JP6755678B2 - Solar cell - Google Patents
Solar cell Download PDFInfo
- Publication number
- JP6755678B2 JP6755678B2 JP2016042312A JP2016042312A JP6755678B2 JP 6755678 B2 JP6755678 B2 JP 6755678B2 JP 2016042312 A JP2016042312 A JP 2016042312A JP 2016042312 A JP2016042312 A JP 2016042312A JP 6755678 B2 JP6755678 B2 JP 6755678B2
- Authority
- JP
- Japan
- Prior art keywords
- solar cell
- organic
- photoelectric conversion
- group
- perovskite compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000006243 chemical reaction Methods 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 59
- 239000003566 sealing material Substances 0.000 claims description 25
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- 230000000737 periodic effect Effects 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 14
- 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 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 229910052762 osmium Inorganic materials 0.000 claims description 11
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 11
- 239000010948 rhodium Substances 0.000 claims description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
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- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Chemical compound C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 description 3
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
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- 229910001631 strontium chloride Inorganic materials 0.000 description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 3
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 3
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- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 2
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Description
本発明は、高い光電変換効率を発揮できる太陽電池に関する。 The present invention relates to a solar cell capable of exhibiting high photoelectric conversion efficiency.
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。 Conventionally, a photoelectric conversion element having a laminate in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between facing electrodes has been developed. In such a photoelectric conversion element, optical carriers are generated by photoexcitation, and an electric field is generated by moving electrons in an N-type semiconductor and holes in a P-type semiconductor.
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 by using an inorganic semiconductor such as silicon. However, since inorganic solar cells are expensive to manufacture, difficult to increase in size, and have a limited range of use, organic solar cells manufactured using organic semiconductors instead of inorganic semiconductors are attracting 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 organic solar cells, fullerenes are used. Fullerenes are known to mainly act as N-type semiconductors. For example, Patent Document 1 describes a semiconductor heterojunction film formed by using an organic compound serving as a P-type semiconductor and fullerenes. However, in organic solar cells manufactured using fullerenes, it is known that the cause of deterioration is fullerenes (see, for example, Non-Patent Document 1), and a material alternative to 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, has been discovered and shown to have high photoelectric conversion efficiency (for example, Non-Patent Document 2). ..
本発明は、高い光電変換効率を発揮できる太陽電池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 capable of exhibiting high photoelectric conversion efficiency.
本発明は、電極と、対向電極と、前記電極と前記対向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と、周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、チタン及びランタンからなる群から選択される１種以上の元素とを含有する部位を有する太陽電池である。
以下、本発明を詳述する。
The present invention is a solar cell having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode, and the photoelectric conversion layer is a general formula RMX 3 (However, R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom.) An organic-inorganic perovskite compound represented by a periodic table group 2 element, a periodic table group 11 element, cesium, ittrium, A solar cell having a moiety containing one or more elements selected from the group consisting of osmium, rhodium, manganese, antimony, titanium and lanthanum.
Hereinafter, the present invention will be described in detail.
本発明者らは、電極と、対向電極と、前記電極と前記対向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。
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太陽電池は、更なる光電変換効率の向上が課題となっていた。これに対して、本発明者らは、光電変換層を、有機無機ペロブスカイト化合物と、周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、チタン及びランタンからなる群から選択される１種以上の元素とを含有する部位（以下、「有機無機ペロブスカイト化合物部位」ともいう。）を有するものとすることにより、光電変換効率を飛躍的に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 have decided to use a specific organic-inorganic perovskite compound for the photoelectric conversion layer in a solar cell having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode. investigated. By using an organic-inorganic perovskite compound, improvement in photoelectric conversion efficiency of a solar cell can be expected.
However, in a solar cell in which the photoelectric conversion layer contains an organic-inorganic perovskite compound, further improvement in photoelectric conversion efficiency has been an issue. On the other hand, the present inventors make the photoelectric conversion layer from an organic-inorganic perovskite compound, a group 2 element of the periodic table, an element of group 11 of the periodic table, cesium, yttrium, osmium, rhodium, manganese, antimony, titanium and lantern. It was found that the photoelectric conversion efficiency can be dramatically improved by having a site containing one or more elements selected from the above group (hereinafter, also referred to as "organic-inorganic perovskite compound site"). The present invention has been completed.
本発明の太陽電池は、電極と、対向電極と、上記電極と上記対向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 counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode.
In the present specification, the layer means not only a layer having a clear boundary but also a layer having a concentration gradient in which the contained elements gradually change. The elemental analysis of the layer can be performed, for example, by 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 intricate structure together with other layers.
上記電極及び上記対向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。なお、上記対向電極は、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。また、上記電極及び上記対向電極は、それぞれ陰極になっても、陽極になってもよい。
The material of the electrode and the counter electrode is not particularly limited, and conventionally known materials can be used. The counter electrode is often a patterned electrode.
As electrode materials, for example, 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 thereof include an Al 2 O 3 mixture and an Al / Li F mixture. Examples of counter electrode materials 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. Further, the electrode and the counter electrode may be a cathode or an anode, respectively.
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有機無機ペロブスカイト化合物部位を有する。
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 is an organic-inorganic compound containing an organic-inorganic perovskite compound represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom). It has a perovskite compound site.
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、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特に好ましい。
The above R is an organic molecule, and is preferably represented by C l N m H n (all l, m, and n are positive integers).
Specifically, the R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl. Amine, tributylamine, trypentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirin, Azetidine, azeto, imidazoline, carbazole, methylcarboxyamine, ethylcarboxyamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, hexylcarboxyamine, formamidinium, guanidine, aniline, pyridine and their ions (eg, methylammonium). (CH 3 NH 3 ), etc.) and phenethylammonium, etc. can be mentioned. Of these, methylamine, ethylamine, propylamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, guanidine and their ions are preferred, with methylamine, ethylamine, pentylcarboxyamine, formamidinium, guanidine and These ions are more preferred. Of these, methylamine, formaminidium and ions thereof are particularly preferable because high photoelectric conversion efficiency can be obtained.
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 above 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, Europium and the like can be mentioned. Of these, lead or tin is preferable from the viewpoint of overlapping electron orbitals. 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 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, a halogen atom is preferable because the inclusion of halogen in the structure makes the organic-inorganic perovskite compound soluble in an organic solvent and can be applied to an inexpensive printing method or the like. Further, 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 at the body center, an organic molecule R is arranged at each apex, and a halogen atom or a chalcogen atom X is arranged at the face center.
FIG. 1 shows an example of the crystal structure of an organic-inorganic perovskite compound, which is a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each apex, and a halogen atom or a chalcogen atom X is arranged at the face center. It is a schematic diagram. Although the details are not clear, the orientation of the octahedron in the crystal lattice can be easily changed by having the above structure, so that the mobility of electrons in the organic-inorganic perovskite compound is high, and the photoelectric of the solar cell is high. It is estimated that the conversion efficiency will improve.
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、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、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る。
The organic-inorganic perovskite compound is preferably a crystalline semiconductor. The crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting the scattering peak.
If 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 solar cell is improved. Further, if the organic-inorganic perovskite compound is a crystalline semiconductor, a decrease in photoelectric conversion efficiency (light deterioration) due to continuous irradiation of the solar cell with light, particularly a decrease in light deterioration due to a decrease in short-circuit current is suppressed.
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、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、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。
It is also possible to evaluate the degree of crystallinity as an index of crystallization. The degree of crystallinity is determined by separating the scattering peak derived from the crystalline substance and the halo derived from the amorphous part detected by the X-ray scattering intensity distribution measurement by fitting, and obtaining the intensity integration of each to obtain the crystal part of the whole. It can be obtained by calculating the ratio of.
The 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. Further, when the crystallinity is 30% or more, a decrease in photoelectric conversion efficiency (photodegradation) due to continuous irradiation of the solar cell with light, particularly photodegradation due to a decrease in short-circuit current is suppressed. The more preferable lower limit of the crystallinity is 50%, and the more preferable lower limit is 70%.
Further, as a method for increasing the crystallinity of the organic-inorganic perovskite compound, for example, thermal annealing (heat treatment), irradiation with strong light such as a laser, plasma irradiation and the like can be mentioned.
上記熱アニール（加熱処理）を行う場合、上記有機無機ペロブスカイト化合物を加熱する温度は特に限定されないが、１００℃以上、２５０℃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２５０℃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、２３０℃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。
When the thermal annealing (heat treatment) is performed, the temperature at which the organic-inorganic perovskite compound is heated is not particularly limited, but is preferably 100 ° C. or higher and lower than 250 ° 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 less than 250 ° C., the heat treatment can be performed without thermally deteriorating the organic-inorganic perovskite compound. More preferable heating temperatures are 120 ° C. or higher and 230 ° 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. If 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 under vacuum or 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.
上記有機無機ペロブスカイト化合物部位は、周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、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種の元素を含有する。
上記有機無機ペロブスカイト化合物部位がこれらの元素を含有することにより、太陽電池の光電変換効率を向上させることができる。
上記周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、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、バリウム、ストロンチウム、カルシウム、銀、銅、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、チタン、ランタン等が挙げられる。より光電変換効率が向上する観点からは、バリウム、ストロンチウム、カルシウム、銀、銅、セシウム、マンガン及びランタンからなる群から選択される１種以上の元素が好ましい。また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）を抑制する観点からは、カルシウム、ストロンチウム、銀、銅、マンガン及びランタンからなる群から選択される１種以上の元素がより好ましく、カルシウム、ストロンチウム、銀及び銅からなる群から選択される１種以上の元素が特に好ましい。
The organic-inorganic perovskite compound moiety contains at least one element selected from the group consisting of Group 2 elements of the Periodic Table, Group 11 elements of the Periodic Table, Cesium, Ittium, Osmium, Rhodium, Manganese, Antimony, Titanium and Lantern. ..
When the organic-inorganic perovskite compound moiety contains these elements, the photoelectric conversion efficiency of the solar cell can be improved.
As at least one element selected from the group consisting of the elements of Group 2 of the Periodic Table, the elements of Group 11 of the Periodic Table, cesium, ittrium, osmium, rhodium, manganese, antimony, titanium and lanthanum, specifically, for example, barium. Examples thereof include strontium, calcium, silver, copper, cesium, yttrium, osmium, rhodium, manganese, antimony, titanium and lantern. From the viewpoint of further improving the photoelectric conversion efficiency, one or more elements selected from the group consisting of barium, strontium, calcium, silver, copper, cesium, manganese and lanthanum are preferable. Further, from the viewpoint of suppressing a decrease in photoelectric conversion efficiency (light deterioration) due to continuous irradiation with light, one or more elements selected from the group consisting of calcium, strontium, silver, copper, manganese and lanthanum are more preferable. , Calcium, strontium, silver and one or more elements selected from the group consisting of copper are particularly preferred.
上記周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、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モル％に対する好ましい下限が０．０１モル％、好ましい上限が２０モル％である。上記含有量の割合（モル％）が０．０１モル％以上であれば、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モル％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モル％、より好ましい上限は１０モル％である。 The ratio (mol%) of the content of at least one element selected from the group consisting of the elements of Group 2 of the Periodic Table, the elements of Group 11 of the Periodic Table, cesium, ittrium, osmium, rhodium, manganese, antimony, titanium and lantern is Although not particularly limited, the preferable lower limit is 0.01 mol% and the preferable upper limit is 20 mol% with respect to 100 mol% of the metal element (M represented by RMX 3 ) in the organic-inorganic perovskite compound. When the content ratio (mol%) is 0.01 mol% or more, the photoelectric conversion efficiency is lowered (photodegradation) due to the continuous irradiation of the solar cell with light, especially the short-circuit current density and the fill factor are lowered. The resulting photodegradation is suppressed. When the content ratio (mol%) is 20 mol% or less, the decrease in initial conversion efficiency due to the presence of the element can be suppressed. The more preferable lower limit of the content ratio (mol%) is 0.1 mol%, and the more preferable upper limit is 10 mol%.
上記周期表２族元素、周期表１１族元素、セシウム、イットリウム、オスミウム、ロジウム、マンガン、アンチモン、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形成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する方法等が挙げられる。 The method for containing at least one element selected from the group consisting of the elements of Group 2 of the periodic table, the elements of Group 11 of the periodic table, cesium, ittrium, osmium, rhodium, manganese, antimony, titanium and lanthanum is not particularly limited. For example, a method of mixing a halide of the above element with a solution used for forming a layer of an organic-inorganic perovskite compound can be mentioned.
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。なお、ここでいう有機半導体又は無機半導体は、後述する電子輸送層又はホール輸送層としての役割を果たしてもよい。
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 effects of the present invention are not impaired. The organic semiconductor or the inorganic semiconductor referred to here may play a role as an electron transport layer or a hole transport layer described later.
Examples of the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene). Further, for example, a conductive polymer having a polyparaphenylene vinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton and the like can be mentioned. Further, for example, a compound having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, or a carbon-containing material such as carbon nanotubes, graphene, or fullerene which may be surface-modified. 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。 As the inorganic semiconductor, e.g., 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, Examples thereof include 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 organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor are contained, the photoelectric conversion layer is a laminate in which a thin-film organic semiconductor or an inorganic semiconductor moiety and a thin-film organic-inorganic perovskite compound moiety are laminated. It may be a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited. A laminated body is preferable in terms of simple manufacturing method, 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 thickness of the thin-film organic-inorganic perovskite compound moiety has a preferable lower limit of 5 nm and a preferable upper limit of 5000 nm. When the thickness is 5 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high. When the thickness is 5000 nm or less, it is possible to suppress the occurrence of a region where charge separation is not possible, 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 is 1000 nm, the further preferable lower limit is 20 nm, and the further preferable upper limit 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 moiety and an organic-inorganic perovskite compound moiety are composited, the preferable lower limit of the thickness of the composite film is 30 nm, and the preferable upper limit is 3000 nm. When the thickness is 30 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high. When the thickness is 3000 nm or less, the electric charge easily reaches the electrode, so that the photoelectric conversion efficiency is high. The more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the further preferable lower limit is 50 nm, and the further preferable upper limit is 1000 nm.
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 for example, N-type conductive polymer, N-type low-molecular-weight organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, and surface activity. Examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymer, vasocuproin, vasophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compound, benzoimidazole compound, naphthalenetetracarboxylic acid compound, perylene derivative, and the like. Examples thereof include phosphine oxide compounds, phosphine sulfide compounds, fluorogroup-containing phthalocyanine, 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（バッファ層）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、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 may be composed of only a thin film electron transport layer (buffer layer), but preferably includes 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 moiety and an organic-inorganic perovskite compound are composited, a more complicated composite film (more complicated structure) can be obtained, and the photoelectric conversion efficiency can be improved. Since it is high, it is preferable that a composite film is formed on the porous electron transport 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 thickness of the electron transport layer has a preferable lower limit of 1 nm and a preferable upper limit of 2000 nm. If the thickness is 1 nm or more, the holes can be sufficiently blocked. When the thickness is 2000 nm or less, it is unlikely to become a resistance during electron transport, and the photoelectric conversion efficiency becomes high. The more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
本発明の太陽電池においては、上記光電変換層と上記対向電極との間に、ホール輸送層の材料が積層されてもよい。
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（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、トリフェニルアミン骨格、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、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、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。
In the solar cell of the present invention, the material of the hole transport layer may be laminated between the photoelectric conversion layer and the counter electrode.
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 compounds having a thiophene skeleton such as poly (3-alkylthiophene). Further, for example, a conductive polymer having a triphenylamine skeleton, a polyparaphenylene vinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton and the like can be mentioned. Further, for example, compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a phthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, sulfide. Examples thereof include molybdenum, tungsten sulfide, copper sulfide, tin sulfide and the like, fluorogroup-containing phosphonic acid, carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI, and carbon-containing materials such as carbon nanotubes and graphene.
上記ホール輸送層の材料は一部が上記光電変換層に浸漬していてもよいし、上記光電変換層上に薄膜状に配置されてもよい。上記ホール輸送層の材料が薄膜状に存在する時の厚みは、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。 A part of the material of the hole transport layer may be immersed in the photoelectric conversion layer, or may be arranged in a thin film on the photoelectric conversion layer. When the material of the hole transport layer is present in the form of a thin film, the preferable lower limit is 1 nm and the preferable upper limit is 2000 nm. If 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 unlikely to occur, and the photoelectric conversion efficiency is high. The more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
本発明の太陽電池は、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、金属基板、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 or the like. The substrate is not particularly limited, and examples thereof include transparent glass substrates such as soda lime glass and non-alkali glass, ceramic substrates, metal substrates, and transparent plastic substrates.
本発明の太陽電池は、上述したような、電極と、対向電極と、上記電極と上記対向電極との間に配置された光電変換層とを有する積層体（即ち、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、必要に応じて上記ホール輸送層及び上記対向電極が形成された上記積層体）が、封止材で封止されていることが好ましい。上記積層体が封止材で封止されていることで、太陽電池の光電変換効率を向上させることができる。ここで、上記封止材は、その端部を閉じるようにして、上記積層体全体を覆うことが好ましい。上記封止材としては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。 The solar cell of the present invention is a laminate having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode as described above (that is, arranged as necessary). The electrode, if necessary, the electron transport layer, the photoelectric conversion layer, and if necessary, the hole transport layer and the laminate in which the counter electrode is formed) are sealed with a sealing material on the substrate. Is preferable. Since the laminate is sealed with a sealing material, the photoelectric conversion efficiency of the solar cell can be improved. Here, it is preferable that the sealing material covers the entire laminated body so as to close the end portion thereof. The sealing material is not particularly limited as long as it has a 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, and poly. Examples thereof include vinyl acetate, ABS resin, polybutadiene, polyamide, polycarbonate, polyimide, polyisobutylene and the like.
上記封止材の厚みは、好ましい下限が１００ｎｍ、好ましい上限が１０００００ｎｍである。上記厚みのより好ましい下限は５００ｎｍ、より好ましい上限は５００００ｎｍであり、更に好ましい下限は１０００ｎｍ、更に好ましい上限は２００００ｎｍである。 The preferable lower limit of the thickness of the sealing material is 100 nm, and the preferable upper limit is 100,000 nm. The more preferable lower limit of the thickness is 500 nm, the more preferable upper limit is 50,000 nm, the further preferable lower limit is 1000 nm, and the further preferable upper limit is 20000 nm.
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 and oxynitrides of Si, Al, Zn, Sn, In, Ti, Mg, Zr, Ni, Ta, W, Cu and alloys containing two or more of them. .. Among them, oxides, nitrides or oxynitrides of metal elements including both Zn and Sn metal elements are preferable in order to impart water vapor barrier property and flexibility to the sealing material.
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。 Among the sealing materials, the method of sealing the laminate with the thermosetting resin and the thermoplastic resin is not particularly limited, and for example, a method of sealing the laminate with a sheet-shaped sealing material. A method of applying a sealing material solution in which a sealing material is dissolved in an organic solvent to the laminate, a method of applying a liquid monomer to be a sealing material to the laminate, and then cross-linking or polymerizing the liquid monomer with heat or UV or the like. Examples thereof include a method of allowing the sealing material to be heated, a method of melting the sealing material, and then cooling the sealing material.
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。
上記封止材は、上記熱硬化性樹脂及び熱可塑性樹脂と、上記無機材料との組み合わせでもよい。
Among the sealing materials, a vacuum deposition method, a sputtering method, a vapor phase reaction method (CVD), and an ion plating method are preferable as a method of covering the laminated body with the inorganic material. 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 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 raw materials and depositing the raw materials on the laminate to form a film.
The sealing material may be a combination of the thermosetting resin and the thermoplastic resin and the inorganic material.
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 further 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 laminate and the other material are sealed, filled or bonded with the sealing material. As a result, even if the sealing material has pinholes, 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、必要に応じて上記ホール輸送層及び上記対向電極をこの順で形成して上記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, the electron transport layer if necessary, the photoelectric conversion layer if necessary, and the above if necessary on the substrate arranged as needed. Examples thereof include a method in which the hole transport layer and the counter electrode are formed in this order to prepare the 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 deposition method, a sputtering method, a vapor phase reaction method (CVD), an electrochemical deposition method, and a printing method. In particular, by adopting the printing method, it is possible to easily form a solar cell capable of exhibiting high photoelectric conversion efficiency in a large area. Examples of the printing method include a spin coating method and a casting method, and examples of the method using the printing method include a roll-to-roll method.
本発明によれば、高い光電変換効率を発揮できる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 solar cell capable of exhibiting high photoelectric conversion efficiency.
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.
（実施例１）
（１）チタンを含有する塗布液の作製
チタン粉末１０ｍｍｏｌを精秤し、ビーカーに入れ、過酸化水素水４０ｇを加え、さらにアンモニア水１０ｇを加えた。これを２時間水冷した後、Ｌ−乳酸３０ｍｍｏｌを添加し、８０℃に設定したホットプレートで一日加温し、そこへ蒸留水１０ｍｌを添加しチタンを含有する塗布液を作製した。
（２）太陽電池の作製
ガラス基板上に、電極（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。
チタンを含有する塗布液を回転数１５００ｒｐｍの条件でスピンコート法により塗布した。塗布後、大気中５５０℃で１０分間焼成し、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３００ｎｍの多孔質状の電子輸送層を形成した。次いで、ハロゲン化金属化合物としてヨウ化鉛をＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）に溶解させて１Ｍの溶液を調製した。さらに銅を添加するために、上記ヨウ化鉛のＤＭＦ溶液に０．０１Ｍの濃度（銅の含有量（表中、添加物濃度）＝鉛１００モル％に対して１モル％）になるように添加物として塩化銅を溶解させて、これを上記多孔質状の電子輸送層上にスピンコート法によって製膜した。更に、アミン化合物としてヨウ化メチルアンモニウムを２−プロパノールに溶解させて１Ｍの溶液を調製した。この溶液内に上記のヨウ化鉛（添加物を含む）を製膜したサンプルを浸漬させることによって有機無機ペロブスカイト化合物であるＣＨ３ＮＨ３ＰｂＩ３を含む層を形成することで、有機無機ペロブスカイト化合物部位を形成した。浸漬後、得られたサンプルに対して８０℃にて３０分間加熱処理を行った。更に、ホール輸送層としてＰｏｌｙ（４−ｂｕｔｙｌｐｈｅｎｙｌ−ｄｉｐｈｅｎｙｌ−ａｍｉｎｅ）（１−Ｍａｔｅｒｉａｌ社製）の１ｗｔ％クロロベンゼン溶液を有機無機ペロブスカイト化合物部位上にスピンコート法によって５０ｎｍの厚みに積層し、光電変換層を形成した。
光電変換層上に、対向電極（陽極）として真空蒸着により厚み１００ｎｍの金膜を形成し、積層体を作製した。得られた積層体上に、封止材としてのポリイソブチレン樹脂（ＢＡＳＦ社製のＯＰＰＡＮＯＬ１００）を１０μｍ積層したアルミホイルを１００℃でラミネートし、太陽電池を得た。
(Example 1)
(1) Preparation of Coating Solution Containing Titanium 10 mmol of titanium powder was precisely weighed, placed in a beaker, 40 g of hydrogen peroxide solution was added, and 10 g of ammonia water was further added. After cooling this with water for 2 hours, 30 mmol of L-lactic acid was added, and the mixture was heated on a hot plate set at 80 ° C. for one day, and 10 ml of distilled water was added thereto to prepare a coating solution containing titanium.
(2) Preparation of Solar Cell An FTO film having a thickness of 1000 nm was formed as an electrode (cathode) on a glass substrate, ultrasonically cleaned with pure water, acetone, and methanol in this order for 10 minutes each, and then dried.
A coating liquid containing titanium was applied by a spin coating method under the condition of a rotation speed of 1500 rpm. After coating, it was fired in the air at 550 ° C. for 10 minutes to form an electron transport layer.
Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle diameter of 10 nm and 30 nm) is applied onto a thin-film electron transport layer by a spin coating method, and then at 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 300 nm. Next, lead iodide as a metal halide compound was dissolved in N, N-dimethylformamide (DMF) to prepare a 1 M solution. In order to further add copper, the concentration of 0.01 M (copper content (additive concentration in the table) = 1 mol% with respect to 100 mol% of lead) was adjusted to the DMF solution of lead iodide. Copper chloride was dissolved as an additive, and a film was formed on the porous electron transport layer by a spin coating method. Further, methylammonium iodide as an amine compound was dissolved in 2-propanol to prepare a 1M solution. By immersing the above-mentioned lead iodide (including additives) film-formed sample in this solution to form a layer containing CH 3 NH 3 PbI 3 , which is an organic-inorganic perovskite compound, the organic-inorganic perovskite compound is formed. A site was formed. After the immersion, the obtained sample was heat-treated at 80 ° C. for 30 minutes. Further, as a hole transport layer, a 1 wt% chlorobenzene solution of Poly (4-butylphenyl-diphenyl-amine) (manufactured by 1-Material) was laminated on the organic-inorganic perovskite compound site by a spin coating method to a thickness of 50 nm, and a photoelectric conversion layer was formed. Was formed.
A gold film having a thickness of 100 nm was formed on the photoelectric conversion layer by vacuum vapor deposition as a counter electrode (anode) to prepare a laminated body. An aluminum foil obtained by laminating 10 μm of polyisobutylene resin (OPPANOL100 manufactured by BASF) as a sealing material on the obtained laminate was laminated at 100 ° C. to obtain a solar cell.
（実施例２〜１０、１２、１４〜１６、参考例１、２）
添加物を表１に記載の化合物・添加量に変更したこと、またホール輸送層を表１に記載のものに変更したこと以外は実施例１と同様にして、太陽電池を得た。
( Examples 2 to 10, 12, 14 to 16, Reference Examples 1, 2 )
A solar cell was obtained in the same manner as in Example 1 except that the additive was changed to the compound / addition amount shown in Table 1 and the hole transport layer was changed to that shown in Table 1.
（実施例１７、１８）
実施例１の多孔質状の電子輸送層上に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ＣＨ３ＮＨ３ＩとＰｂＩ２をモル比１：１で溶かし、Ｐｂの濃度が１Ｍになるように調製した。さらにストロンチウム、またはチタンを添加するために、上記の調製した溶液に０．０１Ｍの濃度（ストロンチウム又はチタンの含有量（表中、添加物濃度）＝鉛１００モル％に対して１モル％）になるように添加物として塩化ストロンチウム又はヨウ化チタンを溶解させて、これを上記多孔質状の電子輸送層上にスピンコート法によって製膜し、有機無機ペロブスカイト化合物部位を形成した。更に、ホール輸送層としてＰｏｌｙ（４−ｂｕｔｙｌｐｈｅｎｙｌ−ｄｉｐｈｅｎｙｌ−ａｍｉｎｅ）（１−Ｍａｔｅｒｉａｌ社製）の１ｗｔ％クロロベンゼン溶液を有機無機ペロブスカイト化合物部位上にスピンコート法によって５０ｎｍの厚みに積層し、光電変換層を形成した。光電変換層上に、対向電極（陽極）として真空蒸着により厚み１００ｎｍの金膜を形成し、積層体を作製した。得られた積層体上に、封止材としてのポリイソブチレン樹脂（ＢＡＳＦ社製のＯＰＰＡＮＯＬ１００）を１０μｍ積層したアルミホイルを１００℃でラミネートし、太陽電池を得た。
(Examples 17 and 18)
CH 3 NH 3 I and Pb I 2 were dissolved on the porous electron transport layer of Example 1 at a molar ratio of 1: 1 using N, N-dimethylformamide (DMF) as a solvent as a solution for forming an organic-inorganic perovskite compound. , The concentration of Pb was adjusted to 1M. In order to further add strontium or titanium, the concentration of 0.01 M (strontium or titanium content (additive concentration in the table) = 1 mol% with respect to 100 mol% of lead) was added to the above-prepared solution. Strontium chloride or titanium iodide was dissolved as an additive so as to form a film on the porous electron transport layer by a spin coating method to form an organic-inorganic perovskite compound moiety. Further, as a hole transport layer, a 1 wt% chlorobenzene solution of Poly (4-butylphenyl-diphenyl-amine) (manufactured by 1-Material) was laminated on the organic-inorganic perovskite compound site by a spin coating method to a thickness of 50 nm, and a photoelectric conversion layer was formed. Was formed. A gold film having a thickness of 100 nm was formed on the photoelectric conversion layer by vacuum vapor deposition as a counter electrode (anode) to prepare a laminated body. An aluminum foil obtained by laminating 10 μm of polyisobutylene resin (OPPANOL100 manufactured by BASF) as a sealing material on the obtained laminate was laminated at 100 ° C. to obtain a solar cell.
（実施例１９）
実施例１の多孔質状の電子輸送層上に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ＣＨ３ＮＨ３ＩとＰｂＣｌ２をモル比３：１で溶かし、Ｐｂの濃度が１Ｍになるように調製した。さらにストロンチウムを添加するために、上記の調製した溶液に０．０１Ｍの濃度（ストロンチウムの含有量（表中、添加物濃度）＝鉛１００モル％に対して１モル％）になるように添加物として塩化ストロンチウムを溶解させて、これを上記多孔質状の電子輸送層上にスピンコート法によって製膜し、有機無機ペロブスカイト化合物部位を形成した。更に、ホール輸送層としてＰｏｌｙ（４−ｂｕｔｙｌｐｈｅｎｙｌ−ｄｉｐｈｅｎｙｌ−ａｍｉｎｅ）（１−Ｍａｔｅｒｉａｌ社製）の１ｗｔ％クロロベンゼン溶液を有機無機ペロブスカイト化合物部位上にスピンコート法によって５０ｎｍの厚みに積層し、光電変換層を形成した。光電変換層上に、対向電極（陽極）として真空蒸着により厚み１００ｎｍの金膜を形成し、積層体を作製した。得られた積層体上に、封止材としてのポリイソブチレン樹脂（ＢＡＳＦ社製のＯＰＰＡＮＯＬ１００）を１０μｍ積層したアルミホイルを１００℃でラミネートし、太陽電池を得た。
(Example 19)
CH 3 NH 3 I and PbCl 2 were dissolved on the porous electron transport layer of Example 1 as a solution for forming an organic-inorganic perovskite compound using N, N-dimethylformamide (DMF) as a solvent at a molar ratio of 3: 1. , The concentration of Pb was adjusted to 1M. In order to further add strontium, the additive is added to the above-prepared solution so as to have a concentration of 0.01 M (strontium content (in the table, additive concentration) = 1 mol% with respect to 100 mol% of lead). Strontium chloride was dissolved as a strontium chloride, and a film was formed on the porous electron transport layer by a spin coating method to form an organic-inorganic perovskite compound moiety. Further, as a hole transport layer, a 1 wt% chlorobenzene solution of Poly (4-butylphenyl-diphenyl-amine) (manufactured by 1-Material) was laminated on the organic-inorganic perovskite compound site by a spin coating method to a thickness of 50 nm, and a photoelectric conversion layer was formed. Was formed. A gold film having a thickness of 100 nm was formed on the photoelectric conversion layer by vacuum vapor deposition as a counter electrode (anode) to prepare a laminated body. An aluminum foil obtained by laminating 10 μm of polyisobutylene resin (OPPANOL100 manufactured by BASF) as a sealing material on the obtained laminate was laminated at 100 ° C. to obtain a solar cell.
（実施例２０）
積層体を封止材で封止しなかったこと以外は実施例１と同様にして、太陽電池を得た。
(Example 20)
A solar cell was obtained in the same manner as in Example 1 except that the laminate was not sealed with a sealing material.
（比較例１）
有機無機ペロブスカイト化合物形成用溶液を調製する際に添加物を使用しないこと以外は実施例１と同様にして、太陽電池を得た。
(Comparative Example 1)
A solar cell was obtained in the same manner as in Example 1 except that no additive was used when preparing the solution for forming an organic-inorganic perovskite compound.
（比較例２）
有機無機ペロブスカイト化合物形成用溶液を調製する際に添加物を使用しないこと以外は実施例３と同様にして、太陽電池を得た。
(Comparative Example 2)
A solar cell was obtained in the same manner as in Example 3 except that no additive was used when preparing the solution for forming an organic-inorganic perovskite compound.
（比較例３−７）
有機無機ペロブスカイト化合物形成用溶液を調製する際に使用した添加物の種類及び濃度を、表１に記載の通りに変更したこと以外は実施例１と同様にして、太陽電池を得た。
(Comparative Example 3-7)
A solar cell was obtained in the same manner as in Example 1 except that the type and concentration of the additive used in preparing the organic-inorganic perovskite compound forming solution were changed as shown in Table 1.
（比較例８）
有機無機ペロブスカイト化合物形成用溶液を調製する際に添加物を使用しないこと以外は実施例１７と同様にして、太陽電池を得た。
(Comparative Example 8)
A solar cell was obtained in the same manner as in Example 17 except that no additive was used when preparing the solution for forming an organic-inorganic perovskite compound.
（比較例９）
有機無機ペロブスカイト化合物形成用溶液を調製する際に添加物を使用しないこと以外は実施例１９と同様にして、太陽電池を得た。
(Comparative Example 9)
A solar cell was obtained in the same manner as in Example 19 except that no additive was used when preparing the solution for forming an organic-inorganic perovskite compound.
＜評価＞
実施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１に示した。
<Evaluation>
The solar cells obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.
（１）初期変換効率
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の光を照射し光電変換効率を測定した。実施例１−１６、２０、比較例２−７については比較例１の変換効率を１に規格化した際、１．１以上であった場合を○○、１以上、１．１未満であった場合を○、１未満であった場合を×とし、実施例１７−１８については比較例８の変換効率を１に規格化した際、１．１以上であった場合を○○、１以上、１．１未満であった場合を○、１未満であった場合を×とし、実施例１９については比較例９の変換効率を１に規格化した際、１．１以上であった場合を○○、１以上、１．１未満であった場合を○、１未満であった場合を×とした。
（２）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○○、０．６以上、０．８未満であった場合を○、０．６未満であった場合を×とした。
(1) Initial conversion efficiency A power supply (KEITHLEY, 236 model) is connected between the electrodes of the solar cell, and light with an intensity of 100 mW / cm 2 is irradiated using a solar simulation (Yamashita Denso) to improve the photoelectric conversion efficiency. It was measured. For Examples 1-16 and 20 and Comparative Example 2-7, when the conversion efficiency of Comparative Example 1 was standardized to 1, the case where it was 1.1 or more was XX, 1 or more, and less than 1.1. When the conversion efficiency of Comparative Example 8 is standardized to 1, the case of XX or more is XX, and the case of Example 17-18 is XX, 1 or more. , If it is less than 1.1, it is evaluated as ◯, if it is less than 1, it is evaluated as ×, and in Example 19, when the conversion efficiency of Comparative Example 9 is standardized to 1, it is 1.1 or more. XX was evaluated as ◯ when it was 1 or more and less than 1.1, and × when it was less than 1.
(2) Photo-deterioration test A power supply (manufactured by KEITHLEY, 236 model) 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). The photoelectric conversion efficiency immediately after the start of light irradiation and the photoelectric conversion efficiency after continuing the light irradiation for 1 hour were measured. Obtain the value of photoelectric conversion efficiency after continuing light irradiation for 1 hour / photoelectric conversion efficiency immediately after starting light irradiation, and when the value is 0.9 or more, ○○○, 0.8 or more, 0 The case where it was less than 9. was evaluated as XX, the case where it was 0.6 or more and less than 0.8 was evaluated as ◯, and the case where it was less than 0.6 was evaluated as ×.
本発明によれば、高い光電変換効率を発揮できる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 solar cell capable of exhibiting high photoelectric conversion efficiency.
Claims (5)
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と、周期表２族元素、周期表１１族元素、イットリウム、オスミウム、ロジウム、マンガン、チタン及びランタンからなる群から選択される１種以上の元素とを含有する部位を有する
ことを特徴とする太陽電池。 A solar cell having an electrode, a counter electrode, and a photoelectric conversion layer arranged between the electrode and the counter electrode.
The photoelectric conversion layer is composed of an organic-inorganic perovskite compound represented by the general formula R-MX 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom), and a periodic table. group 2 elements, periodic table 11 element, Lee Ttoriumu, osmium, rhodium, manganese, solar cell and having a portion containing a one or more elements selected from the group consisting of titanium and lanthanum.
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