JP5906522B2 - Phthalocyanine dye, dye-sensitized solar cell and photoelectric conversion element using phthalocyanine dye - Google Patents
Phthalocyanine dye, dye-sensitized solar cell and photoelectric conversion element using phthalocyanine dye Download PDFInfo
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- JP5906522B2 JP5906522B2 JP2012114541A JP2012114541A JP5906522B2 JP 5906522 B2 JP5906522 B2 JP 5906522B2 JP 2012114541 A JP2012114541 A JP 2012114541A JP 2012114541 A JP2012114541 A JP 2012114541A JP 5906522 B2 JP5906522 B2 JP 5906522B2
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- dye
- ring
- phthalocyanine
- photoelectric conversion
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group 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 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
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- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
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- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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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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- 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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- Hybrid Cells (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Photovoltaic Devices (AREA)
Description
本発明は、光電変換素子用に適するフタロシアニン色素、これらを単独または他の色素と併用する光電変換素子及び色素増感太陽電池に関する。 The present invention relates to a phthalocyanine dye suitable for a photoelectric conversion element, a photoelectric conversion element using these alone or in combination with another dye, and a dye-sensitized solar cell.
光電変換素子は、光センサー、太陽電池等の光発電装置に使用されている。色素によって増感された半導体微粒子を用いる光電変換素子が特許文献1等で知られている。 Photoelectric conversion elements are used in photovoltaic devices such as optical sensors and solar cells. A photoelectric conversion element using semiconductor fine particles sensitized with a dye is known from Patent Document 1 and the like.
太陽電池としては、単結晶、多結晶あるいはアモルファスのシリコン半導体を用いた太陽電池が、電卓などの電気製品や住宅用などに広く用いられている。しかしながら、このようなシリコン半導体を用いた太陽電池の製造には、プラズマCVDや高温結晶成長プロセスなどの高精度プロセスが用いられるため、多大のエネルギーを必要とすると共に、真空を必要とする高価な装置が必要なために製造コストが高くなっている。 As a solar cell, a solar cell using a monocrystalline, polycrystalline, or amorphous silicon semiconductor is widely used for electrical products such as a calculator or for a house. However, since high-precision processes such as plasma CVD and high-temperature crystal growth processes are used for manufacturing solar cells using such silicon semiconductors, they require a lot of energy and are expensive, requiring a vacuum. Manufacturing costs are high due to the need for equipment.
そこで、低コストで製造可能な太陽電池として、例えば、酸化チタンのような酸化物半導体にルテニウム金属錯体のような光増感色素を吸着させた材料を用いた色素増感太陽電池が提案されている。色素増感太陽電池は具体的には、例えばインジウム添加酸化スズのような透明導電層を設けた透明ガラス板あるいは透明樹脂板のような透明絶縁材料の透明導電層側に、例えばルテニウム錯体からなる色素を表面に吸着した酸化チタンなどを半導体層として形成した負極と、正極となる白金などの金属層あるいは導電層を設けた透明ガラス板あるいは透明樹脂板のような透明絶縁材料との間に電解質の液を封入したものがある。色素増感太陽電池に光が照射されると、負極では光を吸収した色素の電子が励起し、励起した電子が半導体層に移動し、更に透明電極へと導かれ、正極では導電層からくる電子により電解質を還元する。還元された電解質は色素に電子を伝えることで酸化され、このサイクルで色素増感太陽電池が発電すると考えられている。 Therefore, as a solar cell that can be manufactured at a low cost, for example, a dye-sensitized solar cell using a material in which a photosensitizing dye such as a ruthenium metal complex is adsorbed on an oxide semiconductor such as titanium oxide has been proposed. Yes. Specifically, the dye-sensitized solar cell is made of, for example, a ruthenium complex on the transparent conductive layer side of a transparent insulating material such as a transparent glass plate or a transparent resin plate provided with a transparent conductive layer such as indium-added tin oxide. An electrolyte between a negative electrode formed with titanium oxide or the like having a dye adsorbed on its surface as a semiconductor layer and a transparent insulating material such as a transparent glass plate or a transparent resin plate provided with a metal layer or conductive layer such as platinum as a positive electrode There is something that encloses the liquid. When the dye-sensitized solar cell is irradiated with light, the electrons of the dye that absorbed the light are excited in the negative electrode, the excited electrons move to the semiconductor layer, and are further guided to the transparent electrode, and from the conductive layer in the positive electrode The electrolyte is reduced by electrons. The reduced electrolyte is oxidized by transferring electrons to the dye, and it is believed that the dye-sensitized solar cell generates electricity during this cycle.
現在、色素増感太陽電池はシリコン太陽電池に比して照射光エネルギーに対する発電エネルギー効率が低く、その効率を上げることが実効的な色素増感太陽電池を製造する上での重要な課題となっている。色素増感太陽電池の効率は、それを構成する各要素の特性や、更にそれら要素の組み合わせによっても影響を受けると考えられており、さまざまな試みがなされている。中でも、光増感作用を持つ色素について、より高効率な増感色素の開発に注力されている。現在知られている高効率色素としてN719等の可視光領域で高性能を示すRu色素があるが、これらの色素は可視光領域の光電変換効率は高いが、近赤外領域の光電変換効率が低く、近赤外領域近傍に吸収帯を有する色素の開発が望まれている。 Currently, dye-sensitized solar cells have lower power generation energy efficiency with respect to irradiation light energy than silicon solar cells, and increasing the efficiency is an important issue in producing effective dye-sensitized solar cells. ing. The efficiency of the dye-sensitized solar cell is considered to be influenced by the characteristics of each element constituting the dye-sensitized solar cell and the combination of these elements, and various attempts have been made. In particular, with regard to dyes having a photosensitizing action, efforts are being made to develop more efficient sensitizing dyes. Currently known high-efficiency dyes such as N719 are Ru dyes that exhibit high performance in the visible light region, but these dyes have a high photoelectric conversion efficiency in the visible light region, but have a high photoelectric conversion efficiency in the near-infrared region. Development of a pigment having a low absorption band near the near infrared region is desired.
この近赤外領域近傍に吸収帯を有する光電変換素子用の有機色素については、特許文献1乃至3等でいくつかの化合物が知られている。また、フタロシアニン色素についても、これらの文献で知られている。 Regarding organic dyes for photoelectric conversion elements having an absorption band in the vicinity of the near infrared region, several compounds are known in Patent Documents 1 to 3 and the like. Also, phthalocyanine dyes are known in these documents.
特許文献1乃至3及び非特許文献1では光電変換素子及び色素増感太陽電池を開示し、それに使用されるフタロシアニン色素を例示している。これらの文献において使用されるフタロシアニン色素は、一般式で表わされており、膨大な数の化合物が含まれる。また、非特許文献2ではフタロシアニン化合物を開示し、長波長領域に吸収を有する化合物を開示している。
Patent Documents 1 to 3 and Non-Patent Document 1 disclose a photoelectric conversion element and a dye-sensitized solar cell, and illustrate phthalocyanine dyes used therein. The phthalocyanine dyes used in these documents are represented by a general formula and include a huge number of compounds. Non-Patent
しかしながら、上記先行文献に開示されるフタロシアニン化合物は、いずれも光電変換素子または色素増感太陽電池用の色素として、十分な変換効率を発現しておらず、更なる改良が求められている。 However, none of the phthalocyanine compounds disclosed in the above-mentioned prior art documents exhibit sufficient conversion efficiency as dyes for photoelectric conversion elements or dye-sensitized solar cells, and further improvements are required.
光電変換素子及び色素増感太陽電池に適した色素を提供するための一つの手法として、色素のHOMO、LUMOを光電変換するために最適な状態になるよう分子設計をする必要がある。しかし、フタロシアニン化合物について、先行文献において多くの構造が開示されながら、いずれの構造も十分な変換効率を発現しないことは、この分子設計の困難さを示している。 As one method for providing a dye suitable for a photoelectric conversion element and a dye-sensitized solar cell, it is necessary to design a molecule so that the HOMO and LUMO of the dye are in an optimum state for photoelectric conversion. However, although many structures of phthalocyanine compounds are disclosed in the prior literature, the fact that none of the structures exhibits sufficient conversion efficiency indicates the difficulty in molecular design.
本発明は、上記の課題に鑑みてなされたものであり、近赤外領域における吸収波長範囲が広く光電変換効率の良好な新規な色素を提供し、これを用いた光電変換素子及び色素増感太陽電池を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a novel dye having a wide absorption wavelength range in the near infrared region and good photoelectric conversion efficiency, and a photoelectric conversion element and dye sensitization using the same. An object is to provide a solar cell.
本発明は下記式(1)で表わされるフタロシアニン色素である。
式(1)において、A1はベンゼン環、ピラジン環、キノキサリン環、ピラジノ[2,3−b]キノキサリン環または後記する式(3)もしくは式(4)で示される原子団を表す。A2はベンゼン環、ナフタレン環またはアントラセン環を表す。Zは酸素または硫黄原子を表す。Mは2個の水素原子、またはフタロシアニンと共有結合もしくは配位結合し得る原子または原子団を表わす。Yはフェニル基またはアルキル基である。nは1または2の数字を表す。mは0乃至2の整数を表す。Xはカルボキシル基または下記式(2)で表される基である。但し、A 1 がベンゼン環、ピラジン環、キノキサリン環、またはピラジノ[2,3−b]キノキサリン環である場合は、Xは式(2)で表される基であり、A 1 が式(3)もしくは式(4)で示される原子団である場合は、Xはカルボキシル基であり、これは含窒素五員環と縮合環を形成しないベンゼン環又はナフタレン環に結合する。
In the formula (1), A 1 represents a benzene ring, a pyrazine ring, a quinoxaline ring, a pyrazino [2,3-b] quinoxaline ring, or an atomic group represented by the following formula (3) or formula (4) . A 2 represents a benzene ring, a naphthalene ring or an anthracene ring. Z represents an oxygen or sulfur atom. M represents two hydrogen atoms, or an atom or atomic group that can be covalently or coordinately bonded to phthalocyanine. Y is a phenyl group or an alkyl group. n represents the
また、本発明は、色素を用いる光電変換素子において、色素が上記フタロシアニン色素であることを特徴とする光電変換素子である。また、本発明は、色素として上記フタロシアニン色素の他に、上記フタロシアニン色素と吸収領域の異なる色素を用いることを特徴とする光電変換素子である。 The present invention is also a photoelectric conversion element using a dye, wherein the dye is the phthalocyanine dye. The present invention also provides a photoelectric conversion element using a dye having an absorption region different from that of the phthalocyanine dye, in addition to the phthalocyanine dye.
また、本発明は、上記光電変換素子を用いて構成したことを特徴とする色素増感太陽電池である。 Moreover, this invention is the dye-sensitized solar cell comprised using the said photoelectric conversion element.
本発明のフタロシアニン色素は、芳香族環の一部に2価のカルコゲン元素を付与し、他の芳香族環にアンカー基としてカルボン酸基またはシアノカルボン酸基を付与した非対称構造であり、従来のフタロシアニン色素よりも吸収波長が長波長領域に達する。そのため、本発明のフタロシアニン色素を使用した光電変換素子及びこれを用いて構成した色素増感太陽電池は、特に近赤外光領域における光電変換効率が高い。 The phthalocyanine dye of the present invention has an asymmetric structure in which a divalent chalcogen element is imparted to a part of an aromatic ring and a carboxylic acid group or a cyanocarboxylic acid group is imparted to another aromatic ring as an anchor group. The absorption wavelength reaches a longer wavelength region than that of the phthalocyanine dye. Therefore, the photoelectric conversion element using the phthalocyanine dye of the present invention and the dye-sensitized solar cell configured using the same have high photoelectric conversion efficiency particularly in the near infrared light region.
本発明の光電変換素子又は色素増感太陽電池は、上記式(1)で表されるフタロシアニン色素を増感色素として含む。なお、色素増感太陽電池は光電変換素子を利用するものであるため、両者の説明の多くが共通するので、共通する説明は色素増感太陽電池で代表して説明する。 The photoelectric conversion element or the dye-sensitized solar cell of the present invention contains a phthalocyanine dye represented by the above formula (1) as a sensitizing dye. In addition, since a dye-sensitized solar cell utilizes a photoelectric conversion element, since both description is common, a common description is demonstrated on behalf of a dye-sensitized solar cell.
式(1)において、A1はベンゼン環またはピラジン環を含む原子団を表すが、好ましくはベンゼン環、ナフタレン環、ピラジン環、ビフェニル環、キノキサリン環、ピラジノ[2,3―b]キノキサリン環または下式(3)もしくは(4)で表される原子団であり、特に好ましくはベンゼン環である。また、A2は独立に、ベンゼン環、ナフタレン環またはアントラセン環を表すが、好ましくはベンゼン環、ナフタレン環であり、特に好ましくはベンゼン環である。これらの環は、隣接する含窒素5員環と縮合して存在する。 In the formula (1), A 1 represents an atomic group containing a benzene ring or a pyrazine ring, and preferably a benzene ring, naphthalene ring, pyrazine ring, biphenyl ring, quinoxaline ring, pyrazino [2,3-b] quinoxaline ring or An atomic group represented by the following formula (3) or (4), particularly preferably a benzene ring. A 2 independently represents a benzene ring, a naphthalene ring or an anthracene ring, preferably a benzene ring or a naphthalene ring, and particularly preferably a benzene ring. These rings are condensed with an adjacent nitrogen-containing 5-membered ring.
また、Zは独立に、酸素、硫黄またはセレン原子を表すが、より好ましくは酸素または硫黄である。nは1または2の数字を表すが、より好ましくは2である。また、Yは独立に、フェニル基またはアルキル基であるが、好ましくはフェニル基である。アルキル基の場合は、炭素原子を4個以上含むことが好ましく、4〜12個含むことがより好ましい。 Z independently represents an oxygen, sulfur or selenium atom, more preferably oxygen or sulfur. n represents a number of 1 or 2, but is more preferably 2. Y is independently a phenyl group or an alkyl group, preferably a phenyl group. In the case of an alkyl group, it preferably contains 4 or more carbon atoms, and more preferably contains 4 to 12 carbon atoms.
mは0乃至2の整数を表す。ただし、A1がピラジンの場合はm=0であることが好ましい。また、Mは2個の水素原子、またはフタロシアニンと共有結合もしくは配位結合し得る原子または原子団を表わす。具体的には、水素原子、Zn、Mg、VO(バナジウムの酸化物)、P、Ni、Ru等を表し、このほかに上記共有結合もしくは配位結合をするものであればよいが、好ましくはZn、Ni、Mn、Ruであり、特に好ましくはZnまたはNiである。また、Xはカルボキシル基または上記式(2)で表される基である。 m represents an integer of 0 to 2. However, when A 1 is pyrazine, m = 0 is preferable. M represents two hydrogen atoms, or an atom or atomic group that can be covalently or coordinated with phthalocyanine. Specifically, it represents a hydrogen atom, Zn, Mg, VO (vanadium oxide), P, Ni, Ru, or the like, and any other material that has the above-described covalent bond or coordinate bond, preferably Zn, Ni, Mn and Ru, particularly preferably Zn or Ni. X is a carboxyl group or a group represented by the above formula (2).
正確な理由は定かではないが、A1、A2及びYで表される置換基は、立体的に嵩高い構造のものが好ましく、フタロシアニン環同士の会合や凝集を防いで、色素間のエネルギー移動に起因する電荷分離損失を低減すると考えられる。また、置換基を長くすると、色素の吸収波長を長波長化させ、カルボン酸上の電子密度が大きくなり、色素間のエネルギー移動に起因する電荷分離損失を低減すると考えられる。また、色素の吸収波長を長波長化させ、カルボン酸上の電子密度が大きくなり、電子注入効率が向上すると考えられる。 Although the exact reason is not clear, the substituents represented by A 1 , A 2 and Y preferably have a sterically bulky structure, which prevents association and aggregation of phthalocyanine rings, and energy between dyes. It is thought that the charge separation loss due to the movement is reduced. Further, it is considered that increasing the substituent lengthens the absorption wavelength of the dye, increases the electron density on the carboxylic acid, and reduces charge separation loss due to energy transfer between the dyes. Further, it is considered that the absorption wavelength of the dye is lengthened, the electron density on the carboxylic acid is increased, and the electron injection efficiency is improved.
以下に式(1)で表されるフタロシアニン色素の好ましい具体例を示す。なお、具体例において、Phはフェニル基を表す。また、M1はZnまたはNiである。 Preferred specific examples of the phthalocyanine dye represented by the formula (1) are shown below. In specific examples, Ph represents a phenyl group. M 1 is Zn or Ni.
式(1)で表されるフタロシアニン色素の合成例を、式(12)で表されるフタロシアニン色素化合物(D−1)を具体例として、以下に示す。 A synthesis example of the phthalocyanine dye represented by the formula (1) is shown below by taking the phthalocyanine dye compound (D-1) represented by the formula (12) as a specific example.
4−carboxy−phthalonitrile(以下、フタロニトリル誘導体X−1という。)はSynthesis, 1993 (2), Pages194−196を参考に合成する。
1,2,4−ベンゼントリカルボン酸無水物をホルムアミドでフタルイミド誘導体へと変換する。次に、フタルイミド誘導体をアンモニア水で処理することにより、フタルアミド誘導体とする。引き続き、フタルアミド誘導体を脱水してフタロニトリル誘導体X−1とする。
4-Carboxy-phthalonitol (hereinafter referred to as phthalonitrile derivative X-1) is synthesized with reference to Synthesis, 1993 (2), Pages 194-196.
1,2,4-benzenetricarboxylic anhydride is converted to phthalimide derivatives with formamide. Next, the phthalimide derivative is treated with ammonia water to obtain a phthalamide derivative. Subsequently, the phthalamide derivative is dehydrated to obtain a phthalonitrile derivative X-1.
3,6―bis(phenylthio)phthalonitrile(以下、フタロニトリル誘導体X−2という。)はJ. Am. Chem. Soc. 2011, Vol 133, Pages 19642−19645を参考に合成する。ヒドロキノン誘導体をトシル化した後に芳香族求核置換反応を行い、目的のフタロニトリル誘導体X−2を合成する。 3,6-bis (phenylthio) phthalontrile (hereinafter referred to as phthalonitrile derivative X-2) is synthesized with reference to J. Am. Chem. Soc. 2011, Vol 133, Pages 19642-19645. After the hydroquinone derivative is tosylated, an aromatic nucleophilic substitution reaction is performed to synthesize the desired phthalonitrile derivative X-2.
上記のフタロニトリル誘導体X−1及びX−2を環化させフタロシアニン骨格を合成する。この反応中あるいは反応後に環内に亜鉛原子を導入し、目的のフタロシアニン色素(D−1)を得る。 The above phthalonitrile derivatives X-1 and X-2 are cyclized to synthesize a phthalocyanine skeleton. During or after this reaction, a zinc atom is introduced into the ring to obtain the desired phthalocyanine dye (D-1).
本発明の色素を用いた光電変換素子又は色素増感太陽電池の基本構成の一例を図1により説明する。図1は光電変換素子の一例を示す断面図であり、基板1上に、導電層2と半導体層に増感用の色素が吸着された色素吸着半導体層3が、積層された電極10と、基板4上に導電層5が設けられた対向電極11を有し、両電極間に電解質層6を配した構成となっている。色素吸着半導体層3は、電極の一部を構成するため半導体電極ともいう。色素吸着半導体層3はチタニアあるいは金属酸化物微粒子を用い1つの層として塗工・焼結されたもの、又は複数回の塗工・焼結により形成された層であり、色素が吸着された半導体層であり、酸化チタン粒子等の金属酸化物粒子とこの粒子の表面を覆うように存在する増感色素からなっている。なお、光は電極10側から入る。そして、本発明の色素増感太陽電池は、上記と同様な基本構成を有するが外部回路で仕事をさせるようにしたものである。そして、色素光電変換素子を色素増感太陽電池とする方法は上記特許文献1〜4等で公知であり、これら公知の方法でよい。
An example of the basic configuration of a photoelectric conversion element or a dye-sensitized solar cell using the dye of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view illustrating an example of a photoelectric conversion element. On a substrate 1, an
基板1としては、透明な絶縁材料であれば特に限定されるものではなく、例えば通常のガラス板やプラスチック板などが挙げられ、更には屈曲性のあるものでも良く、例えばPET樹脂などが挙げられるが、好ましくは約500℃を上限にした酸化チタンを焼付ける工程に耐え得る耐熱材料であることであり、透明なガラス板が挙げられる。 The substrate 1 is not particularly limited as long as it is a transparent insulating material. For example, a normal glass plate or plastic plate may be used, and further, a flexible material may be used. For example, a PET resin may be used. However, it is preferably a heat-resistant material that can withstand the step of baking titanium oxide with an upper limit of about 500 ° C., and a transparent glass plate can be mentioned.
次に、この基板1の表面に基材の透明性を損なわないような導電層2を設けるが、導電層としてはいわゆる透明電極として知られているITO、FTO、ATOあるいはこれらを組み合わせたものでよく、更には透明性を損なわない厚みの金属層であってもよい。これらの導電層を設ける方法は特に限定されるものではなく、スパッタリング、蒸着(CVD及びPVDを含む)、スプレー、レーザアブレーションあるいはペースト化した各材料を用いるスピンコート、バーコート、スクリーン印刷の手法など既知の手法を用いることができる。中でも、スプレー法又は気相で行われるスパッタリング又は蒸着法が適する。
Next, a
この上に、色素吸着半導体層3を設ける。通常は半導体として金属酸化物の層を形成したのち、これに増感色素を吸着させる。金属酸化物としては、光電変換材料と知られているものが使用でき、酸化チタン、酸化亜鉛、酸化タングステン、酸化スズ等を挙げることができる、中でも酸化チタン及び酸化スズが好ましい。酸化チタンとしては、アナターゼ型、ルチル型、ブルッカイト型等の酸化チタンの他、水酸化チタン、含水酸化チタン類であってもよい。また、Nb、V又はTaの各元素の少なくとも1つを酸化チタンに対して30ppm〜5%の重量濃度(金属元素として)になるようドーピングしてもよい。このような金属酸化物であれば、本発明に用いることが可能であるが、平均粒子径が5〜500nm、好ましくは10〜200nmの範囲の微粒子であることがよい。 On this, the dye adsorption semiconductor layer 3 is provided. Usually, after a metal oxide layer is formed as a semiconductor, a sensitizing dye is adsorbed thereto. As a metal oxide, what is known as a photoelectric conversion material can be used, and titanium oxide, zinc oxide, tungsten oxide, tin oxide, and the like can be used. Of these, titanium oxide and tin oxide are preferable. Titanium oxide may be titanium hydroxide such as anatase type, rutile type, brookite type, titanium hydroxide or hydrous titanium oxide. Further, at least one of Nb, V, or Ta may be doped so as to have a weight concentration (as a metal element) of 30 ppm to 5% with respect to titanium oxide. If it is such a metal oxide, it can be used for this invention, but it is good that it is a fine particle with an average particle diameter of 5-500 nm, Preferably it is the range of 10-200 nm.
金属酸化物の層を前記導電層2上に形成するが、その方法については、特に限定されるものではなく、例えばペースト化した金属酸化物をスピンコート、印刷、スプレーコートなどの各手法を用いても良い。また、製膜後に酸化チタン等の金属酸化物の焼結などを目的に焼成することも可能である。次に、金属酸化物に増感用の色素を吸着させて色素吸着金属酸化物として、色素吸着半導体層3とする。
A metal oxide layer is formed on the
本発明では増感色素に特徴があり、その他の層又は材料は公知の構造又は材料とすることができ、図1に示す構造のものに限らない。 The present invention is characterized by a sensitizing dye, and other layers or materials can have a known structure or material, and are not limited to those having the structure shown in FIG.
色素吸着半導体層3を構成する材料は、半導体と色素であるが、通常、半導体は金属酸化物、好ましくは酸化チタン又は酸化スズであるので、半導体を金属酸化物又は酸化チタンで代表することがある。また、色素増感用の色素としては、上記式(1)で表わされるフタロシアニン色素を使用する。なお、必要により吸収波長領域を広げるためにこのフタロシアニン色素とは異なる範囲に最大吸収波長を有する他の色素を併用することも有利である。 The materials constituting the dye-adsorbing semiconductor layer 3 are a semiconductor and a dye. Usually, since the semiconductor is a metal oxide, preferably titanium oxide or tin oxide, the semiconductor may be represented by a metal oxide or titanium oxide. is there. As the dye for dye sensitization, a phthalocyanine dye represented by the above formula (1) is used. It is also advantageous to use another dye having a maximum absorption wavelength in a different range from this phthalocyanine dye in order to broaden the absorption wavelength region if necessary.
色素はこれを溶解する溶媒に溶解してチタニア半導体層に吸着させる。吸着溶媒は色素が可能である溶媒であれば、使用することができる。具体的には、メタノール、エタノール、プロパノール、ノルマルブタノール等の脂肪族アルコール類、アセトニトリル、プロピオニトリル等のニトリル溶媒、アセトン、メチルエチルケトン等のケトン類、ジメチルカーボネート、ジエチルカーボネート等のカーボネート類、ラクトン類、カプロラクタム類を使用することができる。好ましくはメタノール、エタノール又はアセトニトリルである。 The dye is dissolved in a solvent that dissolves the dye and adsorbed to the titania semiconductor layer. The adsorption solvent can be used as long as it is a solvent capable of being dyed. Specifically, aliphatic alcohols such as methanol, ethanol, propanol and normal butanol, nitrile solvents such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, carbonates such as dimethyl carbonate and diethyl carbonate, and lactones Caprolactams can be used. Methanol, ethanol or acetonitrile is preferred.
色素溶液にデオキシコール酸、ケノデオキシコール酸(DCA)等の共吸着剤を溶解した色素溶液を用い、吸着してもよい。 The dye solution may be adsorbed using a dye solution in which a coadsorbent such as deoxycholic acid or chenodeoxycholic acid (DCA) is dissolved.
色素は超臨界流体、加圧流体に溶解して吸着させてもよい。具体的には、炭酸ガスや炭酸ガスにエントレーナーを加えた溶液により吸着させることが好ましい。 The dye may be dissolved and adsorbed in a supercritical fluid or a pressurized fluid. Specifically, it is preferably adsorbed by carbon dioxide or a solution obtained by adding an entrainer to carbon dioxide.
色素の吸着した金属酸化物には、更にCO2超臨界流体中でカルボン酸を吸着させてもよい。カルボン酸を吸着させる効果は、非特許文献J. Photochem.and Photobio.A,Chem.164(2004)117により公知である。しかしながら、色素吸着やリンス処理と同様に、酸化チタン、酸化スズなどの金属酸化物の微細孔内部まで有効に吸着させることが重要である。色素の吸着した金属酸化物(色素の吸着した金属酸化物層を有する基板であってもよい)とカルボン酸を、圧力範囲5〜30Mpaであり、温度範囲が40〜60℃で形成されるCO2超臨界流体中又は加圧CO2中に置くことで、有効にカルボン酸を吸着できる。カルボン酸としては、好ましくは安息香酸、酢酸、アニス酸、ニコチン酸を挙げることができる。これらカルボン酸は、メタノール、エタノール、プロパノール、ブタノールのうちの少なくともいずれか1種類を含むアルコールに溶解した状態で使用することが好ましく、そのカルボン酸濃度が0.01〜10mol/Lの範囲であることが好ましい。さらに、色素の吸着は亜臨界状態の加圧下で吸着することが好ましく色素を溶媒に溶解させた溶液と炭酸ガスとの混合溶液中で吸着させたものであり、その炭酸ガスの圧力が1〜5MPa、温度が40℃〜60℃の範囲であることが好ましい。 The metal oxide adsorbed with the dye may be further adsorbed with carboxylic acid in a CO 2 supercritical fluid. The effect of adsorbing carboxylic acid is described in Non-Patent Document J. Pat. Photochem. and Photobio. A, Chem. 164 (2004) 117. However, it is important to effectively adsorb the fine pores of metal oxides such as titanium oxide and tin oxide as in the case of dye adsorption and rinsing. CO formed with a dye-adsorbed metal oxide (which may be a substrate having a dye-adsorbed metal oxide layer) and a carboxylic acid in a pressure range of 5-30 Mpa and a temperature range of 40-60 ° C. 2 by placing the supercritical fluid or in the pressure CO 2, it can effectively adsorb the carboxylic acid. Preferred examples of the carboxylic acid include benzoic acid, acetic acid, anisic acid, and nicotinic acid. These carboxylic acids are preferably used in a state dissolved in an alcohol containing at least one of methanol, ethanol, propanol, and butanol, and the carboxylic acid concentration is in the range of 0.01 to 10 mol / L. It is preferable. Furthermore, the adsorption of the dye is preferably carried out under subcritical pressure, and the dye is adsorbed in a mixed solution of a solution in which the dye is dissolved in a solvent and carbon dioxide, and the pressure of the carbon dioxide is 1 to 5 MPa and the temperature are preferably in the range of 40 ° C to 60 ° C.
上記のように基板1、導電層2及び色素吸着半導体層3からなる電極10は負極として作用する。もう一方の正極として作用する電極(対向電極)11は図1に示すように、電極10と対向して配置する。正極となる電極は、導電性の金属などでよく、また、例えば通常のガラス板やプラスチック板などの基板4に金属膜や炭素膜等の導電層5を施したものでもよい。
As described above, the
負極となる電極10と、正極となる対向電極11の間には、電解質層6を設ける。この電解質層6を構成する電解質の種類は、光励起され半導体への電子注入を果たした後の色素を還元するための酸化還元種を含んでいれば特に限定されず、液状の電解質であってもよく、これに公知のゲル化剤(高分子又は低分子のゲル化剤)やイオン液体と金属酸化物を混練した擬固体を添加して得られるゲル状の電解質であってもよい。
An
例えば、溶液電解質に用いる電解質の例としては、ヨウ素とヨウ化物(LiI、NaI、KI、CsI、CaI2等の金属ヨウ化物、テトラアルキルアンモニウムヨーダイド、ピリジニウムヨーダイド、イミダゾリウムヨーダイド等の4級アンモニウム化合物ヨウ素塩等)の組み合わせ、臭素と臭化物(LiBr、NaBr、KBr、CsBr、CaBr2 等の金属臭化物、テトラアルキルアンモニウムブロマイド、ピリジニウムブロマイド等の4級アンモニウム化合物臭素塩等)の組み合わせ、ポリ硫化ナトリウム、アルキルチオール、アルキルジスルフィド等のイオウ化合物、ビオロゲン色素、ヒドロキノン、キノン等が挙げられる。電解質は混合して用いてもよい。 For example, examples of the electrolyte used in the solution electrolyte, iodine and iodide (LiI, NaI, KI, CsI, metal iodide such as CaI 2, tetraalkylammonium iodide, pyridinium iodide, such as imidazolium iodide 4 Combination of bromine and bromide (metal bromide such as LiBr, NaBr, KBr, CsBr, CaBr 2 , quaternary ammonium compound bromide such as tetraalkylammonium bromide, pyridinium bromide, etc.), poly Examples thereof include sulfur compounds such as sodium sulfide, alkyl thiol, and alkyl disulfide, viologen dyes, hydroquinone, and quinone. The electrolyte may be used as a mixture.
また、電解質としては、高沸点を有する溶融塩電解質が好ましい。半導体電極が色素吸着酸化チタン層からなる場合は、溶融塩電解質と組み合わせることにより、特に優れた電池特性を発揮する。溶融塩電解質組成物は溶融塩を含む。溶融塩電解質組成物は常温で液体であるのが好ましい。主成分である溶融塩は室温において液状であるか又は低融点の電解質であり、その一般的な例としては「電気化学」、1997年、第65巻、第11号、p.923 等に記載のピリジニウム塩、イミダゾリウム塩、トリアゾリウム塩等が挙げられる。溶融塩は単独で使用しても2種以上混合して使用してもよい。また、LiI、NaI、KI、LiBF4、CF3COOLi、CF3COONa、LiSCN、NaSCN等のアルカリ金属塩を併用することもできる。通常、溶融塩電解質組成物はヨウ素を含有する。溶融塩電解質組成物の揮発性は低いことが好ましく、溶媒を含まないことが好ましい。溶融塩電解質組成物はゲル化して使用してもよい。 Further, as the electrolyte, a molten salt electrolyte having a high boiling point is preferable. When the semiconductor electrode is composed of a dye-adsorbed titanium oxide layer, particularly excellent battery characteristics are exhibited by combining with a molten salt electrolyte. The molten salt electrolyte composition includes a molten salt. The molten salt electrolyte composition is preferably liquid at room temperature. The molten salt as the main component is a liquid at room temperature or an electrolyte having a low melting point, and a general example thereof is “Electrochemistry”, 1997, Vol. 65, No. 11, p. 923, etc., pyridinium salts, imidazolium salts, triazolium salts and the like. The molten salt may be used alone or in combination of two or more. In addition, alkali metal salts such as LiI, NaI, KI, LiBF 4 , CF 3 COOLi, CF 3 COONa, LiSCN, NaSCN can be used in combination. Usually, the molten salt electrolyte composition contains iodine. The molten salt electrolyte composition preferably has low volatility and preferably does not contain a solvent. The molten salt electrolyte composition may be used after gelation.
電解液に溶媒を使用する場合は、粘度が低く高イオン移動度を示し、優れたイオン伝導性を発現できる化合物であることが望ましい。このような溶媒の例としては、エチレンカーボネート、プロピレンカーボネート等のカーボネート化合物、3-メチル-2-オキサゾリジノン等の複素環化合物、ジオキサン、ジエチルエーテル等のエーテル化合物、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールジアルキルエーテル、ポリプロピレングリコールジアルキルエーテル等の鎖状エーテル類、メタノール、エタノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリプロピレングリコールモノアルキルエーテル等のアルコール類、エチレングリコール、プロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン等の多価アルコール類、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル化合物、ジメチルスルホキシド、スルフォラン等の非プロトン極性物質、水等が挙げられる。これらの溶媒は混合して用いることもできる。 When a solvent is used in the electrolytic solution, it is desirable that the compound has a low viscosity and high ion mobility and can exhibit excellent ionic conductivity. Examples of such solvents include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether , Chain ethers such as polyethylene glycol dialkyl ether and polypropylene glycol dialkyl ether, alcohols such as methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether and polypropylene glycol monoalkyl ether, ethylene Glycol, propylene glycol, polyethylene glycol, polypropylene glycol Lumpur, polyhydric alcohols such as glycerin, acetonitrile, glutarodinitrile, methoxy acetonitrile, propionitrile, nitrile compounds such as benzonitrile, dimethyl sulfoxide, aprotic polar substances such as sulfolane, water and the like. These solvents can also be used as a mixture.
電解質層6を設ける方法は特に限定されるものではなく、例えば両電極の間にフィルム状のスペーサ7を配置して隙間を形成し、その隙間に電解質を注入する方法でも良く、また、負極内面に電解質を塗布などした後に正極を適当な間隔をおいて積載する方法でも良い。電解質が流出しないよう、両極とその周囲を封止することが望ましいが、封止の方法や封止材の材質については特に限定するものではない。
The method for providing the
以下、合成例及び実施例に基づいて本発明について更に詳細に説明する。なお、合成例1は実施例であると理解される。 Hereinafter, the present invention will be described in more detail based on synthesis examples and examples. Note that Synthesis Example 1 is understood to be an example.
合成例1
化合物A-1(52 mmmol)をホルムアミド中で4時間還流させて化合物A-2(40 mmol, 80%)を得た。化合物A-2(40 mmol)を28%アンモニア溶液中、室温で48時間反応させ化合物A-3(30 mmol, 75%)を得た。化合物A-3(30 mmol)をN,N−ジメチルホルムアミド(以下DMF)中、氷浴下、塩化チオニルと24時間反応させ化合物A-4(9 mmol, 30%)を得た。
Synthesis example 1
Compound A-1 (52 mmmol) was refluxed in formamide for 4 hours to obtain Compound A-2 (40 mmol, 80%). Compound A-2 (40 mmol) was reacted in a 28% ammonia solution at room temperature for 48 hours to obtain compound A-3 (30 mmol, 75%). Compound A-3 (30 mmol) was reacted with thionyl chloride in N, N-dimethylformamide (hereinafter DMF) in an ice bath for 24 hours to obtain compound A-4 (9 mmol, 30%).
化合物B-1(12 mmol)とパラトルエンスルホニルクロリド(pTsCl)を炭酸カリウム存在下、アセトン還流条件で2時間反応させ化合物B-2(12 mmol, quant.)を得た。化合物B-2(12 mmol)とチオフェノールを炭酸カリウム存在下、ジメチルスルホキシド(DMSO)中、室温で16時間反応させ化合物B-3(9.6 mmol, 80%)得た。 Compound B-1 (12 mmol, quant.) Was obtained by reacting compound B-1 (12 mmol) with paratoluenesulfonyl chloride (pTsCl) in the presence of potassium carbonate under acetone reflux conditions for 2 hours. Compound B-3 (9.6 mmol, 80%) was obtained by reacting compound B-2 (12 mmol) and thiophenol in the presence of potassium carbonate in dimethyl sulfoxide (DMSO) at room temperature for 16 hours.
化合物B-3(8.4 mmol)と化合物A-4(2.8 mmol)を1,8−ジアザビシクロウンデセン(DBU)(11.2 mmol)の存在下、n-ペンタノール還流条件で反応させ化合物C-1(0.25 mmol, 9%)を得た。化合物C-1(0.25 mmol)にDMF中、酢酸亜鉛を加え80℃で2時間攪拌しフタロシアニン色素D−1(0.22 mmol, 89%)を得た。フタロシアニン色素D−1のIRスペクトルを図2に示し、UV-VISスペクトルを図3に示す。 Compound B-3 (8.4 mmol) is reacted with Compound A-4 (2.8 mmol) in the presence of 1,8-diazabicycloundecene (DBU) (11.2 mmol) under reflux conditions of n-pentanol to give Compound C- 1 (0.25 mmol, 9%) was obtained. To compound C-1 (0.25 mmol), zinc acetate in DMF was added and stirred at 80 ° C. for 2 hours to obtain phthalocyanine dye D-1 (0.22 mmol, 89%). The IR spectrum of phthalocyanine dye D-1 is shown in FIG. 2, and the UV-VIS spectrum is shown in FIG.
合成例2
化合物E-1(110 mmmol)をホルムアミド中で4時間還流させて化合物E-2(103 mmol, 94%)を得た。化合物E-2(100 mmol)を28%アンモニア溶液中、室温で24時間反応させ化合物E-3(74 mmol, 74%)を得た。化合物E-3(70 mmol)をDMF中、氷浴下塩化チオニルと24時間反応させ化合物E-4(53 mmol, 75%)を得た。
Synthesis example 2
Compound E-1 (110 mmmol) was refluxed in formamide for 4 hours to obtain compound E-2 (103 mmol, 94%). Compound E-2 (100 mmol) was reacted in a 28% ammonia solution at room temperature for 24 hours to obtain compound E-3 (74 mmol, 74%). Compound E-3 (70 mmol) was reacted with thionyl chloride in DMF in an ice bath for 24 hours to obtain compound E-4 (53 mmol, 75%).
化合物B-3(8.4 mmol)と化合物E-4(2.8 mmol)をDBU(11.2 mmol)存在下、n-ペンタノール還流条件で反応させ化合物F-1(0.28 mmol, 10%)を得た。化合物F-1(0.28 mmol)にDMF中、酢酸亜鉛を加え80℃で2時間攪拌しF-2(0.25 mmol, 90%)を得た。F-2(0.25 mmol)をジクロロビス(トリフェニルホスフィン)パラジウム(II)(PdCl2(PPh3)2)、ヨウ化銅の存在下、トリイソプロピルシリルアセチレンとクロスカップリングさせた後、テトラ―n―ブチルアンモニウムフルオリド(TBAF)処理を行い、化合物F-3(0.19 mmol, 76%)を得た。化合物F-3(0.19 mmol)を4-ヨード安息香酸とクロスカップリングさせフタロシアニン色素D−2(0.11 mmol, 58%)を得た。フタロシアニン色素D−2のIRスペクトルを図5に示し、UV-VISスペクトルを図4に示す Compound F-1 (0.28 mmol, 10%) was obtained by reacting Compound B-3 (8.4 mmol) and Compound E-4 (2.8 mmol) in the presence of DBU (11.2 mmol) under reflux conditions of n-pentanol. To compound F-1 (0.28 mmol), zinc acetate was added in DMF and stirred at 80 ° C. for 2 hours to obtain F-2 (0.25 mmol, 90%). F-2 (0.25 mmol) was cross-coupled with triisopropylsilylacetylene in the presence of dichlorobis (triphenylphosphine) palladium (II) (PdCl 2 (PPh 3 ) 2 ) and copper iodide, and then tetra-n -Butyl ammonium fluoride (TBAF) treatment was performed to obtain Compound F-3 (0.19 mmol, 76%). Compound F-3 (0.19 mmol) was cross-coupled with 4-iodobenzoic acid to obtain phthalocyanine dye D-2 (0.11 mmol, 58%). The IR spectrum of phthalocyanine dye D-2 is shown in FIG. 5, and the UV-VIS spectrum is shown in FIG.
得られたフタロシアニン色素D−1及びD−2の最大吸収波長及び吸収端を表1に示す。 Table 1 shows the maximum absorption wavelength and absorption edge of the obtained phthalocyanine dyes D-1 and D-2.
実施例1
30mm×25mm×3mmの透明導電膜付ガラス基板として日本板ガラス製のFTO(フッ素ドープ酸化スズ)膜付ガラス基板(商品名:Low‐Eガラス)を使用した。
次に、導電性膜付き基板の導電性膜上に、酸化チタン膜を形成した。酸化チタンは、市販の酸化チタンペースト(ソラロニクス社製Dペースト)を使用した。これを、導電性膜付き基板の導電性膜上に、スキージ印刷の手法で5mm×5mmの範囲に塗工し、乾燥後450℃で焼成して厚み15μmの酸化チタン層を形成した積層板を得た。
Example 1
As a glass substrate with a transparent conductive film of 30 mm × 25 mm × 3 mm, a glass substrate with FTO (fluorine-doped tin oxide) film made by Nippon Sheet Glass (trade name: Low-E glass) was used.
Next, a titanium oxide film was formed on the conductive film of the substrate with the conductive film. As titanium oxide, a commercially available titanium oxide paste (D paste made by Solaronics) was used. A laminated plate in which a titanium oxide layer having a thickness of 15 μm was formed by coating this on a conductive film of a substrate with a conductive film by a squeegee printing method in a range of 5 mm × 5 mm, drying and baking at 450 ° C. Obtained.
色素としてフタロシアニン色素D−1を使用した。これを3×10-4mol/L 、DCAを3×10-3mol/Lとなるようにエタノールに溶解させた。色素の吸着は、容器に上記色素溶液を入れ、更に上記酸化チタン層を形成した積層板を配置し、2時間静置後、容器から色素の吸着した積層板を取り出した。 The phthalocyanine dye D-1 was used as the dye. This was dissolved in ethanol so as to be 3 × 10 −4 mol / L and DCA to be 3 × 10 −3 mol / L. For the adsorption of the dye, the above dye solution was placed in a container, and a laminated board on which the above titanium oxide layer was formed was placed.
この積層板の酸化チタンの膜を形成した5mm×5mmの外周4辺に厚み50μmのアイオノマー樹脂からなるシート状の熱可塑性接着剤(三井デュポンポリケミカル社商品名;ハイミランシート)を、電解液が注入できるよう、外周部の2箇所に約1mm程度の隙間を設けるようにして貼り付けた。この熱可塑性接着剤は、封止材であると同時に、両極間のスペーサの役割を果たす。次に、正極となる厚み10nmの白金膜をスパッタリングの手法で形成したガラス基板を、白金側が酸化チタン側と対向するように前記熱可塑性接着剤フィルムを介して貼り合わせた。この熱可塑性接着剤フィルムの隙間から、0.5MのLiI、0.5Mのt−ブチルピリジンと、0.05Mのヨウ素を主成分として含むアセトニトリル溶液を毛細管現象を利用して基材と正極の間に満たした。電解質を満たした後、直ちに前記隙間をエポキシ樹脂接着剤で封止して、光電変換素子F−1を得た。 A sheet-like thermoplastic adhesive (trade name of Mitsui Dupont Polychemical Co., Ltd .; High Milan Sheet) made of an ionomer resin having a thickness of 50 μm is formed on four sides of the outer periphery of 5 mm × 5 mm on which the titanium oxide film of the laminate is formed. So that a gap of about 1 mm is provided at two locations on the outer peripheral portion. This thermoplastic adhesive is not only a sealing material but also serves as a spacer between the two electrodes. Next, a glass substrate on which a platinum film having a thickness of 10 nm serving as a positive electrode was formed by a sputtering method was bonded through the thermoplastic adhesive film so that the platinum side was opposed to the titanium oxide side. From the gap between the thermoplastic adhesive films, an acetonitrile solution containing 0.5M LiI, 0.5M t-butylpyridine, and 0.05M iodine as the main components is utilized for the base material and the positive electrode using capillary action. Filled in between. Immediately after filling the electrolyte, the gap was sealed with an epoxy resin adhesive to obtain a photoelectric conversion element F-1.
作製した光電変換素子F−1を色素増感太陽電池として、ソーラーシミュレータを用いAM1.5、100mW/cm2の擬似太陽光を用い、I−Vカーブトレーサーを用いて特性評価した。変換効率(%)、短絡電流(Jsc: mA/cm2)、開放電圧(Voc: V), フィルファクター(ff:形状係数)の各特性を測定した結果を表2に示す。 The produced photoelectric conversion element F-1 was used as a dye-sensitized solar cell, and its characteristics were evaluated by using a solar simulator, AM1.5, 100 mW / cm 2 simulated sunlight, and an IV curve tracer. Table 2 shows the results of measurement of conversion efficiency (%), short-circuit current (Jsc: mA / cm 2 ), open-circuit voltage (Voc: V), and fill factor (ff: shape factor).
実施例2
色素としてフタロシアニン色素D−2を用いた他は、実施例1と同様にして、光電変換素子F−2を作製し、変換効率(%)、短絡電流(Jsc:mA/cm2)、開放電圧(Voc:V)、フィルファクター(ff:形状係数)の各特性を測定した。結果を表2に示す。
Example 2
A photoelectric conversion element F-2 was produced in the same manner as in Example 1 except that the phthalocyanine dye D-2 was used as the dye, and conversion efficiency (%), short-circuit current (Jsc: mA / cm 2 ), open-circuit voltage Each characteristic of (Voc: V) and fill factor (ff: shape factor) was measured. The results are shown in Table 2.
1:基板、2:導電層、3:色素吸着半導体層、4:基板、5:導電層、6:電解質層、7:スペーサ、10:電極、11:対向電極 1: substrate, 2: conductive layer, 3: dye adsorption semiconductor layer, 4: substrate, 5: conductive layer, 6: electrolyte layer, 7: spacer, 10: electrode, 11: counter electrode
Claims (4)
式(1)において、A1はベンゼン環、ピラジン環、キノキサリン環、ピラジノ[2,3−b]キノキサリン環または下記式(3)もしくは式(4)で示される原子団を表す。A2は独立にベンゼン環、ナフタレン環またはアントラセン環を表す。Zは酸素または硫黄原子を表す。Mは2個の水素原子、またはフタロシアニンと共有結合もしくは配位結合し得る原子または原子団を表わす。Yは独立にフェニル基またはアルキル基である。nは独立に1または2の数字を表す。mは0乃至2の整数を表す。Xはカルボキシル基または下記式(2)で表される基であるが、A 1 がベンゼン環、ピラジン環、キノキサリン環またはピラジノ[2,3−b]キノキサリン環である場合は、Xは式(2)で表される基であり、A 1 が式(3)もしくは式(4)で示される原子団である場合は、Xはカルボキシル基であり、含窒素五員環と縮合環を形成しないベンゼン環又はナフタレン環に結合する。
In formula (1), A 1 represents a benzene ring, a pyrazine ring, a quinoxaline ring, a pyrazino [2,3-b] quinoxaline ring, or an atomic group represented by the following formula (3) or formula (4) . A 2 independently represents a benzene ring, a naphthalene ring or an anthracene ring. Z represents an oxygen or sulfur atom. M represents two hydrogen atoms, or an atom or atomic group that can be covalently or coordinately bonded to phthalocyanine. Y is independently a phenyl group or an alkyl group. n independently represents a number of 1 or 2. m represents an integer of 0 to 2. Although X is a group represented by a carboxyl group or the following formula (2), if A 1 is a benzene ring, a pyrazine ring, a quinoxaline ring or pyrazino [2,3-b] quinoxaline ring, X is the formula ( 2) When A 1 is an atomic group represented by formula (3) or formula (4), X is a carboxyl group and does not form a condensed ring with a nitrogen-containing five-membered ring. Bonded to benzene ring or naphthalene ring.
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