JP2005538519A - N-type metal oxide semiconductor spectrally sensitized with cationic spectral sensitizer - Google Patents
N-type metal oxide semiconductor spectrally sensitized with cationic spectral sensitizer Download PDFInfo
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- metal oxide
- cationic
- oxide semiconductor
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- dihydroxy
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 62
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
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- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 2
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical compound OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 description 2
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- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000004642 Polyimide Substances 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
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- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- H10K85/652—Cyanine dyes
-
- 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
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
-
- 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
-
- 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
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Hybrid Cells (AREA)
Abstract
２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層、吸着されたカチオン系分光増感剤およびｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着を促進させうる共吸着剤を含んでなる層構成、並びに２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層を準備し、ナノ−多孔質ｎ−型金属酸化物半導体層上に共吸着剤を吸着させそしてナノ−多孔質ｎ−型金属酸化物半導体層上にカチオン系分光増感剤を吸着させる段階を含んでなる上記層構成の製造方法。Nano-porous n-type metal oxide semiconductor layer having a band gap greater than 2.7 eV, adsorbed cationic spectral sensitizer and adsorption of cationic spectral sensitizer on n-type metal oxide semiconductor And a layer of nano-porous n-type metal oxide semiconductor having a layer structure comprising a co-adsorbent capable of promoting oxygen and a band gap greater than 2.7 eV, and preparing a nano-porous n-type metal oxide A method for producing the layer structure comprising the steps of adsorbing a co-adsorbent on a physical semiconductor layer and adsorbing a cationic spectral sensitizer on a nano-porous n-type metal oxide semiconductor layer.
Description
本発明は、カチオン系分光増感剤で分光増感されたナノ−多孔質ｎ−型金属酸化物半導体に関する。 The present invention relates to a nano-porous n-type metal oxide semiconductor spectrally sensitized with a cationic spectral sensitizer.
光エネルギー転換用の電気化学的手段としての染料で増感された半導体の基礎は１９７０年代に提示され［非特許文献１参照］そして電極に対する染料で増感されたフィルムの応用に発展した［非特許文献２参照］。染料吸着に利用可能な大きな表面積を有する半導体微粒子の集合体の使用がかなり改良された光捕獲効率をもたらすことが提唱され、それにより染料で増感された半導体を湿潤タイプ太陽電池に適用することが実行可能になった。特に、動作電極（ｗｏｒｋ ｅｌｅｃｔｒｏｄｅ）の如き染料で増感された二酸化チタン半導体粒子のナノ−多孔質フィルムを有する湿潤タイプ太陽電池は転換効率および価格において非晶質珪素太陽電池より優れていることが期待された。これらの基礎技術は非特許文献３並びに特許文献１、特許文献２および特許文献３に開示されている。太陽電池の太陽転換効率をさらに増加させるためには、光電流光効率を増加させることが重要である。１つの方式は、半導体層上の染料増感剤の吸着を改良することである。 The basis of dye-sensitized semiconductors as electrochemical means for light energy conversion was presented in the 1970s [see Non-Patent Document 1] and developed into the application of dye-sensitized films for electrodes [non- See Patent Document 2]. It has been proposed that the use of aggregates of semiconductor particles with a large surface area available for dye adsorption results in significantly improved light capture efficiency, thereby applying dye-sensitized semiconductors to wet-type solar cells Is now executable. In particular, a wet type solar cell having a nanoporous film of titanium dioxide semiconductor particles sensitized with a dye such as a working electrode is superior to an amorphous silicon solar cell in conversion efficiency and cost. Expected. These basic technologies are disclosed in Non-Patent Document 3, Patent Document 1, Patent Document 2, and Patent Document 3. In order to further increase the solar conversion efficiency of the solar cell, it is important to increase the photocurrent photoefficiency. One way is to improve the adsorption of the dye sensitizer on the semiconductor layer.
特許文献４は、好ましくは式（Ｉ）：
Ｒ１−（Ａｒ）ｍ−Ｌ１−ＳＯ３ −Ｍ＋ （Ｉ）
［式中、Ｒ１は水素原子または置換されたもしくは未置換のアルキル基を表わし、Ａｒは置換されたもしくは未置換のアリーレン基を表わし、ｍは０または１を表わし、Ｌ１は単結合または２価結合基を表わし、そしてＭ＋はカチオンを表わし、但し、Ｒ１としての水素原子、ｍとしての０、および単結合Ｌ１の組み合わせは除外される］
により、または式（ＩＩ）：
Ｒ２−Ｐｈ−Ｏ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｌ２−ＳＯ３ −Ｍ＋ （ＩＩ）
［式中、Ｒ２は直鎖状もしくは分枝鎖状のアルキル基を表わし、Ｐｈはフェニレン基を表わし、ｎは０〜５０の整数を表わし、Ｌ２は単結合、置換されたもしくは未置換のアルキレン基または置換されたもしくは未置換のアルキレンオキシ基を表わし、そしてＭ＋はカチオンを表わす］
により表示される、アニオン系スルホン酸誘導体の存在下でそれにより吸着される染料を有する半導体粒子を開示している。
Patent document 4 preferably has formula (I):
R 1 - (Ar) m -L 1 -SO 3 - M + (I)
[Wherein, R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group, Ar represents a substituted or unsubstituted arylene group, m represents 0 or 1, and L 1 represents a single bond or Represents a divalent linking group, and M + represents a cation, except that a combination of a hydrogen atom as R 1 , 0 as m, and a single bond L 1 is excluded.
Or by formula (II):
R 2 -Ph-O- (CH 2 CH 2 O) n -L 2 -SO 3 - M + (II)
[In the formula, R 2 represents a linear or branched alkyl group, Ph represents a phenylene group, n represents an integer of 0 to 50, and L 2 represents a single bond, a substituted or an unsubstituted group. Represents an alkylene group or a substituted or unsubstituted alkyleneoxy group, and M + represents a cation.]
Discloses semiconductor particles having a dye adsorbed thereby in the presence of an anionic sulfonic acid derivative.
特許文献５は、吸着が一般式（Ｉ）：Ｒ−Ｌ−Ｚ［式中、Ｒは場合により置換されていてもよいアルキル、アルケニルまたはアリール基であり、Ｌは単結合または２価結合基であり、そしてＺは酸性基（これはプロトンを解離する）である］により表示される化合物Ａまたはそのアルカリ金属塩により補助される顔料または染料で増感された半導体を含有する光−電気転換物質を開示している。さらに、この光−電気転換物質は一般式（ＩＩ）： Patent Document 5 discloses that adsorption is represented by the general formula (I): RLZ [wherein R is an optionally substituted alkyl, alkenyl or aryl group, and L is a single bond or a divalent linking group. And Z is an acidic group (which dissociates a proton)] containing a semiconductor sensitized with a pigment or dye assisted by a compound A or an alkali metal salt thereof. The substance is disclosed. Further, this photo-electric conversion material has the general formula (II):
［式中、Ｘは水素原子またはＣ１−４アルキル基であり、Ｙは単結合または２価結合基であり、Ｅはエチレン系不飽和を有する化合物から誘導される繰り返し単位であり、Ｚは酸性基（これはプロトンを解離する）であり、そしてｊ、ｋは繰り返し単位の重量組成比である］により表示される高分子量重合体Ｂまたはそのアルカリ金属塩を含有することもできる。プロトンを解離する好ましい酸性基はカルボン酸およびスルホン基であるが、ホウ酸、フェノール酸およびヒドロキシ基も挙げられる。特許文献５に開示された式（Ｉ）に従う全ての具体的化合物はプロトンを解離するそれらの酸性基としてカルボキシ基を有しそして数種の化合物は１個より多いカルボキシ基を有する。 [Wherein, X is a hydrogen atom or a C 1-4 alkyl group, Y is a single bond or a divalent linking group, E is a repeating unit derived from a compound having ethylenic unsaturation, and Z is It can also contain a high molecular weight polymer B or an alkali metal salt thereof represented by an acidic group (which dissociates protons, and j and k are weight composition ratios of repeating units). Preferred acidic groups that dissociate protons are carboxylic acid and sulfone groups, but also boric acid, phenolic acid and hydroxy groups. All the specific compounds according to formula (I) disclosed in US Pat. No. 5,637,097 have carboxy groups as their acidic groups that dissociate protons, and some compounds have more than one carboxy group.
非特許文献４には、カテコールがナノ結晶性二酸化チタンフィルムをベースとした太陽電池に対するルテニウム−ポリピリジン感光剤の付着用の有効な固定基であることが報告されており、水性媒体中での表面チタン−カテコレート複合体の生成がこれまでに報告されており（非特許文献５および非特許文献６参照）、そしてカテコールと二酸化チタン粒子との間の界面電荷移送複合体の生成はこれまでに報告されていた（非特許文献７参照）。さらに、１９９３年 Ｒｅｄｍｏｎｄは、透明なナノ結晶性二酸化チタンフィルムの表面上でのピロカテコールの吸着が最初に適用された電位に対する蓄積に関する速度定数の依存性を帯域内（ｉｎｔｒａｂａｎｄ）表面状態のエネルギー促進に一致する方法で、ナノ結晶性二酸化チタンフィルムの表面における不完全に配位されたＴｉ原子と関連づけて伝導帯中で変えたことを立証した。 Non-Patent Document 4 reports that catechol is an effective anchoring group for the attachment of ruthenium-polypyridine photosensitizers to solar cells based on nanocrystalline titanium dioxide films, and surface in aqueous media. The formation of titanium-catecholate complexes has been reported so far (see Non-Patent Document 5 and Non-Patent Document 6), and the formation of interfacial charge transfer complexes between catechol and titanium dioxide particles has been reported so far. (See Non-Patent Document 7). In addition, 1993 Redmond demonstrated the dependence of the rate constant on the accumulation of potential on the surface to which the adsorption of pyrocatechol on the surface of a transparent nanocrystalline titanium dioxide film was first applied. In a manner consistent with that in the conduction band in relation to incompletely coordinated Ti atoms at the surface of the nanocrystalline titanium dioxide film.
ナノ−多孔質二酸化チタンをベースとした光電池装置の重要な特徴はそれらの分光増感であり、それがそれらの効率を大きく決める。有機金属複合染料（好ましくはルテニウムを包含する）は一般に二酸化チタン半導体中で光励起時に非常に速い電子注入を示す。純粋なアニオン系有機染料化合物（例えば、メロシアニン類）もＴｉＯ２半導体中で光励起時に非常に速い電子注入を示す。カチオン系染料増感剤を用いる二酸化チタン半導体の分光増感は、我々の認識では知られていない。 An important feature of photovoltaic devices based on nano-porous titanium dioxide is their spectral sensitization, which greatly determines their efficiency. Organometallic complex dyes (preferably including ruthenium) generally exhibit very fast electron injection upon photoexcitation in titanium dioxide semiconductors. Pure anionic organic dye compounds (eg, merocyanines) also exhibit very fast electron injection upon photoexcitation in TiO 2 semiconductors. Spectral sensitization of titanium dioxide semiconductors using cationic dye sensitizers is not known to our knowledge.
従って、ｎ−型金属酸化物半導体の促進された分光染料増感並びに染料を用いてナノ−多孔質ｎ−型金属酸化物半導体の促進された分光増感を達成する方法に関する要望がある。さらに、ｎ−型金属酸化物半導体の増感用にカチオン系染料増感剤を使用する手段に関する要望もある。
従って、本発明の一局面はｎ−型金属酸化物半導体層をカチオン系染料増感剤で効率的に分光増感された層構成を提供することである。 Accordingly, one aspect of the present invention is to provide a layer structure in which an n-type metal oxide semiconductor layer is efficiently spectrally sensitized with a cationic dye sensitizer.
本発明の別の局面はカチオン系染料増感剤を用いてｎ−型金属酸化物半導体の効率的な分光増感を達成する方法を提供することである。 Another aspect of the present invention is to provide a method for achieving efficient spectral sensitization of an n-type metal oxide semiconductor using a cationic dye sensitizer.
本発明の一局面は、また、高い短路電流を達成するカチオン系染料で増感された光電池装置を提供することである。 One aspect of the present invention is also to provide a photovoltaic device sensitized with a cationic dye that achieves a high short circuit current.
本発明の一局面は、また、高い転換効率を達成するカチオン系染料で増感された太陽電池を提供することである。 One aspect of the present invention is also to provide a solar cell sensitized with a cationic dye that achieves high conversion efficiency.
本発明の別の局面および利点は以下の記述から明らかになるであろう。 Other aspects and advantages of the invention will become apparent from the following description.
発明の要旨
カチオン系染料増感剤をある種のオルト−ジヒドロキシ−ベンゼン化合物、例えば、３，４，５−トリヒドロキシ−ベンゾニトリルおよび３，４−ジヒドロキシ−ベンゾニトリルと共にナノ−多孔質ｎ−型金属酸化物半導体上で共吸着させることにより、カチオン系染料の吸着がそれらの増感効率と一緒に促進されることが、驚くべきことに見出された。これは、最初にオルト−ジヒドロキシ−ベンゼン化合物を吸着させそして次にカチオン系増感剤を吸着させることによりまたはオルト−ジヒドロキシ−ベンゼン化合物およびカチオン系染料増感剤を同時に吸着させることにより達成しうる。
SUMMARY OF THE INVENTION Cationic dye sensitizers are combined with certain ortho-dihydroxy-benzene compounds such as 3,4,5-trihydroxy-benzonitrile and 3,4-dihydroxy-benzonitrile in nano-porous n-type It has been surprisingly found that co-adsorption on metal oxide semiconductors promotes the adsorption of cationic dyes along with their sensitization efficiency. This can be achieved by first adsorbing the ortho-dihydroxy-benzene compound and then adsorbing the cationic sensitizer or by simultaneously adsorbing the ortho-dihydroxy-benzene compound and the cationic dye sensitizer. .
本発明の局面は、２．７ｅＶより大きいバンドギャップ（ｂａｎｄ−ｇａｐ）を有するナノ−多孔質ｎ−型金属酸化物半導体の層、吸着されたカチオン系分光増感剤、およびｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着を促進させうる共吸着剤（ｃｏａｄｓｏｒｂｅｒ）を含んでなる層構成（ｌａｙｅｒ ｃｏｎｆｉｇｕｒａｔｉｏｎ）により実現される。 Aspects of the present invention include a layer of nano-porous n-type metal oxide semiconductor having a band-gap greater than 2.7 eV, an adsorbed cationic spectral sensitizer, and n-type metal oxidation It is realized by a layer configuration including a coadsorbent capable of promoting adsorption of a cationic spectral sensitizer on a physical semiconductor.
本発明の局面は、また、上記の層構成を含んでなる光電池装置（ｐｈｏｔｏｖｏｌｔａｉｃ ｄｅｖｉｃｅ）によって実現される。 Aspects of the present invention are also realized by a photovoltaic device comprising the above-described layer configuration.
本発明の局面は、また、上記の層構成を含んでなる太陽電池によって実現される。 Aspects of the present invention are also realized by a solar cell comprising the above layer configuration.
本発明の局面は、また、２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層を準備し、ナノ−多孔質ｎ−型金属酸化物半導体層上に共吸着剤を吸着させそしてｎ−型金属酸化物半導体層上にカチオン系分光増感剤を吸着させる段階を含んでなる、上記の層構成の製造方法によって実現される。 Aspects of the present invention also provide a layer of nano-porous n-type metal oxide semiconductor having a band gap greater than 2.7 eV and coadsorbed on the nano-porous n-type metal oxide semiconductor layer It is realized by the above-described method for producing a layer structure comprising the steps of adsorbing an agent and adsorbing a cationic spectral sensitizer on the n-type metal oxide semiconductor layer.
好ましい態様は従属請求項に開示されている。
発明の詳細な記述
非連続層という用語は、単一面が支持体の全領域を被覆せず且つ必ずしも支持体と直接接触する必要のない層をさす。
Preferred embodiments are disclosed in the dependent claims.
DETAILED DESCRIPTION OF THE INVENTION The term non-continuous layer refers to a layer where a single surface does not cover the entire area of the support and need not necessarily be in direct contact with the support.
ナノ−多孔質金属酸化物半導体
本発明の局面は、２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層、吸着されたカチオン系分光増感剤、およびｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着を促進させうる共吸着剤を含んでなる層構成により提供される。
Nano-Porous Metal Oxide Semiconductor Aspects of the invention include a layer of a nano-porous n-type metal oxide semiconductor having a band gap greater than 2.7 eV, an adsorbed cationic spectral sensitizer, and n- Provided by a layer structure comprising a co-adsorbent capable of promoting adsorption of a cationic spectral sensitizer on the metal oxide semiconductor.
本発明に従う層構成の第一の態様によると、ｎ−型金属酸化物半導体は酸化チタン類、酸化錫類、酸化二オブ類、酸化タンタル類および酸化亜鉛類よりなる群から選択される。 According to a first embodiment of the layer configuration according to the invention, the n-type metal oxide semiconductor is selected from the group consisting of titanium oxides, tin oxides, niobium oxides, tantalum oxides and zinc oxides.
本発明に従う層構成の第二の態様によると、ｎ−型金属酸化物半導体は二酸化チタンである。 According to a second embodiment of the layer configuration according to the invention, the n-type metal oxide semiconductor is titanium dioxide.
効率的な太陽電池に関すると、５〜８％までの動力転換効率を発生するのに充分な光吸収を有するためには、ナノ−多孔質ＴｉＯ２のコーティングは８〜１２μｍの間でなければならない。二酸化チタンコーティングが厚くなればなるほど、電荷（電子）を電荷収集電極に移送すべき通路が長くなりそして生じた動力転換効率損失で起きる再結合の確率が大きくなる。この問題を回避するためには、比較的大きい比表面積（ｓｐｅｃｉｆｉｃ ｓｕｒｆａｃｅ）を有しそしてその結果として同じ光吸収値でより薄い層を実現可能な比較的小さい二酸化チタンナノ−粒子を使用することができる。この方法で、電荷収集電極までの電子により横切られる道がより短いことのために再結合の確率が減少する事実によって、より高い効率を有する光電池が得られうる。 For efficient solar cells, the nano-porous TiO 2 coating must be between 8-12 μm in order to have sufficient light absorption to generate power conversion efficiencies up to 5-8%. . The thicker the titanium dioxide coating, the longer the path for charge (electrons) to be transferred to the charge collection electrode and the greater the probability of recombination that occurs with the resulting loss of power conversion efficiency. In order to avoid this problem, it is possible to use relatively small titanium dioxide nanoparticles that have a relatively large specific surface area and consequently can achieve a thinner layer with the same light absorption value. . In this way, a photovoltaic cell with higher efficiency can be obtained due to the fact that the probability of recombination is reduced due to the shorter path traversed by electrons to the charge collection electrode.
本発明に従う方法で使用される２．７ｅＶより大きいバンドギャップを有する金属酸化物半導体ナノ−粒子は、湿潤沈殿および非湿潤沈殿法により製造することができる。非湿潤沈殿法は、デグッサ（ＤＥＧＵＳＳＡ）により実施されている火炎熱分解の如き方法を包含する。湿潤化学法に従い製造される二酸化チタンナノ−粒子は、グラエッツエル（Ｇｒａｅｔｚｅｌ）−タイプ光電池の製造においてｎ−型半導体ナノ−粒子としてしばしば使用されている１３ｎｍの平均粒子寸法および１２０ｍ２／ｇの比表面積を有するナノ−寸法二酸化チタンであるＴｉ−ナノキシド（Ｔｉ−Ｎａｎｏｘｉｄｅ）ＴＭＴとしておよび９ｎｍの平均粒子寸法および１６５ｍ２／ｇの比表面積を有するナノ−寸法二酸化チタンであるＴｉ−ナノキシドＴＭＨＴとしてソラロニックス（ＳＯＬＡＲＯＮＩＸ）ＳＡから市販されているか、または１９９７年にバルベ（Ｂａｒｂｅ）他により引用することにより本発明の内容となるｔｈｅ Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｅｒａｍｉｃ Ｓｏｃｉｅｔｙ、８０（１２）巻、３１５７−３１７１頁に開示されているようなかなり直接的な沈殿技術を用いて容易に合成することができる。 Metal oxide semiconductor nanoparticles having a band gap greater than 2.7 eV used in the method according to the present invention can be produced by wet precipitation and non-wet precipitation methods. Non-wet precipitation methods include methods such as flame pyrolysis carried out by DEGUSSA. Titanium dioxide nanoparticles produced according to wet chemical methods have an average particle size of 13 nm and a specific surface area of 120 m 2 / g, which are often used as n-type semiconductor nanoparticles in the manufacture of Graetzel-type photovoltaic cells. Solaronics (as Ti-Nanoxide ™ T, which is a nano-sized titanium dioxide with Ti-Nanoxide ™ HT, and Ti-Nanoxide TM HT, which is a nano-sized titanium dioxide with an average particle size of 9 nm and a specific surface area of 165 m 2 / g The Journal of the American Ceramic Society, 80 (12), which is commercially available from SOLARONIX SA, or which is incorporated herein by reference by Barbe et al. In 1997. ), Pages 3157-3171 and can be readily synthesized using fairly direct precipitation techniques.
本発明に従う層構成の第三の態様によると、金属酸化物は非湿潤沈殿法により製造される二酸化チタンである。 According to a third embodiment of the layer configuration according to the invention, the metal oxide is titanium dioxide produced by a non-wet precipitation method.
カチオン系分光増感剤
本発明の局面は、２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層、吸着されたカチオン系分光増感剤およびｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着を促進させうる共吸着剤を含んでなる層構成により提供される。
Cationic Spectral Sensitizer Aspects of the present invention include a nano-porous n-type metal oxide semiconductor layer having a band gap greater than 2.7 eV, an adsorbed cationic spectral sensitizer and n-type metal oxidation. Provided by a layer structure comprising a co-adsorbent capable of promoting adsorption of a cationic spectral sensitizer on a physical semiconductor.
本発明に従う層構成の第四の態様によると、カチオン系分光増感剤はシアニン染料である。 According to a fourth embodiment of the layer configuration according to the invention, the cationic spectral sensitizer is a cyanine dye.
本発明における使用に適するカチオン系分光増感剤は下記のものを包含する： Cationic spectral sensitizers suitable for use in the present invention include:
共吸着剤
本発明の局面は、２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層、吸着されたカチオン系分光増感剤およびｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着を促進させうる共吸着剤を含んでなる層構成により提供される。
Coadsorbent Aspects of the present invention include a nano-porous n-type metal oxide semiconductor layer having a band gap greater than 2.7 eV, an adsorbed cationic spectral sensitizer and an n-type metal oxide semiconductor Provided by a layer structure comprising a co-adsorbent capable of promoting the adsorption of the cationic spectral sensitizer.
本発明に従う層構成の第五の態様によると、共吸着剤はオルト−ジヒドロキシ−ベンゼン化合物である。 According to a fifth embodiment of the layer configuration according to the invention, the coadsorbent is an ortho-dihydroxy-benzene compound.
本発明に従う層構成の第六の態様によると、共吸着剤は少なくとも０．６０であり且つ１．００より低いハンメット（Ｈａｍｍｅｔｔ）σ値を有する基を有するオルト−ジヒドロキシ−ベンゼン化合物である。 According to a sixth embodiment of the layer configuration according to the invention, the coadsorbent is an ortho-dihydroxy-benzene compound having a group having a Hammett σ value of at least 0.60 and lower than 1.00.
本発明に従う層構成の第七の態様によると、共吸着剤は少なくとも０．６０であり且つ１．００より低いハンメットσ値を有する基を有するオルト−ジヒドロキシ−ベンゼン化合物であり、ここでオルト−ジヒドロキシ−ベンゼン化合物はオルト−ジヒドロキシ−基および少なくとも０．６０であり且つ１．００より低いハンメットσ値を有する基を同一ベンゼン環上に有する。 According to a seventh embodiment of the layer configuration according to the invention, the coadsorbent is an ortho-dihydroxy-benzene compound having a group having a Hammett σ value of at least 0.60 and lower than 1.00, wherein ortho- The dihydroxy-benzene compound has an ortho-dihydroxy-group and a group on the same benzene ring that has a Hammett σ value of at least 0.60 and lower than 1.00.
本発明に従う層構成の第八の態様によると、共吸着剤はオルト−ジヒドロキシ−基と同じベンゼン環上に置換されたニトリル基を有するオルト−ジヒドロキシ−ベンゼン化合物である。 According to an eighth aspect of the layer configuration according to the invention, the coadsorbent is an ortho-dihydroxy-benzene compound having a nitrile group substituted on the same benzene ring as the ortho-dihydroxy-group.
本発明に従う層構成の第九の態様によると、共吸着剤は２，３−ジヒドロキシ−ベンゾニトリル、３，４−ジヒドロキシ−ベンゾニトリル、３，４，５−トリヒドロキシ−ベンゾニトリル、３，４−ジヒドロキシ−４’−シアノ−ベンゾフェノン、４−ニトロ−カテコール、（３，４−ジヒドロキシ−フェニル）メチル−スルホン、１，２−ジヒドロキシ−アントラキノン、３，４−ジヒドロキシ−アントラキノン−２−スルホン酸、４，５−ジヒドロキシ−ベンゼン−１，３−ジスルホン酸、６，７−ジヒドロキシ−ナフタレン−２−スルホン酸、３，４−ジヒドロキシ−安息香酸およびカテコールよりなる群から選択される。 According to a ninth embodiment of the layer configuration according to the invention, the coadsorbent is 2,3-dihydroxy-benzonitrile, 3,4-dihydroxy-benzonitrile, 3,4,5-trihydroxy-benzonitrile, 3,4 -Dihydroxy-4'-cyano-benzophenone, 4-nitro-catechol, (3,4-dihydroxy-phenyl) methyl-sulfone, 1,2-dihydroxy-anthraquinone, 3,4-dihydroxy-anthraquinone-2-sulfonic acid, Selected from the group consisting of 4,5-dihydroxy-benzene-1,3-disulfonic acid, 6,7-dihydroxy-naphthalene-2-sulfonic acid, 3,4-dihydroxy-benzoic acid and catechol.
本発明に従う層構成の第十の態様によると、共吸着剤は３，４−ジヒドロキシ−ベンゾニトリル、３，４，５−トリヒドロキシ−ベンゾニトリル、１，２−ジヒドロキシ−アントラキノン、（３，４−ジヒドロキシ−フェニル）メチル−スルホン、４，５−ジヒドロキシ−ベンゼン−１，３−ジスルホン酸およびカテコールよりなる群から選択される。 According to a tenth aspect of the layer configuration according to the invention, the coadsorbent is 3,4-dihydroxy-benzonitrile, 3,4,5-trihydroxy-benzonitrile, 1,2-dihydroxy-anthraquinone, (3,4 -Dihydroxy-phenyl) methyl-sulfone, selected from the group consisting of 4,5-dihydroxy-benzene-1,3-disulfonic acid and catechol.
本発明における使用に適する共吸着剤は下記のものを包含する： Suitable coadsorbents for use in the present invention include:
ＣＡ−１０ ２，３−ジヒドロキシ−ベンゾニトリル
ＣＡ−１１ ３，４，５−トリヒドロキシ−ベンゾニトリル
ＣＡ−１２ ３，４−ジヒドロキシ−４’−シアノ−ベンゾフェノン
ＣＡ−１３ ４−ニトロ−カテコール
ＣＡ−１４ （３，４−ジヒドロキシ−フェニル）メチルスルホン
ＣＡ−１５ ３，４−ジヒドロキシ−安息香酸
ＣＡ−１６ カテコール
層構成の製造方法
本発明の局面は、２．７ｅＶより大きいバンドギャップを有するナノ−多孔質ｎ−型金属酸化物半導体の層を準備し、ナノ−多孔質ｎ−型金属酸化物半導体層上に共吸着剤を吸着しそしてナノ−多孔質ｎ−型金属酸化物半導体層上にカチオン系分光増感剤を吸着する段階を含んでなる本発明に従う層構成の製造方法により実現される。
CA-10 2,3-dihydroxy-benzonitrile CA-11 3,4,5-trihydroxy-benzonitrile CA-12 3,4-dihydroxy-4'-cyano-benzophenone CA-13 4-nitro-catechol CA- 14 (3,4-Dihydroxy-phenyl) methylsulfone CA-15 3,4-dihydroxy-benzoic acid CA-16 catechol
Method of manufacturing a layer configuration An aspect of the present invention provides a layer of a nano-porous n-type metal oxide semiconductor having a band gap greater than 2.7 eV, on the nano-porous n-type metal oxide semiconductor layer And a method for producing a layer structure according to the present invention comprising the steps of adsorbing a co-adsorbent and adsorbing a cationic spectral sensitizer on a nano-porous n-type metal oxide semiconductor layer.
本発明に従う層構成の製造方法の第一の態様によると、ナノ−多孔質ｎ−型金属酸化物半導体上のカチオン系分光増感剤の吸着はナノ−多孔質ｎ−型金属酸化物半導体層上の共吸着剤の吸着と同時に行われる。同じ溶液から適用される場合には、ナノ−多孔質ｎ−型金属酸化物半導体層上の吸着前に共吸着剤とカチオン系分光増感剤との間で複合体生成が起きること、すなわち二成分が個別でなく複合体が吸着されること、がありうる。 According to the first aspect of the method for producing a layer structure according to the present invention, the adsorption of the cationic spectral sensitizer on the nano-porous n-type metal oxide semiconductor is the nano-porous n-type metal oxide semiconductor layer. It is performed simultaneously with the adsorption of the upper co-adsorbent. When applied from the same solution, complex formation occurs between the co-adsorbent and the cationic spectral sensitizer before adsorption on the nano-porous n-type metal oxide semiconductor layer, i.e. two It is possible that the components are not individual and the complex is adsorbed.
本発明に従う層構成の製造方法の第二の態様によると、ナノ−多孔質ｎ−型金属酸化物半導体層上のカチオン系分光増感剤の吸着はナノ−多孔質ｎ−型金属酸化物半導体層上の共吸着剤の吸着後に行われる。 According to the second aspect of the method for producing a layer structure according to the present invention, the adsorption of the cationic spectral sensitizer on the nano-porous n-type metal oxide semiconductor layer is performed by nano-porous n-type metal oxide semiconductor. This is done after adsorption of the coadsorbent on the layer.
支持体
本発明に従う使用のための支持体は、場合により処理されてもよく、下塗り層または露光差動可能部品に対する接着を助けるための他の接着促進手段が備えられていてもよい、重合体フィルム、珪素、セラミックス、酸化物、ガラス、重合体フィルム強化ガラス、ガラス／プラスチックラミネート、金属／プラスチックラミネート、紙および積層紙を包含する。適する重合体フィルムは、場合によりコロナ放電もしくはグロー放電により処理されてもよくまたは下塗り層が備えられていてもよい、ポリ（エチレンテレフタレート）、ポリ（エチレンナフタレート）、ポリスチレン、ポリエーテルスルホン、ポリカーボネート、ポリアクリレート、ポリアミド、ポリイミド類、三酢酸セルロース、ポリオレフィン類およびポリ（塩化ビニル）である。
Supports Supports for use in accordance with the present invention may be optionally processed polymers, which may be provided with a subbing layer or other adhesion promoting means to aid adhesion to the exposure-differentiable component. Includes film, silicon, ceramics, oxide, glass, polymer film tempered glass, glass / plastic laminate, metal / plastic laminate, paper and laminated paper. Suitable polymer films are optionally treated by corona discharge or glow discharge or may be provided with an undercoat layer, poly (ethylene terephthalate), poly (ethylene naphthalate), polystyrene, polyethersulfone, polycarbonate , Polyacrylates, polyamides, polyimides, cellulose triacetate, polyolefins and poly (vinyl chloride).
光電池装置
本発明の局面は、本発明に従うかまたは本発明に従う方法に従い製造される層構成を含んでなる光電池装置によっても実現される。
Photovoltaic Device Aspects of the present invention are also realized by a photovoltaic device comprising a layer configuration according to the present invention or manufactured according to a method according to the present invention.
本発明に従う分光増感されたナノ−多孔質ｎ−型金属酸化物半導体を組み入れた光電池装置は、２つのタイプ：光を電力に転換させて実質的な化学変化を残さずに電流担持電子が陽極に移送されそして外部回路および正孔（ｈｏｌｅ）が陰極に移送されそれらが外部回路からの電子により酸化される再生タイプ、並びに１つが半導体電極の表面で正孔と反応しそして１つが逆電極に入る電子と反応し、例えば、水が半導体光陽極で酸化されそして陰極で水素に還元されるような２つのレドックスシステムがある光合成タイプ、でありうる。グラエッツエル電池により例示される光電池の再生タイプの場合には、正孔移送媒体はレドックス反応を助ける液体電解質、レドックス反応を助けるゲル電解質、低分子量物質、例えば２，２’，７，７’−テトラキス（Ｎ，Ｎ−ジ−ｐ−メトキシフェニル−アミン）９，９’−スピロビフルオレン（ＯＭｅＴＡＤ）もしくはトリフェニルアミン化合物または重合体、例えばＰＰＶ−誘導体、ポリ（Ｎ−ビニルカルバゾール）などでありうる有機正孔移送物質、または無機半導体、例えばＣｕＩ、ＣｕＳＣＮなどでありうる。電荷移送方法は、例えば、液体電解質もしくはゲル電解質の場合のようにイオン性であることができ、または、例えば、有機もしくは無機正孔移送物質の場合のように電子性であることもできる。 Photovoltaic devices incorporating spectrally sensitized nano-porous n-type metal oxide semiconductors according to the present invention have two types: current-carrying electrons that convert light into electrical power and leave no substantial chemical changes. Regenerative type that is transferred to the anode and external circuit and holes are transferred to the cathode and they are oxidized by electrons from the external circuit, and one reacts with holes on the surface of the semiconductor electrode and one is the reverse electrode It can be a photosynthetic type that has two redox systems that react with electrons entering it, for example water is oxidized at the semiconductor photoanode and reduced to hydrogen at the cathode. In the case of the photovoltaic cell regeneration type exemplified by the Graetzel cell, the hole transport medium is a liquid electrolyte that aids the redox reaction, a gel electrolyte that aids the redox reaction, a low molecular weight material such as 2,2 ′, 7,7′-tetrakis. (N, N-di-p-methoxyphenyl-amine) 9,9'-spirobifluorene (OMeTAD) or a triphenylamine compound or polymer, such as PPV-derivative, poly (N-vinylcarbazole), etc. It can be an organic hole transport material or an inorganic semiconductor such as CuI, CuSCN, and the like. The charge transfer method can be ionic, for example, as is the case with liquid or gel electrolytes, or it can be electronic, as is the case with organic or inorganic hole transport materials, for example.
そのような再生光電池装置は最終用途に従い種々の内部構造を有することができる。考えられる形態は大よそ２つのタイプ：光を両面から受ける構造および光を一面から受けるもの、に分類される。前者の例は、透明な伝導層、例えばＩＴＯ−層もしくはＰＥＤＯＴ／ＰＳＳ−含有層および透明な逆電極電気伝導性層、例えば間に挟まれた感光層および電荷移送層を有するＩＴＯ−層もしくはＰＥＤＯＴ／ＰＳＳ−含有層から製造される構造である。そのような装置は好ましくは、内部物質の劣化または揮発を防止するために重合体、接着剤などで封着されたそれらの側面を有する。電気伝導性基質および逆電極とそれぞれの導線により連結された外部回路は既知である。 Such a regenerative photovoltaic cell device can have various internal structures according to the end use. The possible forms are roughly classified into two types: structures that receive light from both sides and those that receive light from one side. Examples of the former are transparent conductive layers, such as ITO-layers or PEDOT / PSS-containing layers and transparent reverse electrode electrically conductive layers, such as ITO-layers or PEDOTs having a sandwiched photosensitive layer and charge transport layer This is a structure manufactured from a / PSS-containing layer. Such devices preferably have their sides sealed with polymers, adhesives, etc. to prevent degradation or volatilization of internal materials. External circuits connected to the electrically conductive substrate and the counter electrode by respective conductors are known.
或いは、本発明に従う分光増感されたナノ−多孔質ｎ−型金属酸化物半導体を例えば１９９１年にグラエッツエル他によりＮａｔｕｒｅ、３５３巻、７３７−７４０頁に、１９９８年にＵ．バッハ（Ｂａｃｈ）他により［Ｎａｔｕｒｅ、３９５巻、５８３−５８５頁（１９９８）参照］、そして２００２年にＷ．Ｕ．ヒューン（Ｈｕｙｎｈ）他により［Ｓｃｉｅｎｃｅ、２９５巻、２４２５−２４２７頁（２００２）参照］記載されたようなハイブリッド光電池組成物中に組み込むことができる。全てのこれらの場合には、成分（光吸収剤、電子移送剤または正孔移送剤）の少なくとも１種は無機性（例えば、電子移送剤としてのナノ−ＴｉＯ２、光吸収剤および電子移送剤としてのＣｄＳｅ）でありそして成分の少なくとも１種は有機性（例えば、正孔移送剤としてのトリフェニルアミンまたは正孔移送剤としてのポリ（３−ヘキシルチオフェン））である。 Alternatively, a spectrally sensitized nano-porous n-type metal oxide semiconductor according to the present invention can be obtained, for example, by Graetzel et al. In Nature, 353, 737-740, and in 1998 by U.S. Pat. Bach et al. [Nature, 395, 583-585 (1998)] and in 2002 by W. Bach et al. U. It can be incorporated into a hybrid photovoltaic cell composition as described by Huynh et al. [See Science 295, 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transfer agent or hole transfer agent) is inorganic (eg nano-TiO 2 as electron transfer agent, light absorber and electron transfer agent) And at least one of the components is organic (eg, triphenylamine as a hole transfer agent or poly (3-hexylthiophene) as a hole transfer agent).
工業用途
本発明に従う層構成は光電池装置および太陽電池の中で使用することができる。
Industrial application The layer structure according to the invention can be used in photovoltaic devices and solar cells.
本発明を以下で参考用および本発明の発光装置により説明する。これらの実施例に示された百分率および比は断らない限り重量による。
比較実験で使用されるアニオン系分光増感剤：
The present invention will be described below for reference and the light emitting device of the present invention. The percentages and ratios indicated in these examples are by weight unless otherwise indicated.
Anionic spectral sensitizers used in comparative experiments:
実施例１
ナノ−多孔質ＴｉＯ２層上の染料の吸着
ガラス基質（フラヒグラス（ＦＬＡＣＨＧＬＡＳ）ＡＧ）をエタノール中で５分間にわたり超音波洗浄しそして次に乾燥した。ナノ−ＴｉＯ２分散液（ソラロニックスＳＡ）からのＴｉ−ナノキシドＨＴ）の層をガラス基質にドクターブレードコーターを用いて適用した。この二酸化チタンでコーティングされたガラスを４５０℃に３０分間にわたり加熱した。これが、高度に透明なナノ−多孔質ＴｉＯ２層を生じた。レーザー輪郭法により（デクトラク（ＤＥＫＴＲＡＫ）ＴＭ輪郭計）、ダイヤモンド先端プローブ（ペリソメーター（Ｐｅｒｔｈｏｍｅｔｅｒ））で機械的に、そして干渉法により確かめられた１．５μｍ、３μｍまたは５μｍの乾燥層厚さが、使用するドクターブレードナイフによって、得られた。
Example 1
Nano - adsorption glass substrate of the dye on the porous TiO 2 layer (Furahigurasu (FLACHGLAS) AG) was ultrasonically cleaned in ethanol for 5 minutes and then dried. A layer of nano-TiO 2 dispersion (Ti-nanoxide HT from Solaronics SA) was applied to the glass substrate using a doctor blade coater. The titanium dioxide coated glass was heated to 450 ° C. for 30 minutes. This is highly transparent nano - resulted porous TiO 2 layer. Using dry contour thickness of 1.5 μm, 3 μm or 5 μm confirmed by laser contouring (DEKTRAK TM contour meter), mechanically with a diamond tip probe (Persometer) and by interferometry Obtained by a doctor blade knife.
この焼結段階後に、二酸化チタンでコーティングされたガラス板を１５０℃のホットプレート上に１０分間にわたり置くことによりそれを冷却しそして次に場合によりオルト−ジヒドロキシ−ベンゼン化合物を含有してもよい染料−含有溶液の中に直ちに浸漬し、そこで１５〜１７時間にわたり保った。染料溶液中への浸漬後に、二酸化チタン層をアセトニトリルですすいで吸着されなかった染料を除去しそして次に５０℃で数時間にわたり乾燥した。 After this sintering step, the titanium dioxide-coated glass plate is cooled by placing it on a hot plate at 150 ° C. for 10 minutes and then optionally containing an ortho-dihydroxy-benzene compound Immersed immediately in the containing solution, where it was kept for 15-17 hours. After immersion in the dye solution, the titanium dioxide layer was rinsed with acetonitrile to remove unadsorbed dye and then dried at 50 ° C. for several hours.
ヒューレット−パッカード（Ｈｅｗｌｅｔｔ−Ｐａｃｋａｒｄ）ダイオード−アレイ分光計ＨＰ８４５２Ａを用いて、２００〜８００ｎｍの間の吸収スペクトルが得られた。結果をカチオン系染料の吸着およびアセトニトリル中の染料の基準スペクトルに関して表１に示す。 Absorption spectra between 200-800 nm were obtained using a Hewlett-Packard diode-array spectrometer HP8452A. The results are shown in Table 1 with respect to the adsorption of the cationic dye and the reference spectrum of the dye in acetonitrile.
カチオン系染料であるＤＣ−０１〜ＤＣ−１７のアセトニトリル中２×１０−４Ｍ溶液の中への焼結したての二酸化チタン層の浸漬で、アセトニトリルを用いる洗浄後に検出可能な染料吸着を生じなかった。 Immersion of a freshly sintered titanium dioxide layer in a 2 × 10 −4 M solution of the cationic dyes DC-01 to DC-17 in acetonitrile results in detectable dye adsorption after washing with acetonitrile. There wasn't.
本発明に従うオルト−ジヒドロキシ−ベンゼン化合物と一緒のカチオン系染料の共吸着に関する吸収結果を表２に示す。 The absorption results for co-adsorption of cationic dyes with ortho-dihydroxy-benzene compounds according to the present invention are shown in Table 2.
アセトニトリル中の２×１０−４Ｍカチオン系染料（ＤＣ−０１〜ＤＣ−１７）および２×１０−４Ｍ共吸着剤化合物ＣＡ−０１〜ＣＡ−０９、ＣＡ−１１、Ｃ−１４〜Ｃ−１６の溶液中への焼結したての二酸化チタン層の浸漬はそれぞれ検出可能な染料吸着を生じた。共吸着剤ＣＡ−０１、ＣＡ−０３、ＣＡ−０４、ＣＡ−１１、ＣＡ−１４およびＣＡ−１５と一緒にカチオン系染料を用いると、特に強い吸着が観察された。 2 × 10 −4 M cationic dye (DC-01 to DC-17) and 2 × 10 −4 M coadsorbent compounds CA-01 to CA-09, CA-11, C-14 to C— in acetonitrile Each immersion of the freshly sintered titanium dioxide layer in 16 solutions resulted in detectable dye adsorption. Particularly strong adsorption was observed when cationic dyes were used with the co-adsorbents CA-01, CA-03, CA-04, CA-11, CA-14 and CA-15.
共吸着剤ＣＡ−０１を二酸化チタン層上にＣＡ−０１の２×１０−４Ｍアセトニトリル溶液から上記のように１５〜１７時間にわたる浸漬により吸着し、ＤＣ−０１、ＤＣ−０２およびＤＣ−１１の２×１０−４Ｍアセトニトリル溶液中への浸漬前に５０℃で乾燥し、アセトニトリルで洗浄しそして最後に５０℃で数分間にわたり乾燥する場合には染料吸着における差が観察されなかったことにも注目すべきである。 The co-adsorbent CA-01 was adsorbed on a titanium dioxide layer from a 2 × 10 −4 M acetonitrile solution of CA-01 by immersion for 15-17 hours as described above, and DC-01, DC-02 and DC-11. No difference in dye adsorption was observed when dried at 50 ° C. prior to immersion in 2 × 10 −4 M acetonitrile solution, washed with acetonitrile and finally dried at 50 ° C. for several minutes. Also should be noted.
参考用に、５種のアニオン系染料をＴｉＯ２−表面（１．５μｍ厚さ）：ＤＡ−０１、ＤＡ−０２、ＤＡ−０３、ＤＣ−０４およびＤＣ−０５、の上にカチオン系染料と同じ工程を用いて吸着した。これらの吸着実験の結果を表４に示す。 For reference, five anionic dyes were added to the TiO 2 -surface (1.5 μm thickness): DA-01, DA-02, DA-03, DC-04 and DC-05 with cationic dyes. Adsorption was performed using the same process. The results of these adsorption experiments are shown in Table 4.
表４に示された結果から、本発明に従う共吸着剤と組み合わされたカチオン系分光増感剤を用いるとナノ−多孔質二酸化チタン上でアニオン系分光増感剤で得られうるものに匹敵する光吸収が得られうることを結論づけうる。 From the results shown in Table 4, it is comparable to what can be obtained with anionic spectral sensitizers on nano-porous titanium dioxide when using cationic spectral sensitizers in combination with a co-adsorbent according to the present invention. It can be concluded that light absorption can be obtained.
実施例２
ＴｉＯ２上での吸着された分光増感剤の吸収に対する共吸着剤対カチオン系分光増感剤のモル比の影響
ＤＣ−１６、ＤＣ−１７およびＣＡ−０１の濃度を表５に示されたように変動させたこと以外は、本発明の実験４１〜５０は本発明の実験１６および１７に関して記載された通りにして行われた。
Example 2
Effect of molar ratio of co-adsorbent to cationic spectral sensitizer on absorption of adsorbed spectral sensitizer on TiO 2 The concentrations of DC-16, DC-17 and CA-01 are shown in Table 5. Except as varied, experiments 41-50 of the present invention were performed as described for experiments 16 and 17 of the present invention.
表５に示された結果は、ＣＡ−０１の存在下におけるカチオン系染料の吸着はＤＣ−１６およびＤＣ−１７の両者に関してはＣＡ−０１濃度につれて強く増加したこと、すなわち５×１０−５Ｍの染料濃度および１．５×１０−４ＭのＣＡ−０１濃度においては１×１０−４Ｍの染料濃度および１×１０−４ＭのＣＡ−０１濃度におけるものより高い二酸化チタン上の吸収が観察されたこと、を示す。
実施例３
光電池装置中の評価
光電池１〜８を以下の通りにして製造した：
前面電極の製造
約１５オーム／平方の表面導電率を有する導電性ＳｎＯ２：Ｆ（ピルキングトン（Ｐｉｌｋｉｎｇｔｏｎ）ＴＥＣ１５／３）でコーティングされたガラス板（２×７ｃｍ２）をイソプロパノール中で５分間にわたり超音波洗浄しそして次に乾燥した。
The results shown in Table 5 indicate that the adsorption of cationic dyes in the presence of CA-01 increased strongly with CA-01 concentration for both DC-16 and DC-17, ie 5 × 10 −5 M. At a dye concentration of 1.5 × 10 −4 M and a CA-01 concentration of 1.5 × 10 −4 M, the absorption on titanium dioxide is higher than that at 1 × 10 −4 M dye concentration and 1 × 10 −4 M CA-01 concentration. It is observed.
Example 3
Evaluation photovoltaic cells 1-8 in the photovoltaic device were manufactured as follows:
Manufacture of Front Electrode A glass plate (2 × 7 cm 2 ) coated with conductive SnO 2 : F (Pilkington TEC 15/3) having a surface conductivity of about 15 ohms / square for 5 minutes in isopropanol. Sonicated and then dried.
電極を境界でテープ除去しそして中央（０．７×４．５ｃｍ２）で上記のＴｉＯ２のソラロニックス分散液を用いてドクターブレード−コーティングして、電池の匹敵する光吸収を確保するために、焼結後に１．８または５μｍの層厚さを与えた。共吸着剤の存在下における焼結工程およびカチオン系分光増感剤吸着工程は実施例１に記載された通りであった。それにより前面電極が製造され、それを直ちに電池の組み立てで使用した。
電池組み立て品
（電解質の還元に触媒作用を与えるための白金と共に蒸発させたＳｎＯ２：Ｆガラス（プルキングトンＴＥＣ１５／３）よりなる）背面電極を前面電極と一緒に、間にある２つのスルリン（Ｓｕｒｌｙｎ）（Ｒ）（デュポン（ＤｕＰｏｎｔ））（２×７ｃｍ２、中央で１×６ｃｍ２が除去されていた）を用いて、封着した。これは１００℃のすぐ上の温度においてホットプレート上で行われた。封着が完了したらすぐに、電池を２５℃に冷却しそして電解質を逆電極内の正孔を通して加えた。使用された電解質は、０．５ＭのＬｉＩ、０．０５ＭのＩ２および０．４Ｍのｔ−ブチルピリジンのアセトニトリル中溶液でありそして電池組み立て中に電池内に注入された。正孔を次にスルリン（Ｒ）およびガラスの薄い片で封着した。導電性テープを電池の２つの長辺に付着して測定中に電気を集めた。
装置特性
電池に、金属ハライド１ＡＭ光源を有するステウエルナゲル・ソラー・コンスタント（Ｓｔｅｕｅｒｎａｇｅｌ Ｓｏｌａｒ Ｃｏｎｓｔａｎｔ）５７５太陽刺激剤を照射した。刺激剤は約１の日光当量に調節された。発生した電気をキースレー（Ｋｅｉｔｈｌｅｙ）電位計（タイプ２４００ＳＭＵ）を用いて記録した。発生した電気の量から計算された光電池の開路電圧（Ｖｏｃ）、短路電流密度（Ｉｓｃ）および充填因子（Ｆｉｌｌ Ｆａｃｔｏｒ）（ＦＦ）を表６に示す。
Electrodes were tape removed in the boundary and the doctor blade at the center (0.7 × 4.5cm 2) using Soraronikkusu the above dispersion of TiO 2 - coated, in order to ensure a comparable light absorption of the battery, A layer thickness of 1.8 or 5 μm was given after sintering. The sintering step and cationic spectral sensitizer adsorption step in the presence of the co-adsorbent were as described in Example 1. This produced a front electrode that was immediately used in the assembly of the battery.
Battery assembly (consisting of SnO 2 : F glass (purkington TEC15 / 3) evaporated with platinum to catalyze the reduction of the electrolyte) back electrode together with the front electrode and two sulrins in between Sealed with (Surlyn) (R) (DuPont) (2 × 7 cm 2 , 1 × 6 cm 2 removed in the center). This was done on a hot plate at a temperature just above 100 ° C. As soon as sealing was complete, the battery was cooled to 25 ° C. and electrolyte was added through the holes in the reverse electrode. The electrolyte used was, 0.5M of LiI, an acetonitrile solution of t- butylpyridine I 2 and 0.4M of 0.05M and was poured into the battery during battery assembly. The holes were then sealed with sullin (R) and a thin piece of glass. A conductive tape was attached to the two long sides of the battery to collect electricity during the measurement.
Device Characteristics The cells were irradiated with a Steuernagel Solar Constant 575 solar stimulant with a metal halide 1AM light source. The stimulant was adjusted to about 1 daylight equivalent. The electricity generated was recorded using a Keithley electrometer (type 2400 SMU). The open circuit voltage (V oc ), short circuit current density (I sc ) and fill factor (FF) of the photovoltaic cell calculated from the amount of electricity generated are shown in Table 6.
表６の結果は、特に染料が可視スペクトルの赤色領域で吸収する場合には、アニオン系染料増感で得られうるものに匹敵する短路電流［Ｉｓｃ］が共吸着剤の存在下においてカチオン系染料増感で実現されうることを示している。
実施例４
カチオン系分光増感剤の混合物を用いる分光増感
カチオン系分光増感剤をその吸着を促進させうる共吸着剤と共に用いてナノ−多孔質二酸化チタンの分光増感に基づく光電池装置のスペクトル応答を広げるために、カチオン系染料の混合物を共吸着剤ＣＡ−０１と一緒に使用した。
The results in Table 6 show that, especially when the dye absorbs in the red region of the visible spectrum, a short circuit current [I sc ] comparable to that obtained with anionic dye sensitization can be obtained in the presence of a coadsorbent in the presence of a cationic system. It shows that it can be realized by dye sensitization.
Example 4
Spectral Sensitization Using Mixtures of Cationic Spectral Sensitizers Spectral Response of Photovoltaic Devices Based on Spectral Sensitization of Nano-Porous Titanium Dioxide Using Cationic Spectral Sensitizers with Coadsorbents That Can Promote Its Adsorption For spreading, a mixture of cationic dyes was used with the coadsorbent CA-01.
光電池を実施例３に記載されている通りにして、カチオン系分光増感剤を別個に用いてそしてカチオン系分光増感剤の混合物を用いて、製造した。これらの実験に関しては、湿潤沈殿法により製造されたナノ−二酸化チタンであるソラロニックスからのＴｉ−ナノキシドＨＴの代わりに非湿潤沈殿法により、すなわち火炎熱分解により、製造されたナノ−二酸化チタンであるデグッサ（Ｄｅｇｕｓｓａ）Ｐ２５ ＴｉＯ２ナノ−コロイドを使用し、５ｇのデグッサＰ２５が１５ｍＬの水に加えられ、１ｍＬのトリトン（Ｔｒｉｔｏｎ）Ｘ−１００が引き続き加えられた。生じた二酸化チタンコロイド分散液を氷中で冷却しそして５分間にわたり超音波処理した。この二酸化チタンコロイド分散液を次にＴｉ−ナノキシドＨＴ分散液に関して以上で記載された通りにしてさらに使用した。 Photocells were prepared as described in Example 3, using a cationic spectral sensitizer separately and using a mixture of cationic spectral sensitizers. For these experiments, nano-titanium dioxide produced by non-wet precipitation, i.e. by flame pyrolysis, instead of Ti-nanoxide HT from Solaronix, which is nano-titanium dioxide produced by wet precipitation. Using Degussa P25 TiO 2 nano-colloid, 5 g of Degussa P25 was added to 15 mL of water followed by 1 mL of Triton X-100. The resulting titanium dioxide colloidal dispersion was cooled in ice and sonicated for 5 minutes. This titanium dioxide colloidal dispersion was then further used as described above for the Ti-nanoxide HT dispersion.
染料吸着は３種のカチオン系分光増感剤に関しては１×１０−４Ｍのカチオン系分光増感剤濃度および１×１０−４ＭのＣＡ−１濃度でそして０．５×１０−４ＭのＣＡ−０１、０．３×１０−４ＭのＤＣ−０１、０．７×１０−４ＭのＤＣ−１５および０．５×１０−４ＭのＤＣ−０２の混合物を用いて行われた。同量の３種の染料が使用される場合には、カチオン系分光増感剤の吸着強度における差によって不均一なスペクトルが生じた。従って染料の相対量を調節して可視スペクトル全体にわたり均一な吸収を実現させた。 Dye adsorption is at 1 × 10 −4 M cationic spectral sensitizer concentration and 1 × 10 −4 M CA-1 concentration and 0.5 × 10 −4 M for the three cationic spectral sensitizers. CA-01, 0.3 × 10 −4 M DC-01, 0.7 × 10 −4 M DC-15 and 0.5 × 10 −4 M DC-02. It was. When the same amount of the three dyes was used, a non-uniform spectrum was generated due to the difference in the adsorption intensity of the cationic spectral sensitizer. Therefore, the relative amount of dye was adjusted to achieve uniform absorption throughout the visible spectrum.
それにより製造された光電池にキセノンアーク放出灯（Ｘｅｎｏｎ Ａｒｃ Ｄｉｓｃｈａｒｇｅ ｌａｍｐ）を用いて１００ｍＷ／ｃｍ２の出力で照射した。発生した電流をキースレイ電位計（タイプ２４２０）を用いて記録した。発生した電流の量から計算された光電池の開路電圧（Ｖｏｃ）、短路電流密度（Ｉｓｃ）および充填因子（ＦＦ）を表７に示す。 The photovoltaic cell produced thereby was irradiated with a power of 100 mW / cm 2 using a Xenon Arc Discharge lamp. The current generated was recorded using a Keithley electrometer (type 2420). Table 7 shows the open circuit voltage (V oc ), short circuit current density (I sc ), and packing factor (FF) of the photovoltaic cell calculated from the amount of current generated.
表７からわかるように、染料混合物に関する吸収値は別個に吸着された染料に関する値の半分であるが、より広いスペクトル応答によって匹敵するかもしくはそれより高い短路電流値が得られた。 As can be seen from Table 7, the absorption value for the dye mixture is half that for the separately adsorbed dye, but a comparable short-circuit current value was obtained with a broader spectral response.
本発明は、ここにそれとなくまたは明瞭に開示されたいずれかの特徴もしくは特徴の組み合わせまたはそれがここで特許請求されている発明に関連するかどうかに無関係のいずれかの一般的事項を包括しうる。以上の記述に鑑みて、種々の改変を発明の範囲内で行い得ることは当業者に明らかであろう。 The invention may encompass any general matter whether or not related to any feature or combination of features explicitly or explicitly disclosed herein or whether it relates to the claimed invention. . In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.
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| WO2011049402A2 (en) * | 2009-10-22 | 2011-04-28 | 한양대학교 산학협력단 | Photo electrode for dye-sensitized solar cell having high-molecular coadsorbent |
| JP2014514708A (en) * | 2011-04-04 | 2014-06-19 | ポステック アカデミー‐インダストリー ファウンデーション | Dye-sensitized solar cell including ionic layer and method for producing the same |
| JP2014514707A (en) * | 2011-04-04 | 2014-06-19 | ポステック アカデミー‐インダストリー ファウンデーション | Metal oxide semiconductor electrode formed with porous thin film, dye-sensitized solar cell using the same, and method for producing the same |
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| JP5520258B2 (en) * | 2011-06-29 | 2014-06-11 | 東京エレクトロン株式会社 | Dye adsorption apparatus and dye adsorption method |
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| DE69819712T2 (en) * | 1997-05-07 | 2004-09-23 | Ecole polytechnique fédérale de Lausanne (EPFL) | PHOTO-SENSITIVE METAL COMPLEX AND PHOTOVOLTAIC CELL |
| ATE230517T1 (en) * | 1997-10-23 | 2003-01-15 | Fuji Photo Film Co Ltd | PHOTOELECTRIC CONVERSION ARRANGEMENT AND PHOTOELECTROCHEMICAL CELL |
| JP4443713B2 (en) * | 2000-03-24 | 2010-03-31 | 富士フイルム株式会社 | Semiconductor fine particles, photoelectric conversion element and photovoltaic cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011049402A2 (en) * | 2009-10-22 | 2011-04-28 | 한양대학교 산학협력단 | Photo electrode for dye-sensitized solar cell having high-molecular coadsorbent |
| WO2011049402A3 (en) * | 2009-10-22 | 2011-10-06 | 한양대학교 산학협력단 | Photo electrode for dye-sensitized solar cell having high-molecular coadsorbent |
| KR101137701B1 (en) | 2009-10-22 | 2012-04-25 | 한양대학교 산학협력단 | Photoelectrode with polymer co-adsorbent for dye-sensitized solar cell |
| JP2014514708A (en) * | 2011-04-04 | 2014-06-19 | ポステック アカデミー‐インダストリー ファウンデーション | Dye-sensitized solar cell including ionic layer and method for producing the same |
| JP2014514707A (en) * | 2011-04-04 | 2014-06-19 | ポステック アカデミー‐インダストリー ファウンデーション | Metal oxide semiconductor electrode formed with porous thin film, dye-sensitized solar cell using the same, and method for producing the same |
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