光電変換層を形成した。更に、光電変換層上に、ホール輸送層として、クロロベンゼンを溶媒として用いた塗布法によりニッケルフタロシアニン(中心金属Ni、α位=H、β位=t−ブチル基)を100nmの厚みに積層した。ホール輸送層上に、スズが5%ドープされたITOターゲットを用い、O2(5%)を含むArガスを用い、圧力0.5Paという条件で、スパッタリング法にて透明電極として厚み100nmのITO膜を形成し、太陽電池を得た。なお、本参考例、実施例、比較例において、フタロシアニンの置換基は全て4置換のものを用いた。
( Reference example 1 )
(Production of solar cell)
The titanium substrate was ultrasonically cleaned using pure water, acetone, and methanol in this order for 10 minutes, respectively, and then dried.
A titanium isopropoxide ethanol solution adjusted to 2% by weight was applied on the surface of a titanium substrate 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 20 nm. Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder, titanium oxide (average particle size 25 nm) and ethanol was applied on the thin film electron transport layer by spin coating, and then at 500° C. for 10 minutes. Firing was performed to form a porous electron transport layer having a thickness of 500 nm.
Then, as a solution for forming an organic-inorganic perovskite compound, CH 3 NH 3 I and PbCl 2 were dissolved at a molar ratio of 1:1 using N,N-dimethylformamide as a solvent, and the total weight concentration of CH 3 NH 3 I and PbCl 2 was changed. It was adjusted to 20%. This solution was laminated on the electron transport layer by spin coating to form a photoelectric conversion layer. Further, nickel phthalocyanine (central metal Ni, α-position=H, β-position=t-butyl group) was laminated on the photoelectric conversion layer as a hole-transporting layer to a thickness of 100 nm by a coating method using chlorobenzene as a solvent. On the hole transport layer, an ITO target doped with 5% tin was used, Ar gas containing O 2 (5%) was used, and a pressure of 0.5 Pa was used as a transparent electrode with a thickness of 100 nm ITO as a transparent electrode. A film was formed to obtain a solar cell. In addition, in the present Reference Examples, Examples, and Comparative Examples, the substituents of phthalocyanine were all 4-substituted.
(参考例2〜6、比較例1〜5)
ホール輸送層に用いられる材料(フタロシアニン骨格を有する化合物、又は、フタロシアニン骨格を有する化合物以外の化合物)を、表1に示される材料に変更したこと以外は参考例1と同様にして太陽電池を得た。なお、比較例4、5については、フタロシアニン骨格を有する化合物が溶媒に溶けず、塗布を行うことができなかったため、太陽電池を得ることができなかった。
( Reference Examples 2-6, Comparative Examples 1-5)
A solar cell was obtained in the same manner as in Reference Example 1 except that the material used for the hole transport layer (a compound having a phthalocyanine skeleton or a compound other than the compound having a phthalocyanine skeleton) was changed to the material shown in Table 1. It was In Comparative Examples 4 and 5, solar cells could not be obtained because the compound having a phthalocyanine skeleton did not dissolve in the solvent and coating could not be performed.
(実施例7)
パラジウムフタロシアニン(中心金属Pd、α位=H、β位=t−ブチル基)0.25gと、銀‐ビス(トリフルオロメチルスルフォニル)イミド(Ag−TFSI、Aldrich社製)0.17gとをジクロロメタンに25mLに溶解させ、500rpmで攪拌した。その後1μmメッシュを通して析出物を分離し、回収した溶液をエバポレーターにて濃縮し、パラジウムフタロシアニンカチオンとTFSIアニオンのイオン化合物を得た。次に得られたイオン化合物1mgと上記パラジウムフタロシアニン9mgをクロロベンゼン500μLに溶解させ、その溶液をスピンコート法で塗布することにより、イオン化合物を10%含有するホール輸送層を形成した。ホール輸送層以外については参考例1と同様の方法で成膜を行い、太陽電池を得た。
なお、吸収スペクトルを測定し、イオン結合を形成していないものと比較し、吸収が長波長シフトしていることを確認することにより、パラジウムフタロシアニンとTFSIとがイオン結合を形成していることが確認された。
(Example 7)
0.25 g of palladium phthalocyanine (central metal Pd, α-position=H, β-position=t-butyl group) and 0.17 g of silver-bis(trifluoromethylsulfonyl)imide (Ag-TFSI, manufactured by Aldrich) dichloromethane. Was dissolved in 25 mL and stirred at 500 rpm. Thereafter, the precipitate was separated through a 1 μm mesh, and the recovered solution was concentrated by an evaporator to obtain an ionic compound of palladium phthalocyanine cation and TFSI anion. Next, 1 mg of the obtained ionic compound and 9 mg of the above-mentioned palladium phthalocyanine were dissolved in 500 μL of chlorobenzene, and the solution was applied by spin coating to form a hole transport layer containing 10% of the ionic compound. A film was formed by the same method as in Reference Example 1 except for the hole transport layer to obtain a solar cell.
It should be noted that the palladium phthalocyanine and TFSI may form an ionic bond by measuring the absorption spectrum and comparing the absorption spectrum with that not forming an ionic bond to confirm that the absorption is shifted by a long wavelength. confirmed.
(実施例8)
Ag−TFSIの代わりにAg−NFSI(ビス(ノナフルオロブタンスルホニル)イミド、三菱マテリアル電子化成社製)を用いた以外は実施例7と同様にして太陽電池を得た。
(Example 8)
A solar cell was obtained in the same manner as in Example 7 except that Ag-NFSI (bis(nonafluorobutanesulfonyl)imide, manufactured by Mitsubishi Materials Electronics Corporation) was used instead of Ag-TFSI.
(実施例9)
パラジウムフタロシアニンのβ位の置換基をアルコキシ基(シクロヘキシルオキシ基)に変更したこと以外は、実施例8と同様にして太陽電池を得た。
(Example 9)
A solar cell was obtained in the same manner as in Example 8 except that the substituent on the β-position of palladium phthalocyanine was changed to an alkoxy group (cyclohexyloxy group).
<評価>
実施例、参考例及び比較例で得られた太陽電池について、以下の評価を行った。結果を表2に示した。なお、比較例4、5は、太陽電池が得られなかったため評価を行わなかった。
<Evaluation>
The following evaluations were performed on the solar cells obtained in the examples , reference examples and comparative examples. The results are shown in Table 2. Comparative Examples 4 and 5 were not evaluated because no solar cell was obtained.
(1)光電変換効率
得られた太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定した。なお、比較例1で得られた太陽電池の光電変換効率を1.0として、参考例1〜6、実施例7〜9及び比較例2、3で得られた太陽電池の光電変換効率を規格化した。
(1) Photoelectric conversion efficiency A power source (KEITHLEY, 236 model) was connected between the obtained solar cell electrodes, and the photoelectric conversion efficiency was calculated using a solar simulation (Yamashita Denso Co., Ltd.) with an intensity of 100 mW/cm 2. It was measured. The photoelectric conversion efficiency of the solar cells obtained in Comparative Example 1 was set to 1.0, and the photoelectric conversion efficiency of the solar cells obtained in Reference Examples 1 to 6, Examples 7 to 9 and Comparative Examples 2 and 3 was standardized. Turned into
(2)耐久性
得られた太陽電池上にアクリル樹脂を塗工し、更にSiO2をスパッタリング法により積層し、封止した後、85RH%、85℃の条件に48時間置いて耐久性試験を行った。耐久性試験前及び耐久性試験後の太陽電池の電極間に、電源(KEITHLEY社製、236モデル)を接続し、強度100mW/cm2のソーラーシミュレーション(山下電装社製)を用いて光電変換効率を測定し、耐久性試験後の光電変換効率/耐久性試験前の光電変換効率の値を求めた。
○:耐久性試験後の光電変換効率/耐久性試験前の光電変換効率の値が0.8以上
×:耐久性試験後の光電変換効率/耐久性試験前の光電変換効率の値が0.8未満
(2) Durability Acrylic resin was coated on the obtained solar cell, SiO 2 was further laminated by a sputtering method, and after sealing, it was placed under conditions of 85 RH% and 85° C. for 48 hours for durability test. went. Before and after the durability test, a power supply (KEITHLEY, 236 model) is connected between the electrodes of the solar cell, and a solar simulation (manufactured by Yamashita Denso Co., Ltd.) with a strength of 100 mW/cm 2 is used. Was measured, and the value of photoelectric conversion efficiency after durability test/photoelectric conversion efficiency before durability test was determined.
◯: The value of photoelectric conversion efficiency after durability test/photoelectric conversion efficiency before durability test is 0.8 or more×: photoelectric conversion efficiency after durability test/value of photoelectric conversion efficiency before durability test is 0. Less than 8
本発明によれば、スパッタリング耐性があり、かつ光電変換効率が高く、高温高湿下においても耐えうる太陽電池、及び、有機半導体用材料を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the solar cell which has sputtering resistance and high photoelectric conversion efficiency, and can withstand high temperature and high humidity, and the material for organic semiconductors can be provided.
Claims (4)
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、
前記ホール輸送層は、フタロシアニン骨格を有する化合物を含み、前記フタロシアニン骨格を有する化合物がアルキル基、アルコキシ基、ハロゲン基、及び芳香族基からなる群から選択される少なくとも1種の置換基を有し、ホール輸送層に、下記一般式(1)で表されるフタロシアニン化合物カチオンとフッ素含有化合物アニオンとが結合したイオン化合物を含有することを特徴とする太陽電池。
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,
The hole transporting layer comprises a compound having a phthalocyanine skeleton, possess the compound having a phthalocyanine skeleton is an alkyl group, an alkoxy group, at least one substituent selected from the group consisting of halogen groups, and aromatic groups A solar cell , wherein the hole transport layer contains an ionic compound in which a phthalocyanine compound cation represented by the following general formula (1) and a fluorine-containing compound anion are combined .
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