JP2015198247A - ピリジン系添加剤が含有された長期安定性固体状の染料感応太陽電池 - Google Patents
ピリジン系添加剤が含有された長期安定性固体状の染料感応太陽電池 Download PDFInfo
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- JP2015198247A JP2015198247A JP2014261301A JP2014261301A JP2015198247A JP 2015198247 A JP2015198247 A JP 2015198247A JP 2014261301 A JP2014261301 A JP 2014261301A JP 2014261301 A JP2014261301 A JP 2014261301A JP 2015198247 A JP2015198247 A JP 2015198247A
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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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
- H10K85/30—Coordination compounds
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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Abstract
Description
Sads + hν → S* ads (反応式1)
S* ads → S+ ads + e- inj (反応式2)
S+ ads + R- → Sads + R (反応式3)
R + e- cathode → R- cathode (反応式4)
e- inj + S+ ads → Sads (反応式5)
e- inj + R → R- anode (反応式6)
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を21mM、そしてピリジン2個を連結した二量体を0.11M濃度、60度で1時間ほど溶かして、均一で透明な溶液を得た。
正孔伝達物質の混合溶液は、前記実施例1と同一な方法で用意した。
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を21mM、そしてピリジンを三つ連結した三量体を0.05M濃度、60度で1時間ほど溶かし、均一で透明な溶液を得た。
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を21mM、そしてピリジン4個を連結した四量体を0.05M濃度、60度で1時間ほど溶かし、均一で透明な溶液を得た。
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を21mM、そしてピリジン2個を連結した二量体を0.11M濃度(試料1)から0.2M(試料2)、0.3M(試料3)まで増加させながら、60℃で1時間ほど溶かし、均一で透明な溶液を得た。
正孔伝達物質であるポリ−3−へキシルチオフェン(poly-3-hexylthiophene(P3HT))を15mg/mlの濃度でジクロロベンゼン(1,2-dichlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を10.5mM、そしてピリジン2個を連結した二量体を0.05M濃度、60度で1時間ほど溶かし、均一で透明な溶液を得た。
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を5mM(試料4)、10mM(試料5)、21mM(試料6)、30mM(試料7)の濃度で増加させ、そしてピリジン2個を連結した二量体を0.11M濃度、60度で1時間ほど溶かし、均一で透明な溶液を得た。
正孔伝達物質である2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(2,2',7,7'-tetrakis(diphenylamino)-9.9'-spirobifluorene (spiro-MeOTAD))を0.17M濃度でクロロベンゼン(chlorobenzene)溶媒に溶かし、添加剤としてリチウムリチウムビス(トリフルオロメタンスルフォニル)イミド(lithium Lithium bis(trifluoromethanesulfonyl)imide(Li-TFSI))を21mM、そしてターシャリーブチルピリジン(tert-butylpyridine)を0.11M濃度、60度で1時間ほど溶かし、均一で透明な溶液を得た。
11 - 作動電極(第1電極)
12 - 無機酸化物のち密層
13 - 多孔性酸化物及び光吸収混合層
14 - 正孔伝達層
15 - 相対電極(第2電極)
Claims (17)
- 第1電極として作動電極と;前記第1電極に対向する第2電極と;前記第1電極と前記第2電極の間に形成されて染料が吸着された酸化物層と;前記酸化物層に隣接して、前記式1〜3の中で選択された一つ以上のピリジン化合物を添加剤として含有する正孔伝達層を含む構造を持つ、請求項1に記載の太陽電池。
- 前記化学式1〜3の中で選択された一つ以上のピリジン化合物は、正孔伝達物質のマトリックス成分に添加剤として混合された状態で固体状の正孔伝達層を構成することを特徴とする、請求項1または請求項2に記載の太陽電池。
- 前記化学式1〜3の中で選択された一つ以上のピリジン化合物は、前記正孔伝達層内の固体状の正孔伝達物質を基準にして0.05〜0.5M濃度で含有することを特徴とする、請求項1または請求項2に記載の太陽電池。
- 前記化学式1のピリジン化合物は、前記正孔伝達層内の固体状の正孔伝達物質を基準にして0.1〜0.3M濃度で含有することを特徴とする、請求項1または請求項2に記載の太陽電池。
- 前記化学式3のピリジン化合物は、前記正孔伝達層内の固体状の正孔伝達物質を基準にして0.05〜0.1M濃度で含有することを特徴とする、請求項1または請求項2に記載の太陽電池。
- 正孔伝達層には前記化学式1〜3の中で選択された一つ以上のピリジン化合物と正孔伝達物質としてポリへキシルチオフェン(P3HT)、2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(スピロMeOTAD)、ポリ[2−メトキシ−5−(2−エチルへキシルオキシ)−1,4−フェニレンビニレン](MEHPPV)、ポリ[2,5−ビス(2−デシルドデシル)ピロロ[3,4−c]ピロール−1,4(2H,5H)−ジオン−(E)−1,2−ジ(2,2’−ビチオフェン−5−イル)エテン](PDPPDBTE)の中で選択されたものが一つ以上含有されていることを特徴とする、請求項3に記載の太陽電池。
- 追加的にリチウムビス(トリフルオロメタンスルフォニル)イミド(Li-TFSI)が固体状の正孔伝達物質を基準にして5〜30mM濃度で含有されていることを特徴とする、請求項8に記載の太陽電池。
- 第1電極は、ITO(インジウムスズ酸化物)、FTO(フッ素ドープ酸化スズ)、ZnO(Ga2O3またはAl2O3)またはSnO2-Sb2O3の中で選択されたものを含むことを特徴とする、請求項2に記載の太陽電池。
- 多孔性酸化物及び光吸収混合層は、多孔性の酸化チタンに光吸収物質としてルテニウム系染料が吸着されたことを特徴とする、請求項2に記載の太陽電池。
- 前記第2電極は相対電極として、金、銀またはプラチナを含むことを特徴とする、請求項2に記載の太陽電池。
- 下記化学式1a、2a及び3の中で選択された一つ以上のピリジン化合物と正孔伝達物質としてポリへキシルチオフェン(P3HT)、2,2’,7,7’−テトラキス(ジフェニルアミノ)−9.9’−スピロビフルオレン(スピロMeOTAD)、ポリ[2−メトキシ−5−(2−エチルへキシルオキシ)−1,4−フェニレンビニレン](MEHPPV)、ポリ[2,5−ビス(2−デシルドデシル)ピロロ[3,4−c]ピロール−1,4(2H,5H)−ジオン−(E)−1,2−ジ(2,2’−ビチオフェン−5−イル)エテン](PDPPDBTE)の中で選択されたことが一つ以上含有されていて、これに追加としてリチウムビス(トリフルオロメタンスルフォニル)イミド(Li-TFSI)が固体状の正孔伝達物質を基準にして5〜30mM濃度で含有されていることを特徴とする、請求項13に記載の正孔伝達物質の混合溶液。
- 正孔伝達物質を溶媒に溶かし、前記化学式1〜3の中で選択された一つ以上のピリジン化合物を添加して正孔伝達物質の混合溶液を製造する段階;作動電極の上に無機酸化物のち密層を形成させる段階;前記無機酸化物のち密層の上に多孔性酸化物と光吸収混合層を形成する段階;その上に前記製造した正孔伝達物質の混合溶液を塗布して正孔伝達層を形成する段階;及び前記正孔伝達層の上に相対電極を塗布する段階を含む固体染料感応太陽電池の製造方法。
- 前記無機酸化物のち密層の上に多孔性酸化物と光吸収混合層を形成する段階において、多孔性酸化物に光吸収物質を吸着させる過程を含むことを特徴とする、請求項16に記載の太陽電池の製造方法。
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