JP2017050426A - Additive agent for hole transport layer of organic inorganic perovskite solar battery - Google Patents
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- 230000005525 hole transport Effects 0.000 title claims abstract description 38
- 239000000654 additive Substances 0.000 title claims abstract description 16
- 230000000996 additive effect Effects 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 title abstract 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims abstract description 20
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- -1 fluorosulfonyl Chemical group 0.000 abstract description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003949 imides Chemical class 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229910010941 LiFSI Inorganic materials 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 9
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CXRVNRVRMMXKKA-UHFFFAOYSA-N CC(C)O[Ti+2]OC(C)C Chemical compound CC(C)O[Ti+2]OC(C)C CXRVNRVRMMXKKA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、有機無機ペロブスカイト太陽電池の正孔輸送層用添加剤に関する。 The present invention relates to an additive for a hole transport layer of an organic / inorganic perovskite solar cell.
太陽電池は、再生可能型エネルギーとして着目され、シリコン型太陽電池、色素増感型太陽電池、有機薄膜太陽電池等が知られている。シリコン型太陽電池は、太陽エネルギーを電力に変える際の変換効率が高いが、エネルギー回収に長時間かかり、高コストでもある。色素増感型太陽電池や有機薄膜太陽電池は、シリコン型太陽電池に比べて、軽量、フレキシブル、かつ低コストであるが、日光に弱く耐久性等に問題がある。 Solar cells are attracting attention as renewable energy, and silicon-type solar cells, dye-sensitized solar cells, organic thin-film solar cells, and the like are known. Silicon-type solar cells have high conversion efficiency when converting solar energy into electric power, but it takes a long time for energy recovery and is also expensive. Dye-sensitized solar cells and organic thin-film solar cells are lighter, more flexible, and less expensive than silicon solar cells, but are vulnerable to sunlight and have problems with durability.
こういった中、有機無機ハイブリッド構造のペロブスカイト結晶を光吸収に用いる有機無機ハイブリッド型ペロブスカイト太陽電池（以下、有機無機ペロブスカイト太陽電池）が２００９年に発表され（非特許文献１）、その後、高効率化の成果が続々と発表されている。また、カーボンナノチューブに有機無機ペロブスカイト化合物を被覆した半導体層を、光電変換素子として用いる技術が公開されている（特許文献１）。
有機無機ペロブスカイト太陽電池においては、ペロブスカイト層を、溶液を用いて形成できるため、高速かつ低コストで太陽電池を製造できるというメリットがあり、今後の展開によっては、シリコン型の太陽電池の代替品となる可能性がある。
Under these circumstances, an organic-inorganic hybrid perovskite solar cell (hereinafter referred to as an organic-inorganic perovskite solar cell) using a perovskite crystal having an organic-inorganic hybrid structure for light absorption was announced in 2009 (Non-Patent Document 1), and then highly efficient. The results of the conversion have been announced one after another. Moreover, the technique which uses the semiconductor layer which coat | covered the organic inorganic perovskite compound on the carbon nanotube as a photoelectric conversion element is disclosed (patent document 1).
In organic / inorganic perovskite solar cells, the perovskite layer can be formed using a solution, which has the advantage that solar cells can be manufactured at high speed and at low cost. There is a possibility.
例えば、特許文献２には、正孔輸送層用添加剤としてリチウム（フルオロスルホニル）（トリフルオロメチル）イミドを用いた有機無機複合薄膜太陽電池が開示されている。しかし、この太陽電池は、複数の太陽電池を同じように作製しても、電池特性に大きなばらつきが生じ、歩留まりが悪いという問題があった。 For example, Patent Document 2 discloses an organic-inorganic composite thin film solar cell using lithium (fluorosulfonyl) (trifluoromethyl) imide as an additive for a hole transport layer. However, this solar cell has a problem that even if a plurality of solar cells are produced in the same manner, the battery characteristics vary greatly and the yield is poor.
そこで本発明では、ペロブスカイト層の上に形成される正孔輸送層について検討し、電池特性のばらつきの少ない有機無機ペロブスカイト太陽電池を得ることを課題として掲げた。 Therefore, in the present invention, the hole transport layer formed on the perovskite layer was studied, and an object was to obtain an organic / inorganic perovskite solar cell with little variation in battery characteristics.
上記課題を解決した本発明は、リチウムビス（フルオロスルホニル）イミドからなる有機無機ペロブスカイト太陽電池の正孔輸送層用添加剤である。
上記において、正孔輸送材料がSpiro-OMeTADを含み、上記の正孔輸送層用添加剤は、Spiro-OMeTAD１モルに対し０．４〜０．６モル使用されることが好ましい。
また、本発明には、上記の正孔輸送層用添加剤を含む正孔輸送材料から形成される有機無機ペロブスカイト太陽電池の正孔輸送層、および、この正孔輸送層を有する有機無機ペロブスカイト太陽電池も包含される。
This invention which solved the said subject is an additive for positive hole transport layers of the organic inorganic perovskite solar cell which consists of lithium bis (fluoro sulfonyl) imide.
In the above, it is preferable that the hole transport material contains Spiro-OMeTAD, and the additive for the hole transport layer is used in an amount of 0.4 to 0.6 mol with respect to 1 mol of Spiro-OMeTAD.
Further, the present invention provides a hole transport layer of an organic / inorganic perovskite solar cell formed from a hole transport material containing the above additive for hole transport layer, and an organic / inorganic perovskite solar cell having the hole transport layer. A battery is also included.
本発明では、正孔輸送層用添加剤として、リチウムビス（フルオロスルホニル）イミドを用いたので、最終的に得られる有機無機ペロブスカイト太陽電池の電池特性のばらつきを抑制することができた。従って、特性のばらつきの小さな有機無機ペロブスカイト太陽電池を歩留まりよく作製することができるようになり、さらなる低コスト化が可能となった。 In the present invention, since lithium bis (fluorosulfonyl) imide is used as the additive for the hole transport layer, variations in battery characteristics of the finally obtained organic-inorganic perovskite solar battery can be suppressed. Therefore, organic / inorganic perovskite solar cells with small variations in characteristics can be manufactured with a high yield, and the cost can be further reduced.
本発明の正孔輸送層用添加剤は、下記式で示されるリチウムビス（フルオロスルホニル）イミドからなる。 The additive for a hole transport layer of the present invention comprises lithium bis (fluorosulfonyl) imide represented by the following formula.
これまでは、正孔輸送層用添加剤として下記式で表されるリチウム（フルオロスルホニル）（トリフルオロメチル）イミドが用いられてきた。しかし、前記したように、同じように太陽電池を作製しても、特性がばらつくという問題があった。 Until now, lithium (fluorosulfonyl) (trifluoromethyl) imide represented by the following formula has been used as an additive for a hole transport layer. However, as described above, there is a problem that the characteristics vary even if the solar cells are manufactured in the same manner.
しかし、驚くべきことに、正孔輸送層用添加剤として、リチウム（フルオロスルホニル）（トリフルオロメチル）イミド（以下、ＬｉＴＦＳＩ）に変えてリチウムビス（フルオロスルホニル）イミド（以下、ＬｉＦＳＩ）を用いると、太陽電池の特性のばらつきが抑制されることが本発明者らによって見出され、本発明が完成したのである。ＬｉＦＳＩはＬｉＴＦＳＩのトリフルオロメチル基がフッ素に変わっているだけであるのに、後述する実施例で確認したように、特性のばらつきは有意に抑制されている。その理由は、そもそものばらつきの原因と共に、明確にはなっていない。ＬｉＦＳＩ（分子量１８７ｇ／ｍｏｌ）はＬｉＴＦＳＩ（２８７ｇ／ｍｏｌ）よりも分子量が小さいことや、イオン伝導度がＬｉＦＳＩは９．８ｍＳ／ｃｍと、ＬｉＴＦＳＩの６．８ｍＳ／ｃｍよりも高いことが何か関係があるのではないかと推測される。 However, surprisingly, when lithium bis (fluorosulfonyl) imide (hereinafter referred to as LiFSI) is used instead of lithium (fluorosulfonyl) (trifluoromethyl) imide (hereinafter referred to as LiTFSI) as an additive for the hole transport layer. The present inventors have found that variation in characteristics of solar cells is suppressed, and the present invention has been completed. In LiFSI, although only the trifluoromethyl group of LiTFSI is changed to fluorine, variation in characteristics is significantly suppressed as confirmed in Examples described later. The reason is not clear with the cause of the variation in the first place. LiFSI (molecular weight 187 g / mol) has a smaller molecular weight than LiTFSI (287 g / mol), and ionic conductivity of LiFSI is 9.8 mS / cm, which is higher than 6.8 mS / cm of LiTFSI. It is speculated that there is.
正孔輸送層用材料としては、上記ＬｉＦＳＩの他に、Spiro-OMeTAD（2,2’,7,7’-テトラキス［ビス（4-メトキシフェニル）アミノ］スピロ［9Ｈ-フルオレン-9,9’-[9Ｈ]フルオレン］）、４−ｔ−ブチルピリジン（ＴＢＰ）、Ｃｏ(III)とＴＦＳＩとの錯体を用いることが好ましい。なお、ＬｉＦＳＩ以外の化合物については、これらに代替できる公知の化合物を用いても構わない。Spiro-OMeTADは下記式で表される化合物である。 As a material for the hole transport layer, in addition to the above LiFSI, Spiro-OMeTAD (2,2 ′, 7,7′-tetrakis [bis (4-methoxyphenyl) amino] spiro [9H-fluorene-9,9 ′ -[9H] fluorene]), 4-t-butylpyridine (TBP), and a complex of Co (III) and TFSI is preferably used. In addition, about compounds other than LiFSI, you may use the well-known compound which can substitute for these. Spiro-OMeTAD is a compound represented by the following formula.
ＴＢＰは下記式で表される化合物である。
Ｃｏ(III)とＴＦＳＩの錯体は下記式で表される化合物である。
これらの使用比率は、クロロベンゼンやトルエン等の有機溶媒１Ｌに対して、
Spiro-OMeTAD；４０〜８０ｍｏｌ、
ＬｉＦＳＩ；１６〜４８ｍｏｌ、ただし、Spiro-OMeTAD１ｍｏｌに対し、０．４〜０．６ｍｏｌ、
ＴＢＰ；９０〜３００ｍｏｌ、
Ｃｏ(III)錯体；４〜１６ｍｏｌ
とすることが好ましい。
These usage ratios are based on 1 L of organic solvents such as chlorobenzene and toluene.
Spiro-OMeTAD; 40-80 mol,
LiFSI; 16 to 48 mol, with respect to 1 mol of Spiro-OMeTAD, 0.4 to 0.6 mol,
TBP; 90-300 mol,
Co (III) complex; 4-16 mol
It is preferable that
これらは、例えば、クロロベンゼン等に溶解させて、ペロブスカイト層の上に、スピンコート法、塗布法、スプレー法、ディッピング法等の方法で積層し、適宜乾燥すればよい。正孔輸送層の膜厚は、５０ｎｍ〜１０μｍ程度が好ましい。正孔輸送層は、例えば、基板上に正孔輸送層用溶液を８０〜１２０μｌ程度載せ、２０００〜５０００ｒｐｍで、３０〜６０秒程度スピンコートすることにより成膜し、７０℃程度で３０分間程度乾燥させることにより形成できる。金電極は、真空蒸着法により、０〜５ｎｍ：０．０１ｎｍ／ｓｅｃ、５〜１０ｎｍ：０．０１ｎｍ／ｓｅｃ、１０〜２０ｎｍ：０．０５ｎｍ／ｓｅｃ、２０ｎｍ以上：０．１ｎｍ／ｓｅｃと、段階的に蒸着レートを上昇させ、８０〜１００ｎｍ程度成膜して形成している。 These may be dissolved in, for example, chlorobenzene, and laminated on the perovskite layer by a method such as spin coating, coating, spraying, dipping, or the like, and dried appropriately. The thickness of the hole transport layer is preferably about 50 nm to 10 μm. The hole transport layer is formed, for example, by placing about 80 to 120 μl of the hole transport layer solution on the substrate and spin-coating at 2000 to 5000 rpm for about 30 to 60 seconds, and at about 70 ° C. for about 30 minutes. It can be formed by drying. The gold electrode is formed by the steps of 0 to 5 nm: 0.01 nm / sec, 5 to 10 nm: 0.01 nm / sec, 10 to 20 nm: 0.05 nm / sec, 20 nm or more: 0.1 nm / sec by vacuum deposition. In general, the deposition rate is increased to form a film of about 80 to 100 nm.
本発明の太陽電池は、透明導電性基板（透明電極）、緻密な酸化チタン層、メソポーラス酸化チタン層（多孔質酸化チタン層）、有機無機ペロブスカイト層、正孔輸送層、対極によって形成される。酸化チタン層とメソポーラス酸化チタン層が電子輸送層となる。 The solar cell of the present invention is formed by a transparent conductive substrate (transparent electrode), a dense titanium oxide layer, a mesoporous titanium oxide layer (porous titanium oxide layer), an organic / inorganic perovskite layer, a hole transport layer, and a counter electrode. The titanium oxide layer and the mesoporous titanium oxide layer serve as an electron transport layer.
基板としては、ＦＴＯガラス基板が好ましい。また、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリフェニレンスルフィド、ポリスルホン、ポリアリレート、脂環式ポリオレフィン等の透明樹脂基板にインジウムオキサイド等の導電性化合物を積層した透明導電性樹脂基板等も用いることができる。これらの基板の厚みは、０．０５〜１０ｍｍ程度が好ましい。 As the substrate, an FTO glass substrate is preferable. A transparent conductive resin substrate in which a conductive compound such as indium oxide is laminated on a transparent resin substrate such as polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polysulfone, polyarylate, and alicyclic polyolefin can also be used. The thickness of these substrates is preferably about 0.05 to 10 mm.
上記基板上に、まず緻密な酸化チタン層を形成する。この酸化チタン層の形成には、例えば、以下のようなスプレーピロリシス法が採用できる。まず、基板をホットプレートに並べた後、ＦＴＯガラス基板とコンタクトを取る部分にマスクを置き、４５０℃程度に加熱する。エタノール３９ｍＬに、ジイソプロポキシチタニウム(IV)ビス(アセチルアセトナト)(Ti(OiPr)2(acac)2)を７５質量％含む２−プロパノール溶液１ｍＬを加えた溶液を調製し、基板から約３０ｃｍの高さにスプレーを固定し、水平に約２０ｃｍ／ｓｅｃで基板の上に噴射（キャリアガス：Ｎ2、０．５ＭＰａ）しながら掃引する（１枚を１ラインとして、枚数＋前後１ラインずつ掃引する）。１秒間待って、同じ軌跡でもう一度掃引する。４５０℃のまま３分間待つ（２回掃引、３分待つ）。この１セットを合計３セット行う。別途、ポリエチレン容器に氷冷した蒸留水を１００ｍＬと、四塩化チタン(TiCl4)４４０μＬを加え、５０ｍＭのTiCl4溶液を調製する。室温まで冷却した上記基板をTiCl4溶液に浸漬し、撹拌子を入れ、７０℃のホットプレート上で３０分撹拌する。その後取り出し、蒸留水で２回洗浄し、エアガンで表面に付着した水分を飛ばす。その後、電気炉により、５００℃で２０分間焼結する。これにより、基板上に緻密な酸化チタン層が形成される。なお、上記製造例は、一例であり、各操作に使用したものの量、操作時間、操作温度は、それぞれ２割程度、より好ましくは１割程度の増減があっても構わない。緻密な酸化チタン層の厚みは、３０〜５０ｎｍが好ましい。 A dense titanium oxide layer is first formed on the substrate. For the formation of the titanium oxide layer, for example, the following spray pyrrolesis method can be employed. First, after arranging a board | substrate on a hotplate, a mask is set | placed in the part which contacts a FTO glass substrate, and it heats at about 450 degreeC. A solution was prepared by adding 1 mL of 2-propanol solution containing 75% by mass of diisopropoxytitanium (IV) bis (acetylacetonato) (Ti (OiPr) 2 (acac) 2 ) to 39 mL of ethanol, and about 30 cm from the substrate. The spray is fixed at a height of about 20 cm / sec and swept while being sprayed onto the substrate at a rate of about 20 cm / sec (carrier gas: N 2 , 0.5 MPa). Sweep). Wait one second and sweep again with the same trajectory. Wait for 3 minutes at 450 ° C. (2 sweeps, wait 3 minutes). A total of three sets of this one set are performed. Separately, 100 mL of ice-cooled distilled water and 440 μL of titanium tetrachloride (TiCl 4 ) are added to a polyethylene container to prepare a 50 mM TiCl 4 solution. The substrate cooled to room temperature is immersed in a TiCl 4 solution, and a stirrer is inserted, followed by stirring on a hot plate at 70 ° C. for 30 minutes. Then, it is taken out, washed twice with distilled water, and the water adhering to the surface is blown off with an air gun. Then, it sinters for 20 minutes at 500 degreeC with an electric furnace. Thereby, a dense titanium oxide layer is formed on the substrate. In addition, the said manufacture example is an example, The quantity of what was used for each operation, operation time, and operation temperature may each increase / decrease about about 20%, More preferably, about 10%. The thickness of the dense titanium oxide layer is preferably 30 to 50 nm.
緻密な酸化チタン層が形成されれば、その上に、メソポーラス酸化チタン層を形成する。メソポーラス酸化チタン層（多孔質酸化チタン層）は、例えば、日揮触媒化成社製の酸化チタンペースト「ＰＳＴ−１８ＮＲ」をエタノールで希釈し、スピンコーティング法で緻密な酸化チタン層の上に成膜し、４００〜６００℃の温度で１〜２時間焼成することにより、形成することができる。メソポーラス酸化チタン層の厚みは、１００〜３００ｎｍが好ましい。 If a dense titanium oxide layer is formed, a mesoporous titanium oxide layer is formed thereon. The mesoporous titanium oxide layer (porous titanium oxide layer) is formed by, for example, diluting a titanium oxide paste “PST-18NR” manufactured by JGC Catalysts & Chemicals with ethanol and forming a film on a dense titanium oxide layer by a spin coating method. It can be formed by baking at a temperature of 400 to 600 ° C. for 1 to 2 hours. The thickness of the mesoporous titanium oxide layer is preferably 100 to 300 nm.
続いてペロブスカイト層を形成する。ペロブスカイトとしては、ＣＨ3ＮＨ3ＰｂＸ3（Ｘは、ハロゲン（Ｆ、Ｃｌ、Ｂｒ、Ｉ）を表す）が好ましい。例えばＸがヨウ素であるペロブスカイト層を形成する場合は、ヨウ化鉛（ＰｂＩ2）を例えばジメチルホルムアミド（ＤＭＦ）等に溶解させて、メソポーラス酸化チタン層の上に、スピンコート法等で積層する。続いて、これをＣＨ3ＮＨ3Ｉのイソプロパノール溶液中に浸漬する。浸漬時間は、２０秒〜１分程度が好ましい。その後、イソプロパノールを除去するために、加熱乾燥する。これによりペロブスカイト層が形成される。ペロブスカイト層の形成、正孔輸送層の形成、電極の形成は、水分や酸素の濃度が０．１ｐｐｍ未満に低減された、例えばアルゴンガス等の不活性ガス雰囲気下で行う。 Subsequently, a perovskite layer is formed. The perovskite is preferably CH 3 NH 3 PbX 3 (X represents halogen (F, Cl, Br, I)). For example, when forming a perovskite layer in which X is iodine, lead iodide (PbI 2 ) is dissolved in, for example, dimethylformamide (DMF) or the like, and laminated on the mesoporous titanium oxide layer by a spin coating method or the like. Subsequently, it is immersed in an isopropanol solution of CH 3 NH 3 I. The immersion time is preferably about 20 seconds to 1 minute. Then, in order to remove isopropanol, it heat-drys. Thereby, a perovskite layer is formed. The formation of the perovskite layer, the formation of the hole transport layer, and the formation of the electrode are performed in an inert gas atmosphere such as argon gas in which the concentration of moisture and oxygen is reduced to less than 0.1 ppm.
そして前記した正孔輸送層をペロブスカイト層の上に形成し、金（Ａｕ）等の金属電極（対極）を蒸着法等で正孔輸送層の上に形成すれば、本発明の有機無機ペロブスカイト太陽電池ができあがる。なお、各層の形成に用いた材料は、同等の機能を有する代替品であっても構わない。 If the hole transport layer is formed on the perovskite layer and a metal electrode (counter electrode) such as gold (Au) is formed on the hole transport layer by vapor deposition or the like, the organic / inorganic perovskite solar cell of the present invention is used. The battery is completed. Note that the material used for forming each layer may be a substitute having an equivalent function.
以下、実験例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実験例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to experimental examples.However, the present invention is not limited by the following experimental examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
実施例
ホットプレート上に、耐熱ガラスを置き、その上にＦＴＯガラス基板（旭硝子社製、ＦＴＮ、７５ｍｍ×２５ｍｍ×１．８ｍｍｔ）を並べ、ＦＴＯとコンタクトを取る部分（ＦＴＯをエッチングした辺の逆側）の上にマスク（１ｃｍ幅、２ｍｍ厚のアルミニウム板）を置いた。基板を４５０℃に加熱した。エタノール（和光純薬工業社製、超脱水）３９ｍＬに、ジイソプロポキシチタニウム(IV)ビス(アセチルアセトナト)(Ti(OiPr)2(acac)2)を７５質量％含む２−プロパノール溶液１ｍＬを加え、スプレー液を調製した。エアブラシ（Harder&Steenbeck社製、Evolution A、絵の具カップを１５ｃｃに換装したもの）にスプレー液を加え、基板から約３０ｃｍの高さにスプレーを固定し、水平に約２０ｃｍ／ｓｅｃの速度で基板の上をスプレー（キャリアガス：Ｎ2、０．５ＭＰａ）しながら掃引した（１枚を１ラインとして、枚数＋前後１ラインずつ掃引する）。１秒待って、同じ軌跡でもう一度掃引し、４５０℃のまま３分間待った。この１セットを合計３セット行った後、室温まで冷却した。別途、ポリエチレン容器に氷冷した蒸留水を１００ｍＬと、四塩化チタン（TiCl4；和光純薬工業社製）４４０μＬを加え、５０ｍＭのTiCl4溶液を調製した。上記基板をTiCl4溶液に浸漬し、撹拌子を入れ、７０℃のホットプレート上で３０分撹拌した。その後、基板を取り出し、蒸留水で２回洗浄し、エアガンで表面に付着した水分を飛ばして乾燥した。その後、上記基板を電気炉に入れ、１５分かけて、室温から５００℃まで昇温し、５００℃で２０分間焼結した。その後、室温まで冷却した。これにより、厚みが３０ｎｍの緻密な酸化チタン層がＦＴＯ基板の上に形成された積層体Ａを得た。
Example A heat-resistant glass is placed on a hot plate, and an FTO glass substrate (Asahi Glass Co., Ltd., FTN, 75 mm × 25 mm × 1.8 mmt) is arranged on the hot plate. A mask (1 cm wide, 2 mm thick aluminum plate) was placed on the side. The substrate was heated to 450 ° C. 1 mL of 2-propanol solution containing 75% by mass of diisopropoxytitanium (IV) bis (acetylacetonato) (Ti (OiPr) 2 (acac) 2 ) in 39 mL of ethanol (manufactured by Wako Pure Chemical Industries, Ltd., ultra-dehydrated) In addition, a spray solution was prepared. Spray solution is added to an airbrush (Harder & Steenbeck, Evolution A, paint cup replaced with 15 cc), and the spray is fixed at a height of about 30 cm from the substrate, and horizontally on the substrate at a speed of about 20 cm / sec. Sweeping was performed while spraying (carrier gas: N 2 , 0.5 MPa) (one sheet is taken as one line, and the number of sheets + one line before and after is swept). After waiting for 1 second, it was swept again with the same trajectory, and waited for 3 minutes at 450 ° C. A total of 3 sets of this 1 set were performed, and then cooled to room temperature. Separately, 100 mL of ice-cooled distilled water in a polyethylene container and 440 μL of titanium tetrachloride (TiCl 4 ; manufactured by Wako Pure Chemical Industries, Ltd.) were added to prepare a 50 mM TiCl 4 solution. The substrate was immersed in a TiCl 4 solution, a stirring bar was added, and the mixture was stirred on a hot plate at 70 ° C. for 30 minutes. Thereafter, the substrate was taken out, washed twice with distilled water, and dried by blowing off water adhering to the surface with an air gun. Then, the said board | substrate was put into the electric furnace, and it heated up from room temperature to 500 degreeC over 15 minutes, and sintered for 20 minutes at 500 degreeC. Then, it cooled to room temperature. As a result, a laminate A in which a dense titanium oxide layer having a thickness of 30 nm was formed on the FTO substrate was obtained.
上記積層体Ａの緻密な酸化チタン層上に、日揮触媒化成社製の酸化チタンペースト「ＰＳＴ−１８ＮＲ」をエタノールで希釈して濃度１７質量％にした溶液を用いて、スピンコーティング法で成膜した。その後、５００℃で、０．５時間焼成した。厚み２００ｎｍのメソポーラス酸化チタン層が形成された積層体Ｂを得た。 Using a solution of titanium oxide paste “PST-18NR” manufactured by JGC Catalysts & Chemicals Co., Ltd. diluted with ethanol to a concentration of 17% by mass on the dense titanium oxide layer of the laminate A, a film is formed by spin coating. did. Then, it baked at 500 degreeC for 0.5 hour. A layered product B on which a mesoporous titanium oxide layer having a thickness of 200 nm was formed was obtained.
ヨウ化鉛（ＰｂＩ2）をジメチルホルムアミド（ＤＭＦ）に溶解させて１．０ｍｏｌ／ＬのＰｂＩ2溶液を調製した。これを用いて、積層体Ｂの上にスピンコート法で成膜し、積層体Ｃを得た。続いて、積層体ＣをＣＨ3ＮＨ3Ｉのイソプロパノール溶液（１０ｍｇ／ｍＬ濃度）中に浸漬した。浸漬時間は、４０秒とした。その後、イソプロパノールを除去するために、７０℃で６０分乾燥した。ペロブスカイト層が形成された積層体Ｄを得た。ペロブスカイト層の厚みは、２００〜３００ｎｍであった。 Lead iodide (PbI 2 ) was dissolved in dimethylformamide (DMF) to prepare a 1.0 mol / L PbI 2 solution. Using this, a film was formed on the layered product B by a spin coating method, and a layered product C was obtained. Subsequently, the laminate C was immersed in an isopropanol solution of CH 3 NH 3 I (concentration of 10 mg / mL). The immersion time was 40 seconds. Then, in order to remove isopropanol, it dried at 70 degreeC for 60 minutes. A laminate D in which a perovskite layer was formed was obtained. The thickness of the perovskite layer was 200 to 300 nm.
Spiro-OMeTADを５９ｍＭ、ＬｉＦＳＩを３２ｍＭ、４−ｔ−ブチルピリジンを１９５ｍＭおよび前記したＣｏ(III)錯体８．９ｍＭをクロロベンゼン１．０ｍＬに溶解させた。この正孔輸送層用の溶液を用いて、スピンコート法で、積層体Ｄのペロブスカイト層の上に成膜した。正孔輸送層の厚みは、２００〜３００ｎｍであった。 Spiro-OMeTAD (59 mM), LiFSI (32 mM), 4-t-butylpyridine (195 mM) and the Co (III) complex (8.9 mM) were dissolved in chlorobenzene (1.0 mL). Using this hole transport layer solution, a film was formed on the perovskite layer of the laminate D by spin coating. The thickness of the hole transport layer was 200 to 300 nm.
最後に、正孔輸送層の上に、金（Ａｕ）からなる電極を蒸着法で形成し、本発明の太陽電池を得た。金電極の厚みは、８０ｎｍであった。 Finally, an electrode made of gold (Au) was formed on the hole transport layer by a vapor deposition method to obtain the solar cell of the present invention. The thickness of the gold electrode was 80 nm.
比較例
正孔輸送層用の溶液を調製する際に、ＬｉＦＳＩに代えてＬｉＴＦＳＩを用いた以外は実施例と同様にして太陽電池を形成した。
Comparative Example When preparing a solution for the hole transport layer, a solar cell was formed in the same manner as in Example except that LiTFSI was used instead of LiFSI.
実施例と比較例で作製した太陽電池の特性を、分光計器製太陽電池特性評価システム(OTENTO-SunIII)を用いて評価した。評価はｎ＝５で行った。
なお、Ｊｓｃは短絡電流密度であり、太陽電池素子に光照射した際の電圧が０Ｖのときの単位面積あたりの電流値（ｍＡ／ｃｍ2）を表す。Ｖｏｃは開放電圧であり、短絡電流密度Ｊｓｃが０となるときの電圧の値（Ｖ）を表す。ＦＦは曲線因子であり、太陽電池素子の最大出力を、短絡電流密度Ｊｓｃと開放電圧Ｖｏｃとの積で割った値である。すなわちＦＦは１に近いほどよい。ＰＣＥは太陽電池素子の変換効率（最大出力）である。Ｒｓは直列抵抗である。このＲｓは、発生した電子および正孔が再結合を起こし、電荷が失われる場合等に上昇する。すなわち、Ｒｓは小さいほどよい。Ｒｓｈは並列抵抗である。Ｒｓｈは素子内の流れるべきでない経路に流れる電流（リーク電流）に対する抵抗である。すなわち、Ｒｓｈは大きいほどよい。
The characteristics of the solar cells produced in the examples and comparative examples were evaluated using a spectrometer-equipped solar cell characteristics evaluation system (OTENTO-SunIII). Evaluation was performed at n = 5.
Jsc is a short-circuit current density and represents a current value per unit area (mA / cm 2 ) when the voltage when the solar cell element is irradiated with light is 0V. Voc is an open-circuit voltage and represents a voltage value (V) when the short-circuit current density Jsc becomes zero. FF is a curve factor, which is a value obtained by dividing the maximum output of the solar cell element by the product of the short-circuit current density Jsc and the open-circuit voltage Voc. That is, the closer FF is to 1, the better. PCE is the conversion efficiency (maximum output) of the solar cell element. Rs is a series resistance. This Rs rises when the generated electrons and holes recombine and the charge is lost. That is, Rs is better as it is smaller. Rsh is a parallel resistance. Rsh is a resistance against a current (leakage current) flowing in a path that should not flow in the element. That is, Rsh is better as it is larger.
結果を表１と図１および図２に示す。表１には、最もよいデータを載せている。表１から、最高性能値はＬｉＴＦＳＩとＬｉＦＳＩとでは、大きな差はないが、図１および図２から、５サンプルの特性値のばらつきは、ＬｉＴＦＳＩの方がＬｉＦＳＩよりも大きいことがわかる。 The results are shown in Table 1 and FIGS. Table 1 contains the best data. From Table 1, it can be seen that the maximum performance value is not significantly different between LiTFSI and LiFSI, but from FIG. 1 and FIG. 2, the variation in the characteristic values of the five samples is larger in LiTFSI than in LiFSI.
本発明では、有機無機ペロブスカイト太陽電池の正孔輸送層用添加剤としてＬｉＦＳＩを用いたので、電池特性のばらつきを小さくすることが可能となった。従って、有機無機ペロブスカイト太陽電池を歩留まりよく作製でき、低コスト化につながると考えられる。 In the present invention, since LiFSI is used as the additive for the hole transport layer of the organic / inorganic perovskite solar cell, it is possible to reduce the variation in battery characteristics. Accordingly, it is considered that an organic / inorganic perovskite solar cell can be manufactured with a high yield, leading to cost reduction.
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