JPWO2011096508A1 - 光電気素子 - Google Patents
光電気素子 Download PDFInfo
- Publication number
- JPWO2011096508A1 JPWO2011096508A1 JP2011552831A JP2011552831A JPWO2011096508A1 JP WO2011096508 A1 JPWO2011096508 A1 JP WO2011096508A1 JP 2011552831 A JP2011552831 A JP 2011552831A JP 2011552831 A JP2011552831 A JP 2011552831A JP WO2011096508 A1 JPWO2011096508 A1 JP WO2011096508A1
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- Prior art keywords
- electron transport
- transport layer
- electrode
- conductive
- organic compound
- Prior art date
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Images
Classifications
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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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- 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
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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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
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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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Abstract
Description
ゲル乾燥体とは、ゲル層2を乾燥させたものを指す。ゲル層2を乾燥させるとは、ゲル層2に内包される溶液の除去すること、特には溶媒を除去することを指す。ゲル層2を乾燥させる方法としては、加熱による方法、真空環境中で溶液または溶媒を除去する方法、別の溶媒を利用してゲル層2に内包される溶液又は溶媒を除去する方法などが挙げられる。
(Xi)nはゲル部位を示し、Xiはゲル部位を構成する化合物のモノマーを示す。ゲル部位はポリマー骨格から形成され得る。モノマーの重合度nは、n=1〜10万の範囲が好ましい。Yは(Xi)nに結合している酸化還元部を示す。j,kはそれぞれ1分子中に含まれる(Xi)n、Yの数を表す任意の整数であり、いずれも1〜10万の範囲が好ましい。酸化還元部Yはゲル部位(Xi)nを形成するポリマー骨格のいかなる部位に結合していてもよい。酸化還元部Yは種類の異なる部位を含んでいてもよく、この場合は電子交換反応の観点から酸化還元電位が近い部位が好ましい。
(ガルビモノマーの合成)
反応容器内に、4−ブロモ−2,6−ジ−tert−ブチルフェノール(135.8g;0.476mol)と、アセトニトリル(270ml)とを入れ、さらに不活性雰囲気下で、N,O−ビス(トリメチルシリル)アセトアミド(BSA)(106.3g;129.6ml)を加え、70℃で終夜撹拌することで、完全に結晶が析出するまで反応さえた。析出した白色結晶を濾過し、真空乾燥した後、エタノールで再結晶して精製することによって、[化25]において符号「1」で示す、(4−ブロモ−2,6−ジ−tert−ブチルフェノキシ)トリメチルシラン(150.0g;0.420mol)の白色板状結晶を得た。
上記ガルビモノマーの合成で得られたガルビモノマー(p−ヒドロガルビノキシルスチレン)1gと、テトラエチレングリコールジアクリレート57.7mgと、アゾビスイソブチロニトリル15.1mgを、テトラヒドロフラン2mlに溶解した後、窒素置換し、一晩還流することで、ガルビモノマーを重合させ、[化25]において符号「4」で示すガルビポリマーを得た。
第一の電極4が設けられた第一の基材7として、厚み0.7mm、シート抵抗100Ω/□の導電性ガラス基板を用意した。この導電性ガラス基板はガラス基板と、このガラス基板の一面に積層された、フッ素ドープされたSnO2からなるコーティング膜とから構成され、前記ガラス基板が第一の基板7、コーティング膜が第一の電極4となる。なお、前記コーティング膜のラフネスファクターは1.5である。
上記電子輸送層1の形成における導電性ガラス基板と同じ構成を有する導電性ガラス基板を用意した。
実施例1において、導電助材3及び電子輸送層1を形成する際、ITO粒子の代わりに棒状(繊維状)の導電性材料(三井金属鉱業製、TYPE−V、平均軸比8.0、平均短軸径1μm)を濃度約5質量%で分散させた液を調製して使用した。それ以外は実施例1と同様にして光電気素子を作製した。前記、棒状(繊維状)の導電性材料からなる導電助材3のラフネスファクターは150、空隙率は60%である。
電子輸送層1を形成するにあたり、まずエチルセルロースを20質量%含むターピネオール溶液に、酸化スズ(平均粒径20nmφ)をその濃度が20質量%となるように分散し、酸化スズペーストを調製した。この酸化スズペーストを、実施例1と同じ構成を有する導電性ガラス基板上に塗布し、450℃で30分間焼成し、厚み3μmの多孔質導電膜からなる導電助材3を作製した。この導電助材3のラフネスファクターは500、空隙率は40%である。
導電助材3を形成するにあたり、実施例3の場合と同じ手法で、厚み10μmの多孔質導電膜からなる導電助材3を作製した。この導電助材3のラフネスファクターは2000、空隙率は40%である。
電子輸送層1を形成するにあたり、まずポリビニルアセテート(分子量50万)の濃度が14質量%のジメチルホルムアミド溶液を調製し、これをA液とした。また、13.5gの塩化スズ水和物を100mlのエタノールに溶解し、3時間還流を行うことで酸化スズゾルを調製、これをB液とした。そして、A液とB液とを質量比0.8:1で混合し、6時間撹拌して得た液をC液とした。このC液を、導電性ガラス基板の透明電極上に、エレクトロスピニング法によって塗布し、450℃で30分間焼成した。これにより、平均外径(短軸径)100nmの繊維状導電材料で構成される、厚み1μmの多孔質導電膜からなる導電助材3を作製した。この多孔質導電膜の、平面視での電子顕微鏡写真を図2に示す。この導電助材3のラフネスファクターは200、空隙率は80%である。
実施例1において、ITO粒子を用いない以外は実施例1と同様にして光電気素子を作製した。尚、コーティング膜からなる第一の電極4のラフネスファクターは、実施例1と同様1.5である。
各実施例及び比較例で得られた光電気素子の平面視面積1cm2の領域に200ルックスの光を照射しながら、Keithley 2400source meter(ケースレイ社製の2400型汎用ソースメータ)を用いたIV測定により各光電気素子の開放電圧および短絡電流値を測定した。光源には蛍光灯(ラピッド蛍光灯FLR20S・W/M、パナソニック株式会社製)を使用し、25℃環境下での測定を行った。また、光電変換部1cm2が受光する条件において光電気素子の評価を行った。その結果を下記表1に示す。
2 ゲル層
3 導電助材
4 第一の電極
5 正孔輸送層
6 第二の電極
7 第一の基板
8 第二の基板
9 繊維状集電材
Claims (7)
- 第一の電極と、第二の電極と、前記第一の電極と前記第二の電極との間に挟まれている電子輸送層及び正孔輸送層と、電解質溶液と、導電助材とを備え、
前記電子輸送層が、繰り返し酸化還元が可能な酸化還元部を有する有機化合物を備え、
前記電解質溶液が前記酸化還元部の還元状態を安定化させる機能を有し、
前記有機化合物と前記電解質溶液とがゲル層を形成し、
前記導電助材が前記ゲル層内に存在していると共に前記導電助材の少なくとも一部が前記第一の電極と接していることを特徴とする光電気素子。 - 前記導電助材のラフネスファクターが5以上2000以下であることを特徴とする請求項1に記載の光電気素子。
- 前記導電助材が粒子状の導電性材料の連結体から構成されていることを特徴とする請求項1および2に記載の光電気素子。
- 前記導電助材が繊維状の導電性材料から構成されていることを特徴とする請求項1および2に記載の光電気素子。
- 前記繊維状の導電性材料の平均外径が50nm以上1000nm以下であることを特徴とする請求項4に記載の光電気素子。
- 前記繊維状の導電性材料から構成されている導電助材の空隙率が50%以上95%以下であることを特徴とする請求項4または5に記載の光電気素子。
- 前記繊維状の導電性材料の平均繊維長/平均繊維径比が1000以上であることを特徴とする請求項4乃至6のいずれかに記載の光電気素子。
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