JP5292766B2 - 半導体膜形成用塗布液、半導体膜、色素増感型太陽電池 - Google Patents
半導体膜形成用塗布液、半導体膜、色素増感型太陽電池 Download PDFInfo
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- JP5292766B2 JP5292766B2 JP2007281493A JP2007281493A JP5292766B2 JP 5292766 B2 JP5292766 B2 JP 5292766B2 JP 2007281493 A JP2007281493 A JP 2007281493A JP 2007281493 A JP2007281493 A JP 2007281493A JP 5292766 B2 JP5292766 B2 JP 5292766B2
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 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
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- ZRXVCYGHAUGABY-UHFFFAOYSA-O tris(4-bromophenyl)azanium Chemical compound C1=CC(Br)=CC=C1[NH+](C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 ZRXVCYGHAUGABY-UHFFFAOYSA-O 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
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- 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
- Y02E10/542—Dye sensitized solar cells
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
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Description
即ち、
1.金属酸化物粒子と溶媒、及び下記一般式〔I〕で表される化合物を含有することを特徴とする半導体膜形成用塗布液。
<ポリオキシアルキレン鎖を有する基>
−(R″O) m −R′
で表される基であり、ここにおいてR″は、炭素原子数2〜4のアルキレン基である。また、R′は水素原子或いは炭素原子数1〜30のアルキル基、アルケニル基、また炭素原子数10以下のアリール基、また、炭素原子数22以下のアシル基を表す。また、mは1〜16の整数を表す。
<ポリエステル鎖>
炭素原子数1〜8のアルカンジオールと炭素原子数1〜10のアルカンジカルボン酸またはベンゼンジカルボン酸(フタル酸)とのエステルからなる構造単位を1個以上10個以下有してなる一価のポリエステル鎖
<2価のポリエステル鎖>
炭素原子数1〜8のアルカンジオールと炭素原子数1〜10のアルカンジカルボン酸またはベンゼンジカルボン酸(フタル酸)とのエステルからなる構造単位を1個以上10個以下有してなる二価のポリエステル鎖
<ポリオキシアルキレン鎖を有する2価の基>
−(R″O) m −
で表されるポリ(オキシアルキレン)鎖(ここで、R″は炭素原子数2〜4のアルキレン基であり、mは1〜16の整数を表す。)であるか、または、該ポリ(オキシアルキレン)鎖が、アルキレン基(炭素原子数1〜22)、アリーレン基、また、イミノ基、カルボニル基を有し、これらの基を介して、R 1 および尿素構造単位の窒素原子と、またR 6 および尿素構造単位の窒素原子と、結合するものであること
<置換基群>
アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、ハロゲン原子、シアノ基、ヒドロキシル基、カルボキシル基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アルキルおよびアリールアミノ基、アニリノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルおよびアリールスルホニルアミノ基、スルファモイル基、スルホ基、アルキルおよびアリールスルフィニル基、アルキルおよびアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、イミド基、ウレイド基、ボロン酸基、ホスファト基、スルファト基
2.前記一般式〔I〕で表される化合物の含有量が1質量%以上10質量%以下であることを特徴とする前記1に記載の半導体膜形成用塗布液。
−(R″O) m −R′
で表される基であり、ここにおいてR″は、炭素原子数2〜4のアルキレン基、好ましくはエチレン、プロピレン等の基である。また、R′は水素原子或いは炭素原子数1〜30のアルキル基、アルケニル基、また炭素原子数10以下のアリール基、また、炭素原子数22以下のアシル基、例えば、アセチル基、プロピオニル基等を、また、ベンゾイル基等を表す。また、mは1〜16、好ましくは3〜10の整数を表す。
−(R″O) m −
で表される2価の基が挙げられ、R″については前記同様、炭素原子数2〜4のアルキレン基、好ましくはエチレン、プロピレン等の基が挙げられる。また、ここで、mは、1〜16、好ましくは3〜10の整数を表す。
本発明に係る金属酸化物半導体電極について説明する。
次に、本発明の金属酸化物半導体電極の作製方法を説明する。
本発明で用いられる導電性基材1としては、当該導電性基材側を受光面とする場合には、導電性基材は実質的に透明であることが好ましい。実質的に透明であるとは光の透過率が10%以上であることを意味し、50%以上であることが好ましく、80%以上であることが特に好ましい。
本発明の色素増感型太陽電池においては、前述した導電層と金属酸化物半導体電極との間に、短絡防止層を設けることができる。これにより、電解質と金属酸化物半導体の短絡電流を低減することができる。特に、電解質として固体のp型半導体を用いる場合は、この層を有することが好ましい。
本発明に係る色素について説明する。
本発明に係る一般式(2)で表される化合物(色素ともいう)について説明する。
本発明において、金属酸化物半導体層に、一般式(1)で表される化合物(色素)または一般式(2)で表される化合物(色素)を吸着させる方法としては、特に限定されず、公知の方法が用いることができる。
本発明に係る電荷移動層について説明する。
本発明に係る対向電極は、上記の導電性基材と同様に、それ自体が導電性を有する基材の単層構造、またはその表面に対極導電層を有する基材を利用することができる。後者の場合、対極導電層に用いる導電性材料、基材、更にその製造方法としては、前述した導電性基材1の場合と同様で、公知の種々の材料及び方法を適用することができる。
〈半導体膜形成用塗布液CC−01の作製〉
結晶性酸化チタン粉末(日本アエロジル製P25)60質量部を水1200質量部中に攪拌しながら添加した後、硝酸15質量部を加えた反応系を80℃に加熱した後、8時間攪拌を続けた。放冷した後、エバポレータにより水分を留去して、粉末状にしてから乳鉢でよく粉砕した。得られた酸化チタン微粒子の平均粒径は30nmであった。
CC−01の作製において、t−ブタノール80質量部を25質量%のポリエチレングリコールが溶解されたt−ブタノール溶液80質量部と変更した以外はCC−01と同様に作製し、半導体膜形成用塗布液CC−02を作製した。
CC−02の作製において、ポリエチレングリコールを一般式〔I〕で表される化合物(化合物例No.1)に変更し、更にt−ブタノールへの濃度を10質量%に変更した以外はCC−02と同様に作製し、半導体膜形成用塗布液CC−03を作製した。
CC−03の作製において、ポリエチレングリコールを化合物例No.2の化合物に変更した以外はCC−03と同様に作製し、半導体膜形成用塗布液CC−04を作製した。
CC−03の作製において、ポリエチレングリコールを化合物例No.10の化合物に変更した以外はCC−03と同様に作製し、半導体膜形成用塗布液CC−05を作製した。
CC−03の作製において、10質量%の化合物No.1の化合物が溶解されたt−ブタノール溶液80質量部を、5質量%の化合物No.1の化合物が溶解されたt−ブタノール溶液80質量部に変更した以外はCC−03と同様に作製し、半導体膜形成用塗布液CC−06を作製した。
〈色素増感型太陽電池SC−01の作製〉
透明導電性プラスチック基材として、ITOを導電膜(厚み150nm)として担持したフィルム厚み200μm、表面抵抗15Ω/□のポリエチレンテレフタレート(PET)を用いた。このITO/PET基材のITO面に、ドクターブレード法によって上記の半導体膜形成用塗布液CC−01を30μmの液厚みで塗布し、室温で乾燥後、更に120℃で60分間乾燥、焼成を行って、多孔性の金属酸化物粒子層を形成した。
色素増感型太陽電池SC−01の作製において、半導体形成用塗布液、及び焼成温度を表1に記載の通りに変更した以外はSC−01の作製と同様に行い、色素増感型太陽電池SC−02〜08を作製した。尚、焼成温度が500℃の場合は、基材としてガラス基板を使用しており、焼成時間は10分間とした。
上記で得られた太陽電池SC−01〜SC−08の各々にソーラーシミュレーター(JASCO(日本分光)製、低エネルギー分光感度測定装置CEP−25)により100mW/m2の強度の光を照射した時の短絡電流密度Jsc(mA/cm2)、開放電圧値Voc(V)、形状因子(F.F.)、を求め、これらから光電変換効率(η(%))を求めた。これを表1に示した。示した値は、同じ構成及び作製方法の太陽電池3つずつ作製して評価した測定結果の平均値とした。
ここで、Pは入射光強度[mW/cm-2]、Vocは開放電圧[V]、Jscは短絡電流密度[mA・cm-2]、F.F.は形状因子を示す。
2 金属酸化物
3 色素
4 電荷移動層
5 対向電極
Claims (4)
- 金属酸化物粒子と溶媒、及び下記一般式〔I〕で表される化合物を含有することを特徴とする半導体膜形成用塗布液。
(式中、R1、R6はアルキル基、アルケニル基、アリール基を表すか、下記ポリオキシアルキレン鎖を有する基、また下記ポリエステル鎖を表す。R3、R4はそれぞれ水素原子またはアルキル基を表す。R2、R5はアルキレン基、アルケニレン基、アリーレン基を表すか、下記2価のポリエステル鎖、また、下記ポリオキシアルキレン鎖を有する2価の基を表し、またnは10以上14以下の整数を表す。R1、R6、またR2、R5で表される基は、当該一般式〔I〕で表される化合物が、前記溶媒に溶解する範囲で選ばれる。R 1 、R 6 、R 2 及びR 5 は、下記置換基群から選ばれる置換基で置換されていてもよい。)
<ポリオキシアルキレン鎖を有する基>
−(R″O) m −R′
で表される基であり、ここにおいてR″は、炭素原子数2〜4のアルキレン基である。また、R′は水素原子或いは炭素原子数1〜30のアルキル基、アルケニル基、また炭素原子数10以下のアリール基、また、炭素原子数22以下のアシル基を表す。また、mは1〜16の整数を表す。
<ポリエステル鎖>
炭素原子数1〜8のアルカンジオールと炭素原子数1〜10のアルカンジカルボン酸またはベンゼンジカルボン酸(フタル酸)とのエステルからなる構造単位を1個以上10個以下有してなる一価のポリエステル鎖
<2価のポリエステル鎖>
炭素原子数1〜8のアルカンジオールと炭素原子数1〜10のアルカンジカルボン酸またはベンゼンジカルボン酸(フタル酸)とのエステルからなる構造単位を1個以上10個以下有してなる二価のポリエステル鎖
<ポリオキシアルキレン鎖を有する2価の基>
−(R″O) m −
で表されるポリ(オキシアルキレン)鎖(ここで、R″は炭素原子数2〜4のアルキレン基であり、mは1〜16の整数を表す。)であるか、または、該ポリ(オキシアルキレン)鎖が、アルキレン基(炭素原子数1〜22)、アリーレン基、また、イミノ基、カルボニル基を有し、これらの基を介して、R 1 および尿素構造単位の窒素原子と、またR 6 および尿素構造単位の窒素原子と、結合するものであること
<置換基群>
アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、ハロゲン原子、シアノ基、ヒドロキシル基、カルボキシル基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アルキルおよびアリールアミノ基、アニリノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルおよびアリールスルホニルアミノ基、スルファモイル基、スルホ基、アルキルおよびアリールスルフィニル基、アルキルおよびアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、イミド基、ウレイド基、ボロン酸基、ホスファト基、スルファト基 - 前記一般式〔I〕で表される化合物の含有量が1質量%以上10質量%以下であることを特徴とする請求項1に記載の半導体膜形成用塗布液。
- 請求項1又は2に記載の半導体膜形成用塗布液を導電性基材上に塗布して製造されたことを特徴とする半導体膜。
- 導電性基材上に、色素が表面に吸着された半導体膜から構成される金属酸化物半導体電極と、電荷移動層と、対向電極とを順次有する色素増感型太陽電池であって、該半導体膜として請求項3に記載の半導体膜を用いることを特徴とする色素増感型太陽電池。
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JP2015018664A (ja) * | 2013-07-10 | 2015-01-29 | 大日本印刷株式会社 | 色素増感型太陽電池の製造方法および多孔質層形成用塗工液 |
JP2015115488A (ja) * | 2013-12-12 | 2015-06-22 | 日立化成株式会社 | パッシベーション層形成用組成物、パッシベーション層付半導体基板、パッシベーション層付半導体基板の製造方法、太陽電池素子、太陽電池素子の製造方法及び太陽電池 |
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