JP6082006B2 - 光電変換層用組成物および光電変換素子 - Google Patents
光電変換層用組成物および光電変換素子 Download PDFInfo
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- JP6082006B2 JP6082006B2 JP2014526972A JP2014526972A JP6082006B2 JP 6082006 B2 JP6082006 B2 JP 6082006B2 JP 2014526972 A JP2014526972 A JP 2014526972A JP 2014526972 A JP2014526972 A JP 2014526972A JP 6082006 B2 JP6082006 B2 JP 6082006B2
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone 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
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- WCYJXDMUQGVQQS-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1 WCYJXDMUQGVQQS-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical compound C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- FHNRXCZVLIJCGL-UHFFFAOYSA-N ruthenium(2+) tetrabutylazanium Chemical compound [Ru+2].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC FHNRXCZVLIJCGL-UHFFFAOYSA-N 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明の組成物は、半導体およびイオン性ポリマーを少なくとも含む。このような組成物は、後述するように、特に、電極を構成する光電変換層(又は電極を構成する光電変換層)を形成するための組成物として有用である。
半導体としては、無機半導体、有機半導体に大別でき、本発明では、無機半導体を好適に用いることができる。無機半導体としては、半導体特性を有する無機物であればよく、用途に応じて適宜選択でき、例えば、金属単体、金属化合物(金属酸化物、金属硫化物、金属窒化物など)が挙げられる。
本発明は、半導体とイオン性ポリマーとを組み合わせる(複合化する)ことに特徴を有している。このような組み合わせにより、光電変換機能と蓄電機能とを兼ね備えた光電変換層(いわゆる電気二重層又はキャパシタとしての機能を備えた光電変換層)を形成できる。また、イオン性ポリマーがバインダー的に作用するためか、半導体(酸化チタンナノ粒子など)を焼結しなくても、光電変換特性に優れた光電変換層を形成できる。この理由は定かではないが、所定量のイオン性ポリマーと半導体[特に、ナノサイズの半導体粒子(半導体ナノ粒子)]との組み合わせにより、半導体の分散安定性を向上でき、半導体特性を有効に発揮できることや、イオン性のポリマーの種類によってはイオン性ポリマー自体が光電変換により発生した電荷を輸送する電解質(固体電解質)としても機能することなどが考えられる。
本発明の組成物は、さらに、色素を含んでいてもよい。色素を含有させることで、色素増感型の光電変換層又は色素増感型の光電変換素子(色素増感太陽電池など)を効率よく形成することができる。
(式中、IAはイオン性ポリマー中のイオン性基の数、ISはイオン性基1個あたりの占有面積、DAは色素(色素分子)の数、DSは色素1個あたりの占有面積、SSは、半導体の表面積を示す。)
上記式において、IAはイオン性基の総数であり、例えば、イオン性ポリマーのイオン交換容量(meq/g)にイオン性ポリマーの重量(g)及びアボガドロ数を掛けることで求めることができ、通常、IA×IS<SSである。IS、DSは、それぞれ、イオン性基1つの占有面積(m2)、色素1分子の占有面積(m2)であり、面積が最大となるよう投影した時の値を用いることができる。
本発明の積層体(電極)は、基板と、この基板上に積層された光電変換層(前記組成物で形成された光電変換層)とで構成される。
光電変換素子は、前記積層体(電極)を備えている。すなわち、光電変換素子(電池)は、前記電極と、この電極に対する対極とを備えている。代表的な光電変換素子の一例としては、太陽電池が挙げられる。特に、光電変換層が色素を含む場合、光電変換素子は、色素増感太陽電池を形成する。
酸化チタン粒子(石原産業(株)製、「ST−01」、平均一次粒子径7nm、比表面積300m2/g、アナターゼ型結晶)10重量部、アニオン性ポリマーを含む分散液(アルドリッチ社製「ナフィオン117」、20%の割合で含む水および1−プロパノール分散液、イオン交換容量0.95〜1.03meq/g、pH(25℃)=1、1分子当たりの占有面積約0.024nm2)25重量部(すなわち、アニオン性ポリマー5重量部)、色素(N719、東京化成工業(株)製、分子量1188.57、1分子当たりの占有面積約1nm2)0.1重量部およびメタノール65重量部を混合して酸化チタン分散液を調製した。
多孔質層を有する対極として、ITO付ガラス基板と、このITO層上にITO粉末(アルドリッチ(株)製、粒子径<50nm、比表面積27m2/g)を含むスラリー(ITO粉末1重量部に対してメチルセルロース(東京化成工業(株)製)0.1重量部を含む10重量%水分散液)を塗布することにより形成された多孔質層(厚み5μm)とで構成された基板にさらにスパッタリング法により白金を3.5nmの厚みで被覆した電極を用いたこと以外は、実施例1と同様にして色素増感太陽電池を作製し、評価した。
多孔質層を有する対極として、ITO付ガラス基板と、このITO層上に白金担持炭素粉末(石福金属興業(株)製、IFPC40−II)を含むスラリー(白金担持炭素粉末1重量部に対してメチルセルロース(東京化成工業(株)製)0.1重量部を含む10重量%水分散液)を塗布することにより形成された多孔質層(厚み5μm)とで構成された電極を用いたこと以外は、実施例1と同様にして色素増感太陽電池を作製し、評価した。
実施例1において、対極として、非多孔質構造の電極[ITO付ガラス基板(Luminescence Technology社製 サイズ25mm×25mm、ITO層の厚み0.14μm)と、このITO層上にスパッタリング法により形成された白金層(白金層厚み3.5nm、電極面積6.25cm2/g)とで構成された電極]を用いたこと以外は、実施例1と同様にして色素増感太陽電池を作製し、評価した。
Claims (22)
- 蓄電機能を備え、半導体およびイオン性ポリマーを含む光電変換層を形成するための組成物であって、半導体およびイオン性ポリマーを含み、かつイオン性ポリマーの割合が、半導体1重量部に対して0.05〜100重量部であり、イオン性ポリマーが強酸性イオン交換樹脂である光電変換層用組成物。
- 半導体が、金属酸化物である請求項1記載の組成物。
- 半導体が酸化チタンナノ粒子で構成されている請求項1又は2記載の組成物。
- イオン性ポリマーの25℃における水溶液又は水分散液のpHが7未満である請求項1〜3のいずれかに記載の組成物。
- イオン性ポリマーの割合が、半導体1重量部に対して0.05〜10重量部である請求項1〜4のいずれかに記載の組成物。
- 半導体が酸化チタンナノ粒子で構成され、イオン性ポリマーがスルホ基を有するフッ素含有樹脂を含み、水溶液又は水分散液のpHがpH3以下のイオン性ポリマーであり、かつイオン性ポリマーの割合が、半導体1重量部に対して0.05〜1重量部である請求項1〜5のいずれかに記載の組成物。
- さらに、色素を含む請求項1〜6のいずれかに記載の組成物。
- 色素が、ルテニウム錯体色素である請求項7記載の組成物。
- 導電性基板と、この基板上に積層され、半導体およびイオン性ポリマーを含む光電変換層とで構成された積層体であって、光電変換層が、請求項1〜8のいずれかに記載の組成物で形成されている積層体。
- 導電性基板が、導電体層が形成されたプラスチック基板である請求項9記載の積層体。
- 光電変換層の厚みが0.1〜100μmである請求項9又は10記載の積層体。
- 導電性基板に、請求項1〜8のいずれかに記載の組成物をコーティングし、半導体を焼結させることなく、請求項9〜11のいずれかに記載の積層体を製造する方法。
- 請求項9〜11のいずれかに記載の積層体を備えた光電変換素子。
- 電極としての色素を含む光電変換層で構成された積層体と、この電極に対向して配置される対極と、これらの電極間に介在し、封止処理された電解質層とで構成された光電変換素子であって、
光電変換層が半導体およびイオン性ポリマーを含み、かつイオン性ポリマーの割合が、半導体1重量部に対して0.05〜100重量部であり、イオン性ポリマーが強酸性イオン交換樹脂であり、
対極が多孔質層を有する光電変換素子。 - 半導体が、金属酸化物である請求項13又は14記載の光電変換素子。
- 半導体が酸化チタンナノ粒子で構成されている請求項13〜15のいずれかに記載の光電変換素子。
- イオン性ポリマーの割合が、半導体1重量部に対して0.05〜10重量部である請求項13〜16のいずれかに記載の光電変換素子。
- 半導体が酸化チタンナノ粒子で構成され、イオン性ポリマーがスルホ基を有するフッ素含有樹脂を含み、かつイオン性ポリマーの割合が、半導体1重量部に対して0.05〜1重量部である請求項13〜17のいずれかに記載の光電変換素子。
- 色素が、ルテニウム錯体色素である請求項13〜18のいずれかに記載の光電変換素子。
- 導電性基板が、導電体層が形成されたプラスチック基板である請求項13〜19のいずれかに記載の光電変換素子。
- 光電変換層の厚みが0.1〜100μmである請求項13〜20のいずれかに記載の光電変換素子。
- 半導体を含む光電変換層に、半導体1重量部に対して0.05〜100重量部の割合でイオン性ポリマーを含有させて、光電変換層に蓄電機能を付与する方法であって、イオン性ポリマーが、強酸性イオン交換樹脂を含む、方法。
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