TWI829856B - 鈣鈦礦光電變換元件用電荷輸送性組成物 - Google Patents
鈣鈦礦光電變換元件用電荷輸送性組成物 Download PDFInfo
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- TWI829856B TWI829856B TW109102485A TW109102485A TWI829856B TW I829856 B TWI829856 B TW I829856B TW 109102485 A TW109102485 A TW 109102485A TW 109102485 A TW109102485 A TW 109102485A TW I829856 B TWI829856 B TW I829856B
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- photoelectric conversion
- perovskite
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- perovskite photoelectric
- carbon atoms
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- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
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- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JMXLWMIFDJCGBV-UHFFFAOYSA-N n-methylmethanamine;hydroiodide Chemical compound [I-].C[NH2+]C JMXLWMIFDJCGBV-UHFFFAOYSA-N 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
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- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- LUJALESCMWZZQD-UHFFFAOYSA-M sodium;quinolin-8-olate Chemical compound [Na+].C1=CN=C2C([O-])=CC=CC2=C1 LUJALESCMWZZQD-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- TULWUZJYDBGXMY-UHFFFAOYSA-N tellurophene Chemical compound [Te]1C=CC=C1 TULWUZJYDBGXMY-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
-
- H—ELECTRICITY
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Abstract
本發明提供鈣鈦礦光電變換元件用電荷輸送性組成物,其含有包含導電性聚合物之電荷輸送性物質、有機矽烷化合物及溶劑。
Description
本發明有關鈣鈦礦光電變換元件用電荷輸送性組成物。
電子元件,尤其是有機光電變換元件係使用有機半導體而將光能轉換為電能之裝置,舉例為例如有機太陽能電池。
有機太陽能電池係活性層或電荷輸送性物質使用有機物之太陽能電池元件,由M. Gratzel開發之色素增感太陽能電池與由C.W. Tan開發之有機薄膜太陽能電池等已為熟知(非專利文獻1、2)。
由於均為輕量・薄膜,且可撓化之方面、可藉輥對輥生產之方面等,而具有與現金主流之無機系太陽能電池不同之優點,故期待形成新的市場。
其另一方面,近年已報導有使用金屬鹵化物作為具有鈣鈦礦型結晶構造之化合物(以下稱為「鈣鈦礦半導體化合物」)之太陽能電池可達成比較高的光電轉換效率之研究成果,而備受矚目。例如專利文獻1中,記載具備含有鈣鈦礦半導體化合物之活性層之光電變換元件及太陽能電池。
然而,於活性層使用鈣鈦礦半導體化合物之光電變換元件中,根據組合於該活性層之其他層之條件,而有元件之安定性降低之情況,而期望進一步改善。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開2016-178193號公報
[非專利文獻1] Nature, vol.353, 737-740(1991)
[非專利文獻2] Appl. Phys. Lett., Vol.48, 183-185 (1986)
[發明欲解決之課題]
本發明係鑒於上述情況而完成者,目的在於提供可較佳地使用作為鈣鈦礦光電變換元件之電洞捕集層且可獲得兼具高轉換效率(PCE)與優異安定性之鈣鈦礦光電變換元件之電荷輸送性組成物。
[用以解決課題之手段]
本發明人等,為達成上述目的而重複積極檢討之結果,發現藉由將含有包含導電性聚合物之電荷輸送性物質、有機矽烷化合物及溶劑之組成物,使用於鈣鈦礦光電變換元件之電洞捕集層,可獲得兼具高PCE與優異安定性之鈣鈦礦光電變換元件,因而完成本發明。
亦即,本發明提供
1. 一種鈣鈦礦光電變換元件用電荷輸送性組成物,其特徵係含有包含導電性聚合物之電荷輸送性物質、有機矽烷化合物及溶劑。
2. 如1之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述導電性聚合物係p型共軛均聚物。
3. 如1或2之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述導電性聚合物係聚噻吩衍生物。
4. 如1至3中任一項之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述導電性聚合物係含有式(1)表示之重複單位之聚噻吩衍生物,
(式中,R1
及R2
相互獨立為氫原子、碳數1~40之烷基、碳數1~40之氟烷基、碳數1~40之烷氧基、碳數1~40之氟烷氧基、碳數6~20之芳氧基、-O-[Z-O]p
-Re
或磺酸基,或R1
及R2
鍵結形成之-O-Y-O-,Y係可含有醚鍵,可經磺酸基取代之碳數1~40之伸烷基,Z為可經鹵原子取代之碳數1~40之伸烷基,p為1以上,Re
為氫原子、碳數1~40之烷基、碳數1~40之氟烷基或碳數6~20之芳基)。
5. 如1至4中任一項之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述有機矽烷化合物為烷氧基矽烷。
6. 如5之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述烷氧基矽烷包含選自三烷氧基矽烷及四烷氧基矽烷之至少1種。
7. 如1至6中任一項之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述電荷輸送性組成物係鈣鈦礦光電變換元件之電洞捕集層用。
8. 如7之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述鈣鈦礦光電變換元件係太陽能電池。
9. 一種薄膜,其係由如1至6中任一項之鈣鈦礦光電變換元件用電荷輸送性組成物所得。
10. 如9之薄膜,其中上述薄膜係鈣鈦礦光電變換元件之電洞捕集層。
11. 一種鈣鈦礦光電變換元件,其具備如9或10之薄膜。
12. 一種鈣鈦礦光電變換元件,其具有如10之電洞捕集層及與其連接地設置之活性層,該活性層包含鈣鈦礦半導體化合物。
13. 一種鈣鈦礦光電變換元件,其係具有一對電極、設於上述一對電極間之活性層、及設於上述活性層與上述電極之間之電洞捕集層的鈣鈦礦光電變換元件,
上述活性層係包含鈣鈦礦半導體化合物者,上述電洞捕集層係如10之薄膜。
14. 一種太陽能電池,其具備如11至13中任一項之鈣鈦礦光電變換元件。
[發明效果]
本發明之鈣鈦礦光電變換元件用電荷輸送性組成物可較佳地採用於形成鈣鈦礦光電變換元件之電洞捕集層且使用該組成物所得之薄膜使用作為電洞捕集層時可獲得兼具高PCE與優異安定性之鈣鈦礦光電變換元件。
以下,針對本發明更詳細說明。
本發明之鈣鈦礦光電變換元件用電荷輸送性組成物含有包含導電性聚合物之電荷輸送性物質、有機矽烷化合物及溶劑。
本發明中,作為上述導電性聚合物,基於使所製作之光電變換元件發揮高PCE之觀點,較佳為p型共軛均聚物,更佳為聚噻吩衍生物,又更佳為含有下述式(1)表示之重複單位之聚噻吩衍生物。
式(1)中,R1
及R2
相互獨立為氫原子、碳數1~40之烷基、碳數1~40之氟烷基、碳數1~40之烷氧基、碳數1~40之氟烷氧基、碳數6~20之芳氧基、-O-[Z-O]p
-Re
或磺酸基,或R1
及R2
鍵結形成之-O-Y-O-,Y係可含有醚鍵,可經磺酸基取代之碳數1~40之伸烷基,Z為可經鹵原子取代之碳數1~40之伸烷基,p為1以上,Re
為氫原子、碳數1~40之烷基、碳數1~40之氟烷基或碳數6~20之芳基。
作為碳數1~40之烷基,可為直鏈狀、分支鏈狀、環狀之任一者,作為其具體例,舉例為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基、二十二烷基、三十烷基、四十烷基等,但較佳為碳數1~18之烷基,更佳為碳數1~8之烷基。
作為碳數1~40之氟烷基,可舉例為上述之碳數1~40之烷基中至少1個氫原子經氟原子取代之基,並未特別限定,但舉例為例如氟甲基、二氟甲基、三氟甲基、全氟甲基、1-氟乙基、2-氟乙基、1,2-二氟乙基、1,1-二氟乙基、2,2-二氟乙基、1,1,2-三氟乙基、1,2,2-三氟乙基、2,2,2-三氟乙基、1,1,2,2-四氟乙基、1,2,2,2-四氟乙基、全氟乙基、1-氟丙基、2-氟丙基、3-氟丙基、1,1-二氟丙基、1,2-二氟丙基、1,3-二氟丙基、2,2-二氟丙基、2,3-二氟丙基、3,3-二氟丙基、1,1,2-三氟丙基、1,1,3-三氟丙基、1,2,3-三氟丙基、1,3,3-三氟丙基、2,2,3-三氟丙基、2,3,3-三氟丙基、3,3,3-三氟丙基、1,1,2,2-四氟丙基、1,1,2,3-四氟丙基、1,2,2,3-四氟丙基、1,3,3,3-四氟丙基、2,2,3,3-四氟丙基、2,3,3,3-四氟丙基、1,1,2,2,3-五氟丙基、1,2,2,3,3-五氟丙基、1,1,3,3,3-五氟丙基、1,2,3,3,3-五氟丙基、2,2,3,3,3-五氟丙基、全氟丙基、全氟丁基、全氟戊基、全氟己基、全氟庚基及全氟辛基等。
作為碳數1~40之烷氧基,其中之烷基可為直鏈狀、分支鏈狀、環狀之任一者,舉例為甲氧基、乙氧基、正丙氧基、異丙氧基、環丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、正壬氧基、正癸氧基、正十一烷氧基、正十二烷氧基、正十三烷氧基、正十四烷氧基、正十五烷氧基、正十六烷氧基、正十七烷氧基、正十八烷氧基、正十九烷氧基及正二十烷氧基。
作為碳數1~40之氟烷氧基,若為碳原子上之至少1個氫原子經氟原子取代之烷氧基,則未特別限定,但舉例為例如氟甲氧基、二氟甲氧基、三氟甲氧基、1-氟乙氧基、2-氟乙氧基、1,2-二氟乙氧基、1,1-二氟乙氧基、2,2-二氟乙氧基、1,1,2-三氟乙氧基、1,2,2-三氟乙氧基、2,2,2-三氟乙氧基、1,1,2,2-四氟乙氧基、1,2,2,2-四氟乙氧基、1,1,2,2,2-五氟乙氧基、1-氟丙氧基、2-氟丙氧基、3-氟丙氧基、1,1-二氟丙氧基、1,2-二氟丙氧基、1,3-二氟丙氧基、2,2-二氟丙氧基、2,3-二氟丙氧基、3,3-二氟丙氧基、1,1,2-三氟丙氧基、1,1,3-三氟丙氧基、1,2,3-三氟丙氧基、1,3,3-三氟丙氧基、2,2,3-三氟丙氧基、2,3,3-三氟丙氧基、3,3,3-三氟丙氧基、1,1,2,2-四氟丙氧基、1,1,2,3-四氟丙氧基、1,2,2,3-四氟丙氧基、1,3,3,3-四氟丙氧基、2,2,3,3-四氟丙氧基、2,3,3,3-四氟丙氧基、1,1,2,2,3-五氟丙氧基、1,2,2,3,3-五氟丙氧基、1,1,3,3,3-五氟丙氧基、1,2,3,3,3-五氟丙氧基、2,2,3,3,3-五氟丙氧基及全氟丙氧基等。
作為碳數1~40之伸烷基,可為直鏈狀、分支鏈狀、環狀之任一者,舉例為亞甲基、伸乙基、伸丙基、三亞甲基、四亞甲基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基、伸十二烷基、伸十三烷基、伸十四烷基、伸十五烷基、伸十六烷基、伸十七烷基、伸十八烷基、伸十九烷基、伸二十烷基等。
作為碳數6~20之芳基,舉例為例如苯基、甲苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基及9-菲基等,較佳為苯基、甲苯基及萘基。
作為碳數6~20之芳氧基,舉例為例如苯氧基、蒽氧基、萘氧基、菲氧基及茀氧基等。
作為鹵原子舉例為氟原子、氯原子、溴原子及碘原子。
含有上述式(1)表示之重複單位之聚噻吩衍生物中,較佳R1
及R2
相互獨立為氫原子、碳數1~40之氟烷基、碳數1~40之烷氧基、-O[C(Ra
Rb
)-C(Rc
Rd
)-O]p
-Re
、-ORf
或磺酸基,或R1
及R2
鍵結形成之-O-Y-O-者。Ra
~Rd
相互獨立表示氫原子、碳數1~40之烷基、碳數1~40之氟烷基或碳數6~20之芳氧基。Re
與上述相同。p較佳為1、2或3。Rf
較佳為碳數1~40之烷基、碳數1~40之氟烷基或碳數6~20之芳氧基。
本發明中,更佳為R1
及R2
鍵結形成之-O-Y-O-者。
作為上述聚噻吩衍生物之較佳態樣舉例為例如含有R1
及R2
鍵結形成之-O-Y-O-的重複單位之態樣。
作為上述聚噻吩衍生物之進而其他較佳態樣舉例為例如含有R1
及R2
為下述式(Y1)表示之基的重複單位之態樣。
作為上述聚噻吩衍生物之較佳具體例可舉例為例如含有下述式(1-1)表示之重複單位之聚噻吩。
再者,上述聚噻吩衍生物可為均聚物或共聚物(統計上,包含無規、梯度及嵌段共聚物)。作為包含單體A及單體B之聚合物,嵌段聚合物包含例如A-B二嵌段共聚物、A-B-A三嵌段共聚物及(AB)m
-多嵌段共聚物。聚噻吩亦可包含自其他類型之單體(例如噻吩并噻吩、硒吩、吡咯、呋喃、碲吩、苯胺、芳基胺及伸芳基(例如伸苯基、伸苯基伸乙烯基及伸茀基等)等)衍生之重複單位。
本發明中,聚噻吩衍生物中之式(1)表示之重複單位之含量,相對於重複單位總質量較佳超過50質量%,更佳為80質量%以上,又更佳為90質量%以上,更佳為95質量%以上,最佳為100質量%。
本發明中,對應於聚合所使用之起始單體化合物之純度,所形成之聚合物可含有自雜質衍生之重複單位。本發明中,上述「均聚物」之用語意指包含自1種類單體衍生之重複單位之聚合物,但可含有自雜質衍生之重複單位。本發明中,上述聚噻吩衍生物較佳基本上全部重複單位為上述式(1)表示之重複單位之均聚物,更佳為上述式(1-1)表示之重複單位之均聚物。
式(1)表示之聚噻吩衍生物之重量平均分子量較佳約1,000~1,000,000,更佳約5,000~100,000,又更佳約10,000~約50,000。藉由使重量平均分子量為下限以上,可獲得良好導電性,藉由設為上限以下,可提高對於溶劑之溶解性。又,重量平均分子量係利用凝膠滲透層析之聚苯乙烯換算值。
又,本發明之組成物中,含有式(1)表示之重複單位之聚噻吩衍生物可單獨使用,亦可組合2種以上之化合物而使用。
且,含有式(1)表示之重複單位之聚噻吩衍生物亦可使用市售品,亦可藉由使用以噻吩衍生物等作為起始原料之習知方法聚合者,但任一情況均較佳使用藉由再沉澱或離子交換等之方法純化者。藉由使用純化者,可更提高具備由包含該化合物之組成物所得之薄膜之鈣鈦礦光電變換元件之特性。
作為有機矽烷化合物,較佳為烷氧基矽烷,更佳為三烷氧基矽烷及四烷氧基矽烷。作為上述烷氧基矽烷可舉例為四乙氧基矽烷(TEOS)、四甲氧基矽烷、四異丙氧基矽烷、苯基三乙氧基矽烷、苯基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三甲氧基矽烷、3,3,3-三氟丙基三甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二甲氧基矽烷等。本發明中,該等中,可較佳使用TEOS、四甲氧基矽烷、四丙氧基矽烷。該等有機矽烷化合物可單獨使用1種,或可組合2種以上使用。
有機矽烷化合物之調配量,相對於上述導電性聚合物,且於包含後述電子接受性摻雜物質之情況,係相對於導電性聚合物及電子接受性摻雜物質之總量,以質量比計,較佳為0.1~10倍,更佳0.5~7倍,又更佳為1.0~5倍。藉由使有機矽烷化合物之調配量為上述範圍,可提高所得光電變換元件之安定性。
鈣鈦礦光電變換元件中,電洞捕集層之離子化電位,較佳為接近活性層中之p型半導體材料(鈣鈦礦半導體材料)之離子化電位之值。其差的絕對值較佳為0~1eV,更佳為0~0.5eV,又更佳為0~0.2eV。然而,本發明之電荷輸送性組成物中,基於調節使用其所得之電荷輸送性薄膜之離子化電位之目的,亦可包含電子接受性摻雜物質。作為電子接受性摻雜物質,若為可溶解於使用之至少1種溶劑者,則未特別限定。
作為電子接受性摻雜物質之具體例,舉例為氯化氫、硫酸、硝酸、磷酸等之無機強酸;氯化鋁(III)(AlCl3
)、四氯化鈦(IV)(TiCl4
)、三溴化硼(BBr3
)、三氟化硼醚錯合物(BF3
・OEt2
)、氯化鐵(III)(FeCl3
)、氯化銅(II)(CuCl2
)、五氯化銻(V)(SbCl5
)、五氟化砷(V)(AsF5
)、五氟化磷(PF5
)、三(4-溴苯基)鋁六氯銻酸酯(TBPAH)等之路易士酸;苯磺酸、甲苯磺酸、羥基苯磺酸、5-磺基水楊酸、十二烷基苯磺酸、聚苯乙烯磺酸、及樟腦磺酸等之有機強酸;7,7,8,8-四氰基苯醌二甲烷(TCNQ)、2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)、碘等之有機氧化劑,該等中,較佳為聚苯乙烯磺酸。該等可個別單獨使用,亦可組合2種以上使用。
又,本發明之組成物中,只要可達成本發明之目的,則亦可調配其他添加劑。
作為添加劑之種類,可對應於期望效果自習知者適當選擇使用。
作為電荷輸送性組成物之調製所用之溶劑,可使用能良好溶解導電性聚合物及電子接受性摻雜物質之高溶解性溶劑。高溶解性溶劑可單獨使用1種,或可混合2種以上使用,其使用量,相對於組成物中使用之溶劑全體,可為5~100質量%。
作為此等高溶解性溶劑,舉例為例如水;乙醇、2-丙醇、1-丁醇、2-丁醇、第二丁醇、第三丁醇、1-甲氧基-2-丙醇等之醇系溶劑、N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、1,3-二甲基-2-咪唑啶酮等之醯胺系溶劑等之有機溶劑。
該等中,較佳為選自水及醇系溶劑之至少1種,更佳為水、乙醇、2-丙醇。
電荷輸送性物質及電子接受性摻雜物質均完全溶解於上述溶劑,或成均一分散之狀態。
本發明之電荷輸送性組成物之固形分濃度可考慮組成物之黏度及表面張力等或製作之薄膜厚度等而適當設定,但通常為0.1~20.0質量%左右,較佳為0.5~15.0質量%,更佳為1.0~10.0質量%。又,此處所謂固形分濃度之固形分意指本發明之電荷輸送性組成物中所含之溶劑以外之成分。
又,電荷輸送性物質及電子接受性摻雜物質之質量比,亦考慮所展現之電荷輸送性、電荷輸送性物質等之種類而適當設定,但通常相對於電荷輸送性物質1,電子接受性摻雜物質為0~10,較佳為0.1~8.0,更佳為0.2~7.0。
而且,本發明中所用之電荷輸送性組成物之黏度可考慮所製作之薄膜厚度等或固形分濃度,對應於塗佈方法而適當調節,但通常於25℃為0.1~50mPa・s左右。
調製本發明之電荷輸送性組成物之際,只要固形分可均一溶解或分散於溶劑,則可以任意順序混合電荷輸送性物質、有機矽烷化合物、電子接受性摻雜物質、溶劑等。亦即,可採用例如將作為導電性聚合物之聚噻吩衍生物溶解於溶劑後,於該溶液中溶解電子接受性摻雜物質之方法,將電子接受性摻雜物質溶解於溶劑後,於該溶液中溶解聚噻吩衍生物之方法,將聚噻吩衍生物與電子接受性摻雜物質混合後,將該混合物投入溶劑中使之溶解之方法之任一種方法,只要固形分可均一溶解或分散於溶劑中即可。
又,通常電荷輸送性組成物之調製係在常溫、常壓之惰性氣體環境下進行,但只要組成物中之化合物不分解、組成不大為變化,則亦可在大氣環境下(氧存在下)進行,亦可邊加熱進行。
以上說明之電荷輸送性組成物於順積層型鈣鈦礦太陽能電池之情況係塗佈於陽極上,於逆積層型鈣鈦礦太陽能電池之情況係塗佈於活性層上,並燒成,可形成本發明之電洞捕集層,但作為本發明中之較佳態樣為順積層型。
塗佈時,考慮組成物之黏度與表面張力、期望之薄膜厚度等,可自滴下澆鑄法、旋轉塗佈法、刮刀塗佈法、浸塗法、輥塗法、棒塗法、狹縫塗佈法、噴墨法、印刷法(凸版、凹版、平版、網板印刷等)等之各種濕製程法中採用最適者。
又,通常塗佈係在常溫、常壓之惰性氣體環境下進行,但只要組成物中之化合物不分解、組成不大為變化,則亦可在大氣環境下(氧存在下)進行,亦可邊加熱進行。
膜厚並未特別限定,但任一情況均較佳為0.1~500nm左右,更佳為1~100nm左右。作為使膜厚變化之方法,有使組成物中之固形分濃度變化、或使塗佈時之溶液量變化等之方法。
以下,針對使用本發明之電荷輸送性組成物作為電洞捕集層形成用組成物之鈣鈦礦太陽能電池之製造方法加以說明,但並不限定於此。
(1)順積層型鈣鈦礦太陽能電池[陽極層之形成]:於透明基板表面上形成陽極材料之層,製造透明電極之步驟
作為陽極材料可使用銦錫氧化物(ITO)、銦鋅氧化物(IZO)等之無機氧化物,或金、銀、鋁等之金屬、聚噻吩衍生物、聚苯胺衍生物等之高電荷輸送性有機化合物。該等中,最佳為ITO。又,作為透明基板,可使用玻璃或由透明樹脂所成之基板。
陽極材料之層(陽極層)之形成方法,係對應於陽極材料之性質而適當選擇。通常於難溶性、難分散性昇華性材料之情況係選擇真空蒸鍍法或濺鍍法等之乾製程,於溶液材料或分散液材料之情況,係考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中採用最適者。
又,亦可使用市售之透明陽極基板,該情況下,基於提高元件良率之觀點,較佳使用經平滑化處理之基板。使用市售透明陽極基板之情況,本發明之鈣鈦礦太陽能電池之製造方法不包含形成陽極層之步驟。
使用ITO等之無機氧化物作為陽極材料形成透明陽極基板之情況,於積層上層之前,較佳以洗劑、醇、純水等洗淨後使用。再者,較佳於即將使用前,實施UV臭氧處理、氧-電漿處理等之表面處理。陽極材料以有機物為主成分之情況,亦可不進行表面處理。
[電洞捕集層之形成]:於所形成之陽極材料之層上形成電洞捕集層之步驟
依據上述方法,於陽極材料之層上,使用本發明之電荷輸送性組成物形成電洞捕集層。
[活性層之形成]:於形成之電洞捕集層上形成活性層之步驟
本發明中作為活性層係使用含有鈣鈦礦半導體化合物之活性層。
所謂鈣鈦礦半導體化合物係指具有鈣鈦礦構造之半導體化合物。作為鈣鈦礦半導體化合物可使用習知化合物,並未特別限定,但舉例為例如以通式A+
M2+
X- 3
表示者或以通式A+ 2
M2+
X- 4
表示者。此處,A+
表示1價陽離子,M2+
表示2價陽離子,X-
表示1價陰離子。
作為1價陽離子A+
舉例為包含例如週期表第1族及第13族~第16族元素之陽離子。該等中,較佳為銫離子、銣離子、可具有取代基之銨離子、或可具有取代基之鏻離子。
作為可具有取代基之銨離子舉例為例如1級銨離子或2級銨離子。上述取代基並未特別限定,但較佳為烷基銨離子或芳基銨離子。尤其,為了避免立體障礙,更佳為成為三次元結晶構造之單烷基銨離子。上述烷基銨離子中所含之烷基碳數較佳為1~30,更佳為1~20,又更佳為1~10。上述芳基銨離子所含之芳基之碳數較佳為6~30,更佳為6~20,又更佳為6~12。
作為1價陽離子A+
之具體例舉例為甲基銨離子、乙基銨離子、異丙基銨離子、正丙基銨離子、異丙基銨離子、正丁基銨離子、第三丁基銨離子、二甲基銨離子、二乙基銨離子、苯基銨離子、苄基銨離子、苯乙基銨離子、胍鎓離子、甲脒鎓離子、乙脒鎓離子及咪唑鎓離子等。上述陽離子A+
可單獨使用1種,或可組合2種以上使用。
作為2價陽離子M2+
,較佳為2價金屬陽離子或半金屬陽離子,更佳為週期表第14族元素之陽離子。作為2價之陽離子M的具體例舉例為鉛陽離子(Pb2+
)、錫陽離子(Sn2+
)、鍺陽離子(Ge2+
)等。本發明中,基於獲得安定性優異之光電變換元件之觀點,較佳包含鉛陽離子。上述陽離子M2+
可單獨使用1種,或可組合2種以上使用。
作為1價之陰離子X-
,舉例為鹵化物離子、乙酸離子、硝酸離子、乙醯基丙酮酸離子、硫代氰酸離子及2,4-戊二酸離子等,較佳為鹵化物離子。上述陰離子X-
可單獨使用1種,或可組合2種以上使用。
作為鹵化物離子,舉例為氯化物離子、溴化物離子及碘化物離子等。本發明中,基於不過於擴大半導體之帶隙之觀點,較佳包含碘化物離子。
作為鈣鈦礦半導體化合物較佳為例如有機-無機鈣鈦礦半導體化合物,更佳為鹵化物系有機-無機鈣鈦礦半導體化合物。作為鈣鈦礦半導體化合物之具體例舉例為CH3
NH3
PbI3
、CH3
NH3
PbBr3
、CH3
NH3
PbCl3
、
CH3
NH3
SnI3
、CH3
NH3
SnBr3
、CH3
NH3
SnCl3
、
CH3
NH3
PbI(3-x)
Clx
、CH3
NH3
PbI(3-x)
Brx
、CH3
NH3
PbBr(3-x)
Clx
、CH3
NH3
Pb(1-y)
Sny
I3
、CH3
NH3
Pb(1-y)
Sny
Br3
、
CH3
NH3
Pb(1-y)
Sny
Cl3
、CH3
NH3
Pb(1-y)
Sny
I(3-x)
Clx
、
CH3
NH3
Pb(1-y)
Sny
I(3-x)
Brx
、CH3
NH3
Pb(1-y)
Sny
Br(3-x)
Clx
等。又,x表示0~3,y表示0~1之任意數。
基於提高光電變換效率之觀點,作為鈣鈦礦半導體化合物,較佳使用具有1.0~3.5eV之能量帶隙之半導體化合物。
活性層中亦可含有2種以上之鈣鈦礦半導體化合物。例如活性層中亦可含有上述A+
、M2+
及X-
中之至少1個不同之2種以上之鈣鈦礦半導體化合物。
活性層中之鈣鈦礦半導體化合物含量,基於獲得良好光電變換特性之觀點,較佳為50質量%以上,更佳為70質量%以上,又更佳為80質量%以上。關於上限並未特別限定,但通常為100質量%以下。
又,活性層根據需要亦可含有其他添加物。作為本發明中可使用之添加物舉例為例如界面活性劑、電荷賦予劑、1,8-二碘化辛烷、N-環己基-2-吡咯啶酮等。
活性層中之該等添加劑含量,基於獲得良好PCE之觀點,較佳為50質量%以下,更佳為30質量%以下,又更佳為20質量%以下。關於下限並未特別限定,但通常為0質量%以上。
活性層之形成方法亦與上述同樣,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中採用最適者。
[電子捕集層之形成]:於形成之活性層上形成電子捕集層之步驟
根據需要,以使電荷移動效率化等為目的,亦可於活性層與陰極層之間形成電子捕集層。
作為形成電子捕集層之材料,舉例為富勒烯類、氧化鋰(Li2
O)、氧化鎂(MgO)、氧化鋁(Al2
O3
)、氟化鋰(LiF)、氟化鈉(NaF)、氟化鎂(MgF2
)、氟化鍶(SrF2
)、碳酸銫(Cs2
CO3
)、8-羥基喹啉鋰鹽(Liq)、8-羥基喹啉鈉鹽(Naq)、浴銅靈(bathocuproine)(BCP)、4,7-二苯基-1,10-菲咯啉(BPhen)、聚伸乙基亞胺(PEI)、乙氧化聚伸乙基亞胺(PEIE)等。
作為富勒烯類較佳為富勒烯及其衍生物,但並未特別限定。具體而言,舉例為以C60、C70、C76、C78、C84等作為基本骨架之富勒烯及其衍生物。富勒烯衍生物之富勒烯骨架中之碳原子可經任意官能基修飾,亦可該官能基彼此鍵結形成環。富勒烯衍生物中包含富勒烯鍵結之聚合物。較佳為具有對溶劑之親和性高之官能基、對溶劑之可溶性高的富勒烯衍生物。
作為富勒烯衍生物中之官能基,舉例為例如氫原子、羥基、氟原子、氯原子等之鹵原子,甲基、乙基等之烷基,乙烯基等之烯基,氰基,甲氧基、乙氧基等之烷氧基,苯基、萘基等之芳香族烴基,噻吩基、吡啶基等之芳香族雜環基等。具體而言,舉例為C60H36、C70H36等之氫化富勒烯、C60、C70等之氧化富勒烯、富勒烯金屬錯合物等。作為富勒烯衍生物,更佳使用[6,6]-苯基C61丁酸甲酯([60]PCBM)或[6,6]-苯基C71丁酸甲酯([70]PCBM)。
電子捕集層之形成方法,亦與上述同樣,於電子捕集材料為難溶性昇華性材料之情況,選擇上述之各種乾製程,於溶液材料或分散液材料之情況,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中選擇最適者。
[陰極層之形成]:於形成之電子捕集層上形成陰極層之步驟
作為陰極材料舉例為鋁、鎂-銀合金、鋁-鋰合金、鋰、鈉、鉀、銫、鈣、鋇、銀、金等之金屬或銦錫氧化物(ITO)、銦鋅氧化物(IZO)等之無機氧化物,或聚噻吩衍生物、聚苯胺衍生物等之高電荷輸送性有機化合物,亦可積層、混合複數陰極材料而使用。
陰極層之形成方法,亦與上述同樣,於陰極層材料為難溶性、難分散性昇華性材料之情況,選擇上述之各種乾製程,於溶液材料或分散液材料之情況,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中選擇最適者。
[載子阻擋層之形成]
根據需要,以控制光電流之整流性等為目的,於任意層間亦可設置載子阻擋層。設置載子阻擋層之情況,通常大多情況係於活性層與電洞捕集層或陽極之間插入電子阻擋層,於活性層與電子捕集層或陰極之間插入電洞阻擋層,但不限定於此。
作為形成電洞阻擋層之材料,舉例為氧化鈦、氧化鋅、氧化錫、浴銅靈(BCP)、4,7-二苯基1,10-菲咯啉(BPhen)等。
作為形成電子阻擋層之材料,舉例為N,N’-二(1-萘基)-N,N’-二苯基聯苯胺(α-NPD)、聚(三芳基胺)(PTAA)等之三芳基胺系材料等。
載子阻擋層之形成方法,亦與上述同樣,於載子阻擋層材料為難溶性、難分散性昇華性材料之情況,選擇上述之各種乾製程,於溶液材料或分散液材料之情況,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中選擇最適者。
(2)逆積層型鈣鈦礦太陽能電池
[陰極層之形成]:於透明基板表面形成陰極材料層,製造透明陰極基板之步驟
作為陰極材料,除了上述順積層型之陽極材料所例示者以外,舉例為氟摻雜氧化錫(FTO),作為透明基板,舉例為上述順積層型之陽極材料所例示者。
陰極材料層(陰極層)之形成方法,亦於難溶性、難分散性昇華性材料之情況,選擇上述之乾製程,於溶液材料或分散液材料之情況,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中選擇最適者。
又,該情況亦可較佳地使用市售透明陰極基板,基於提高元件良率之觀點,較佳使用經平滑化處理之基板。使用市售之透明陰極基板之情況,本發明之鈣鈦礦太陽能電池之製造方法不包含形成陰極層之步驟。
使用無機氧化物作為陰極材料形成透明陰極基板之情況,亦可實施與順積層型之陽極材料同樣之洗淨處理或表面處理。
[電子捕集層之形成]:於形成之陰極上形成電子捕集層之步驟
根據需要,以使電荷移動效率化等為目的,亦可於活性層與陰極層之間形成電子捕集層。
作為形成電子捕集層之材料,除了上述順積層型之材料所例示者以外,舉例為氧化鋅(ZnO)、氧化鈦(TiO)、氧化錫(SnO)等。
電子捕集層之形成方法,亦於難溶性、難分散性昇華性材料之情況,選擇上述之乾製程,於溶液材料或分散液材料之情況,考慮組成物之黏度與表面張力、期望之薄膜厚度等,自上述各種濕製程法中選擇最適者。且亦可採用使用濕製程(尤其是旋轉塗佈法或狹縫塗佈法)於陰極上形成無機氧化物之前驅物層,進行燒成而形成無機氧化物之層的方法。
[活性層之形成]:於形成之電子捕集層上形成活性層之步驟
形成含有上述鈣鈦礦半導體化合物之活性層作為活性層。
活性層之形成方法與上述順積層型之活性層所說明之方法相同。
[電洞捕集層之形成]:於形成之活性層材料之層上形成電洞捕集層之步驟
依據上述方法,於活性層材料之層上使用本發明之組成物形成電洞捕集層。
[陽極層之形成]:於形成之電洞捕集層上形成陽極層之步驟
作為陽極材料,舉例為與上述順積層型之陽極材料相同者,作為陽極層之形成方法,亦與順積層型之陰極層相同。
[載子阻擋層之形成]
與順積層型之元件同樣,根據需要,以控制光電流之整流性等為目的,於任意層間亦可設置載子阻擋層。
作為形成電洞阻擋層之材料及形成電子阻擋層之材料舉例為與上述相同者,載子阻擋層之形成方法亦與上述相同。
藉由上述例示方法製作之鈣鈦礦太陽能電池元件,為了防止因大氣所致之元件劣化,可再度導入手套箱內於氮氣等之惰性氣體環境下進行密封操作,以密封之狀態作為太陽能電池發揮功能,可進行太陽能電池特性之測定。
作為密封法,舉例有將端部附著有UV硬化樹脂之凹型玻璃基板,於惰性氣體環境下,附著於鈣鈦礦太陽能電池元件之成膜面側,藉由UV照射使樹脂硬化之方法,或於真空下,藉由濺鍍等方法進行膜密封類型之密封的方法等。
[實施例]
以下,列舉實施例及比較例更具體說明本發明,但本發明並非限定於下述實施例。又,使用之裝置如以下。
(1)太陽模擬器:分光計器(股)製,OTENTOSUN-III
(2)源測量單元:KEITHLEY Instruments(股)製 2401
(3)膜厚測定裝置:Bulker公司製,DEKTAK XT
(4)光電子分光裝置:理研計器(股)製,AC-2
[1]電洞捕集層用組成物之調製
[實施例1-1]
將PEDOT-PSS(HERAEUS公司製,型號AI4083,PEDOT:PSS=1:6,固形分濃度:1.3~1.7質量%) 2,462 mg溶解於乙醇2,425mg中,添加TEOS(多摩化學工業(股)製) 113mg,調製深藍色溶液。所得深藍色液體以0.45μm針筒過濾器過濾,獲得電洞捕集層用組成物A(固形分濃度:3.0質量%)。
又,上述固形分濃度係將PEDOT:PSS之固形分濃度設為1.5質量%,TEOS之全量設為固形分而計算之值(以下同)。
[實施例1-2]
除了將TEOS量變更為80mg以外,與實施例1同樣獲得電洞捕集層用組成物B(固形分濃度:2.3質量%)。
[實施例1-3]
除了將TEOS量變更為60mg以外,與實施例1同樣獲得電洞捕集層用組成物C(固形分濃度:1.9質量%)。
[實施例1-4]
除了將TEOS量變更為30mg以外,與實施例1同樣獲得電洞捕集層用組成物D(固形分濃度:1.3質量%)。
[2]鈣鈦礦太陽能電池之製作與評價
[實施例2-1]
將碘化鉛(PbI2
)與碘化甲基銨(CH3
NH3
I)分別以1M之濃度溶解於二甲基亞碸(DMSO)中調製鈣鈦礦前驅物溶液。
另一方面,於形成有膜厚100nm之由銦・錫氧化物(ITO)而成之正極的玻璃基板上,藉由旋轉塗佈法,塗佈電洞捕集層用組成物A,於200℃進行退火處理形成膜厚71nm之電洞捕集層A。該形成有電洞捕集層之基板搬入經氮氣置換之手套箱內。接著,使上述調製之前驅物溶液通過孔徑0.45μm之過濾器滴加於電洞捕集層A上,使基板以500rpm旋轉10秒後,以6,000rpm旋轉30秒而旋轉塗佈,製膜鈣鈦礦前驅物膜。其次,於充滿脫氧甲苯(第2溶劑)之浸漬槽於冷卻板上進行溫度調整為25℃。邊攪拌該溶劑,邊將形成有鈣鈦礦前驅物膜之基板於該溶劑中浸漬2分鐘。隨後,取出基板,藉由進行5分鐘之90℃退火處理,製造鈣鈦礦膜。於該鈣鈦礦膜上,藉由真空蒸鍍法,以1×10-4
Pa之真空度形成2層有機層與電極。首先,於鈣鈦礦膜上,蒸鍍30nm厚之富勒烯(C60
),於其上,蒸鍍10nm厚之BCP,形成2層有機層。再者,於其上蒸鍍100nm厚之Ag,形成電極。所得積層體(基板/ITO正極/電洞捕集層/鈣鈦礦膜/C60
層/BCP層/Ag負極)收容於玻璃密封管內,以UV硬化樹脂密封,獲得太陽能電池。
[實施例2-2]
除了使用電洞捕集層用組成物B作為電洞捕集層以外,使用與實施例2-1同樣順序,製作太陽能電池。
[實施例2-3]
除了使用電洞捕集層用組成物C作為電洞捕集層以外,使用與實施例2-1同樣順序,製作太陽能電池。
[實施例2-4]
除了使用電洞捕集層用組成物D作為電洞捕集層以外,使用與實施例2-1同樣順序,製作太陽能電池。
[比較例2-1]
除了使用PEDOT-PSS(HERAEUS公司製,型號AI4083)作為電洞捕集層以外,使用與實施例2-1同樣順序,製作太陽能電池。
[3]特性評價
針對上述實施例2-1~2-4及比較例2-1製作之鈣鈦礦太陽能電池,使用太陽模擬器,以擬似AM1.5之太陽光以100mW/cm2
放射照度進行照射,進行短路電流密度(Jsc)、開放電壓(Voc)、曲線因子(FF)、PCE之評價。結果示於表1。
又,PCE[%]係由下式算出。
PCE[%]=Jsc[mA/cm2
]×Voc[V]×FF÷入射光強度(100 [mW/cm2
])×100
由表1之結果,可知藉由使用本發明之電洞捕集層用組成物,可獲得具有非常安定特定之鈣鈦礦太陽能電池。
[4]化學耐性評價用之附電洞捕集層之基板的製作
[實施例2-5]
於形成有膜厚100nm之由銦・錫氧化物(ITO)而成之膜的玻璃基板上,藉由旋轉塗佈法,塗佈電洞捕集層用組成物A,於200℃進行退火處理而形成膜厚71nm之電洞捕集層,製作附電洞捕集層之基板。製作3片上述之附電洞捕集層之基板。
[比較例2-2]
除了使用PEDOT-PSS(HERAEUS公司製,型號AI4083)作為電洞捕集層形成用組成物以外,使用與實施例2-5同樣順序,形成膜厚40nm之電洞捕集層,製作附電洞捕集層之基板。製作3片上述之附電洞捕集層之基板。
[5]化學耐性之評價
於上述製作之附電洞捕集層之基板的電洞捕集層上,滴加二甲基亞碸(DMSO) 3mL,靜置10秒後,於6,000rpm旋轉塗佈30秒,而形成DMSO液膜。隨後於200℃乾燥10分鐘,而製作DMSO處理基板。
其次,於另一附電洞捕集層之基板的電洞捕集層上,滴加調整為1M濃度之碘化甲基銨(MAI)之DMSO溶液3mL,靜置10秒後,於6,000rpm旋轉塗佈30秒,於電洞捕集層上形成MAI(DMSO)液膜。進而,滴加DMSO 3mL,靜置10秒後,邊滴加DMSO 3mL邊於6,000rpm旋轉塗佈30秒,進行清洗處理。其次,於200℃乾燥10分鐘,而製作MAI(DMSO)處理基板。
針對DMSO處理基板、MAI(DMSO)處理基板及未處理基板,使用光電子分光裝置測定電洞捕集層之離子化電位。結果示於表2。
由表2之結果,使用比較例之組成物形成電洞捕集層之情況,暴露於MAI時離子化電位為0.1eV以上變淺,相對地,使用電洞捕集層用組成物A形成電洞捕集層之情況,離子化電位之變化較小。暴露於DMSO之情況亦見到同樣傾向。
Claims (14)
- 一種鈣鈦礦光電變換元件用電荷輸送性組成物,其特徵係含有包含導電性聚合物之電荷輸送性物質、有機矽烷化合物及溶劑,其中上述溶劑包含選擇自由水、乙醇、2-丙醇、1-丁醇、2-丁醇、第二丁醇、第三丁醇、1-甲氧基-2-丙醇、N-甲基甲醯胺、N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、及1,3-二甲基-2-咪唑啶酮所成群組之至少一種的高溶解性溶劑。
- 如請求項1之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述導電性聚合物係p型共軛均聚物。
- 如請求項1或2之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述導電性聚合物係聚噻吩衍生物。
- 如請求項1或2之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述有機矽烷化合物為烷氧基矽烷。
- 如請求項5之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述烷氧基矽烷包含選自三烷氧基矽烷及四烷氧基矽烷之至少1種。
- 如請求項1或2之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述電荷輸送性組成物係鈣鈦礦光電變換元件之電洞捕集層用。
- 如請求項7之鈣鈦礦光電變換元件用電荷輸送性組成物,其中上述鈣鈦礦光電變換元件係太陽能電池。
- 一種薄膜,其係由如請求項1至6中任一項之鈣鈦礦光電變換元件用電荷輸送性組成物所得。
- 如請求項9之薄膜,其中上述薄膜係鈣鈦礦光電變換元件之電洞捕集層。
- 一種鈣鈦礦光電變換元件,其具備如請求項9或10之薄膜。
- 一種鈣鈦礦光電變換元件,其具有如請求項10之電洞捕集層及與其連接地設置之活性層,該活性 層包含鈣鈦礦半導體化合物。
- 一種鈣鈦礦光電變換元件,其係具有一對電極、設於上述一對電極間之活性層、及設於上述活性層與上述電極之間之電洞捕集層的鈣鈦礦光電變換元件,上述活性層係包含鈣鈦礦半導體化合物者,上述電洞捕集層係如請求項10之薄膜。
- 一種太陽能電池,其具備如請求項11至13中任一項之鈣鈦礦光電變換元件。
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