JP5114900B2 - Method for producing dye-sensitized solar cell electrode - Google Patents
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Description
本発明は色素増感型太陽電池に用いられる電極の製造方法に関する。 The present invention relates to a method for producing an electrode used in a dye-sensitized solar cell.
１９９１年のＧｒａｔｚｅｌらの報告（非特許文献１）以来、太陽電池の一種として、色素増感型太陽電池について検討が行なわれている。
色素増感型太陽電池は、光を受け電子を放出する受光電極、対電極、対電極から電子を輸送する電解質層から構成される。上記の受光電極は、フッ素やインジウムを含む酸化スズ導電層や、アルミニウムなどを含む酸化亜鉛導電層などの金属酸化物透明導電層上に、酸化チタンや酸化ニオブなどの半導体粒子層を形成し、該半導体粒子層に色素を吸着させることで得られる。
色素増感型太陽電池の光電変換効率（η）は開放電圧（Ｖｏｃ）と短絡電流密度（Ｊｓｃ）の積に比例して大きくなる。短絡電流密度（Ｊｓｃ）は、色素増感型太陽電池が発生する短絡電流（Ｉｓｃ）と有効受光面積に関係している。このため光電変換効率（η）を向上させる目的で、開放電圧（Ｖｏｃ）や短絡電流（Ｉｓｃ）を高める検討が行われている。なかでも、金属酸化物透明導電層と半導体粒子層との間に金属酸化物膜の下引き層を設けることによって開放電圧（Ｖｏｃ）を高くして光電変換効率（η）を向上させることが行われている。
Since a report by Gratzel et al. In 1991 (Non-Patent Document 1), a dye-sensitized solar cell has been studied as a kind of solar cell.
A dye-sensitized solar cell includes a light receiving electrode that receives light and emits electrons, a counter electrode, and an electrolyte layer that transports electrons from the counter electrode. The light receiving electrode is formed on a metal oxide transparent conductive layer such as a tin oxide conductive layer containing fluorine or indium or a zinc oxide conductive layer containing aluminum or the like, and a semiconductor particle layer such as titanium oxide or niobium oxide is formed. It can be obtained by adsorbing a dye to the semiconductor particle layer.
The photoelectric conversion efficiency (η) of the dye-sensitized solar cell increases in proportion to the product of the open circuit voltage (Voc) and the short circuit current density (Jsc). The short-circuit current density (Jsc) is related to the short-circuit current (Isc) generated by the dye-sensitized solar cell and the effective light receiving area. For this reason, studies are being made to increase the open circuit voltage (Voc) and the short circuit current (Isc) for the purpose of improving the photoelectric conversion efficiency (η). In particular, by providing an undercoat layer of a metal oxide film between the metal oxide transparent conductive layer and the semiconductor particle layer, the open circuit voltage (Voc) is increased to improve the photoelectric conversion efficiency (η). It has been broken.
例えば特許文献１では、乾式製膜法であるイオンスパッタ蒸着により、酸化チタン、酸化ケイ素、酸化マグネシウムなどの下引き層を形成させる方法が開示されている。しかし、このような乾式製膜法は特殊かつ高額な製膜装置が必要であり、また、金属酸化物の種類により、下引き層の形成に要する消費電力が高くなり、製膜できる金属種が限定される場合がある。しかも、大面積の下引き層の製膜を行うには非効率である。
そこで、乾式製膜法と比較して、特殊かつ高額な装置を用いることなく、より低い消費電力で、簡便かつ効率的に製膜できる湿式製膜法を用いて、金属酸化物透明導電層の表面に下引き層を形成する方法が示されている。例えば非特許文献２では、ニオブエトキシド、マグネシウムメトキシド、アルミニウムイソプロポキシド、塩化ユーロピウム、アセチルアセトンスズ、アセチルアセトン亜鉛の溶液を、加熱した金属酸化物透明導電層表面にスプレー噴霧し焼成する湿式製膜法を用いる方法が示されている。しかし、このような化合物の溶液を用いて下引き層を製膜した色素増感型太陽電池は、下引き層が金属酸化物透明導電層と半導体粒子層間の導電性を阻害するため、短絡電流密度（Ｊｓｃ）が低下するという問題があった。非特許文献２の、ニオブエトキシドを用いて製膜した酸化ニオブを下引き層とした色素増感型太陽電池の例では、開放電圧（Ｖｏｃ）、短絡電流密度（Ｊｓｃ）はそれぞれ７１０ｍＶ、９．５４ｍＡとなり、下引き層を有さない色素増感型太陽電池と比較して、開放電圧（Ｖｏｃ）は６ｍＶ増加するが、短絡電流密度（Ｊｓｃ）は０．６３ｍＡ低下している。
For example,
Therefore, compared to the dry film forming method, the metal oxide transparent conductive layer can be formed by using a wet film forming method that can be easily and efficiently formed with lower power consumption without using a special and expensive apparatus. A method of forming an undercoat layer on the surface is shown. For example, in Non-Patent
このように、上述の方法を用いた色素増感型太陽電池の場合、下引き層による金属酸化物透明導電層と半導体粒子層間の導電性阻害による短絡電流密度（Ｊｓｃ）の低下がおこり、十分に光電変換効率（η）が高い色素増感型太陽電池を得ることが困難であった。
本発明の課題は、金属酸化物透明導電層表面の金属酸化物膜の下引き層の短絡電流密度（Ｊｓｃ）の低下を防止し、高い光電変換効率（η）を有する色素増感型太陽電池用受光電極の製造方法を提供することである。 An object of the present invention is to prevent a decrease in short-circuit current density (Jsc) of an undercoat layer of a metal oxide film on the surface of a metal oxide transparent conductive layer and to have a high photoelectric conversion efficiency (η). It is providing the manufacturing method of the light-receiving electrode for water.
モノカルボン酸金属塩は、金属アルコキシドや無機金属塩など他の金属化合物にはないアシル基を分子中に有している。このため、モノカルボン酸金属塩分子は、お互いのアシル基間に生じるファンデル・ワールス力によって相互作用し、分子同士が自己組織化する能力を有していることから、界面において均一な吸着膜を形成すると推察される。そこで我々はこのモノカルボン酸金属塩の特徴に着目し、色素増感型太陽電池の金属酸化物透明導電層と半導体粒子層との間の下引き層に応用すべく検討を行った。その結果、モノカルボン酸金属塩溶液を金属酸化物透明導電層に塗布し、塗布膜から溶媒を除去後、焼成するという、金属酸化物透明導電層と半導体粒子層との間に下引き層を形成した色素増感型太陽電池用電極を製造する方法を見出した。そして、該電極を用いた色素増感型太陽電池が、これまでの下引き層を有する色素増感型太陽電池や、下引き層をもたない色素増感型太陽電池と比較して、短絡電流密度（Ｊｓｃ）と開放電圧（Ｖｏｃ）を高くすることができ、高い光電変換効率（η）を発現する色素増感型太陽電池を見出すに至った。
すなわち本発明は、
（１）金属酸化物透明導電層と半導体粒子層の間に、モノカルボン酸と、スズ、ゲルマニウム、ニオブ、チタン、亜鉛、マグネシウムおよびアルミニウムからなる群から選ばれる少なくとも１種の金属との塩であるモノカルボン酸金属塩溶液を塗布し、溶媒を除去した後に焼成し、金属酸化物膜の下引き層を形成することを特徴とする色素増感型太陽電池用電極の製造方法
（２）上記（１）に記載の製造方法において、モノカルボン酸金属塩を形成するモノカルボン酸が炭素数４〜１０のモノカルボン酸である色素増感型太陽電池用電極の製造方法
である。
The monocarboxylic acid metal salt has an acyl group in the molecule that is not found in other metal compounds such as metal alkoxides and inorganic metal salts. For this reason, monocarboxylic acid metal salt molecules have the ability to interact with each other by van der Waals forces generated between the acyl groups, and the molecules self-assemble. It is inferred to form. Therefore, we focused on the characteristics of this monocarboxylic acid metal salt and studied to apply it to the subbing layer between the metal oxide transparent conductive layer and the semiconductor particle layer of the dye-sensitized solar cell. As a result, an undercoat layer was applied between the metal oxide transparent conductive layer and the semiconductor particle layer, in which the monocarboxylic acid metal salt solution was applied to the metal oxide transparent conductive layer, the solvent was removed from the coating film, and then fired. The present inventors have found a method for producing the formed dye-sensitized solar cell electrode. And, the dye-sensitized solar cell using the electrode is short-circuited as compared with the conventional dye-sensitized solar cell having an undercoat layer and the dye-sensitized solar cell having no undercoat layer. The present inventors have found a dye-sensitized solar cell that can increase the current density (Jsc) and the open circuit voltage (Voc) and exhibits high photoelectric conversion efficiency (η).
That is, the present invention
(1) A salt of a monocarboxylic acid and at least one metal selected from the group consisting of tin, germanium, niobium, titanium, zinc, magnesium and aluminum between the metal oxide transparent conductive layer and the semiconductor particle layer. A method for producing an electrode for a dye-sensitized solar cell, which comprises applying a certain monocarboxylic acid metal salt solution, removing the solvent, and firing to form an undercoat layer of the metal oxide film (2) (1) In the manufacturing method as described in (1), it is a manufacturing method of the electrode for dye-sensitized solar cells whose monocarboxylic acid which forms monocarboxylic acid metal salt is a C4-C10 monocarboxylic acid.
本発明により、金属酸化物透明導電層表面の金属酸化物膜の下引き層の短絡電流密度（Ｊｓｃ）の低下を防止し、高い光電変換効率（η）を有した色素増感型太陽電池を得ることができる。 According to the present invention, a dye-sensitized solar cell having a high photoelectric conversion efficiency (η) that prevents a decrease in short-circuit current density (Jsc) of an undercoat layer of a metal oxide film on the surface of a metal oxide transparent conductive layer is provided. Obtainable.
本発明の色素増感型太陽電池用電極の製造方法は、金属酸化物透明導電層と半導体粒子層との間に、モノカルボン酸金属塩溶液を塗布し、溶媒を除去した後に焼成し、金属酸化膜の下引き層を形成することを特徴としている。
本発明に用いる金属酸化物透明導電層を有した基板は、一般的に知られているものを用いることができる。例えば、ガラス基板、ポリカーボネート樹脂やエポキシ樹脂などの樹脂基板などが挙げられる。特に焼成により金属酸化膜を形成する場合は、ガラス基板が好ましく、樹脂基板を用いる場合は紫外線やマイクロ波の照射による金属酸化膜の形成が好ましい。
In the method for producing a dye-sensitized solar cell electrode of the present invention, a metal salt of a monocarboxylic acid metal salt is applied between a metal oxide transparent conductive layer and a semiconductor particle layer, the solvent is removed, and firing is performed. It is characterized by forming an undercoat layer of an oxide film.
As the substrate having the metal oxide transparent conductive layer used in the present invention, a generally known substrate can be used. For example, a glass substrate, a resin substrate such as a polycarbonate resin and an epoxy resin, and the like can be given. In particular, when a metal oxide film is formed by firing, a glass substrate is preferable, and when a resin substrate is used, it is preferable to form a metal oxide film by irradiation with ultraviolet rays or microwaves.
本発明に用いる金属酸化物透明導電層は、一般的に知られているものを用いることができる。例えば、インジウム錫酸化物（ＩＴＯ）、フッ素をドーピングした二酸化スズ（ＦＴＯ）や、アルミニウムをドープした酸化亜鉛（ＡＺＯ）などが好ましく用いられ、特に、下引き層や半導体粒子層の形成時における加熱や焼成に対して耐熱性を充分に有しているＦＴＯを用いることが特に好ましい。金属酸化物透明導電層は表面抵抗が低い程よい。好ましい表面抵抗の範囲として１００Ω／□（□は単位面積を示す）以下であり、さらに好ましくは４０Ω／□以下である。表面抵抗には下限はないが、通常０．１Ω／□程度である。 As the metal oxide transparent conductive layer used in the present invention, those generally known can be used. For example, indium tin oxide (ITO), fluorine-doped tin dioxide (FTO), aluminum-doped zinc oxide (AZO), and the like are preferably used. In particular, heating during the formation of the undercoat layer and the semiconductor particle layer It is particularly preferable to use FTO that has sufficient heat resistance against firing. The lower the surface resistance of the metal oxide transparent conductive layer, the better. The range of the surface resistance is preferably 100Ω / □ (□ indicates a unit area) or less, more preferably 40Ω / □ or less. There is no lower limit to the surface resistance, but it is usually about 0.1Ω / □.
色素増感型太陽電池用電極に用いられる金属酸化物透明導電層の製造方法としては、例えば「エレクトロニク・セラミクス」，第２２巻，ｐ５９（１９９１）に記載されている、電子ビーム蒸着法、スパッタリング法およびＣＶＤ法等の乾式製膜法や、特開２００１−０７６７７６号公報に記載されている、金属酸化物粉末を含むペーストを塗布焼成して形成する湿式製膜法などがある。この中で、可視光領域で良好な光透過性を示し、かつ比抵抗が約２×１０−４Ω・ｃｍの低抵抗性を示すことから、色素増感型太陽電池用電極においては乾式製膜法により得られる金属酸化物透明導電層が好適に用いられる。 As a method for producing a metal oxide transparent conductive layer used for an electrode for a dye-sensitized solar cell, for example, an electron beam evaporation method described in “Electronic Ceramics”, Vol. 22, p59 (1991), There are dry film forming methods such as a sputtering method and a CVD method, and a wet film forming method described in Japanese Patent Application Laid-Open No. 2001-077676, which is formed by applying and baking a paste containing a metal oxide powder. Among these, since it shows good light transmittance in the visible light region and has a low resistivity of about 2 × 10 −4 Ω · cm, the dye-sensitized solar cell electrode is manufactured by a dry process. A metal oxide transparent conductive layer obtained by a film method is preferably used.
本発明に用いるモノカルボン酸金属塩を形成するモノカルボン酸は、飽和モノカルボン酸、不飽和モノカルボン酸のいずれでもよい。飽和モノカルボン酸としては、ｎ−酪酸、吉草酸、ｎ−カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、イソ酪酸、イソ吉草酸、２−エチル酪酸、２−エチルヘキサン酸、イソパルミチン酸、イソステアリン酸などが挙げられ、不飽和モノカルボン酸としてはミリストレイン酸、パルミトレイン酸、オレイン酸、リノレイン酸、エルカ酸などが挙げられる。この中で、金属酸化物膜の下引き層を焼成により調製する際に分解しやすく、分解物が金属酸化物膜の下引き層に残存し難く、より均質な金属酸化物膜の下引き層を得やすい飽和モノカルボン酸が好ましい。中でも溶媒に溶解するのが容易である炭素数４〜１０のモノカルボン酸、例えばｎ−酪酸、吉草酸、ｎ−カプロン酸、エナント酸、カプリル酸、イソ酪酸、イソ吉草酸、２−エチル酪酸、２−エチルヘキサン酸などが特に好ましい。 The monocarboxylic acid forming the monocarboxylic acid metal salt used in the present invention may be either a saturated monocarboxylic acid or an unsaturated monocarboxylic acid. Saturated monocarboxylic acids include n-butyric acid, valeric acid, n-caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, isobutyric acid, isovaleric acid, 2-ethylbutyric acid, 2 -Ethylhexanoic acid, isopalmitic acid, isostearic acid and the like, and examples of the unsaturated monocarboxylic acid include myristoleic acid, palmitoleic acid, oleic acid, linolenic acid, erucic acid and the like. Among these, the undercoat layer of the metal oxide film is easily decomposed when it is prepared by firing, and the decomposed product is unlikely to remain in the undercoat layer of the metal oxide film. Saturated monocarboxylic acids that are easy to obtain are preferred. Among these, monocarboxylic acids having 4 to 10 carbon atoms that are easy to dissolve in a solvent, such as n-butyric acid, valeric acid, n-caproic acid, enanthic acid, caprylic acid, isobutyric acid, isovaleric acid, 2-ethylbutyric acid 2-ethylhexanoic acid and the like are particularly preferable.
本発明に用いるモノカルボン酸金属塩を形成する金属は、周期律表のＩＩ〜Ｖ族に属する金属である。ＩＩ〜Ｖ族に属する金属を用いることにより、開放電圧（Ｖｏｃ）を高くすることができる。ＩＩ〜Ｖ族に属する金属として、例えば、ベリリウム、マグネシウム、ストロンチウム、バリウム、スカンジウム、イットリウム、ランタン、アクチニウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、銅、銀、亜鉛、カドミウム、アルミニウム、ガリウム、インジウム、タリウム、シリコン、ゲルマニウム、スズ、鉛、アンチモン、ビスマスなどが挙げられる。中でも、金属酸化物膜の下引き層が良好な透明性を有するスズ、ゲルマニウム、ニオブ、チタン、亜鉛、マグネシウム、アルミニウムが好適に用いられ、金属酸化物透明導電層に用いられる金属と同一元素であるスズが特に好ましい。これらは単独で用いても良く、また２種以上を併用しても良い。 The metal that forms the monocarboxylic acid metal salt used in the present invention is a metal belonging to Groups II to V of the periodic table. By using a metal belonging to Group II to Group V, the open circuit voltage (Voc) can be increased. Examples of metals belonging to Group II to V include beryllium, magnesium, strontium, barium, scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, copper, silver, zinc, cadmium, aluminum, gallium , Indium, thallium, silicon, germanium, tin, lead, antimony, bismuth, and the like. Of these, tin, germanium, niobium, titanium, zinc, magnesium, and aluminum, which have a good transparency in the undercoat layer of the metal oxide film, are preferably used, and the same element as the metal used in the metal oxide transparent conductive layer. Certain tins are particularly preferred. These may be used alone or in combination of two or more.
金属酸化物膜の下引き層の厚みとしてはいずれの厚みでもよいが、均質な膜を調製しやすい３〜７００ｎｍが好ましく、１５〜３００ｎｍが特に好ましい。
本発明に用いるモノカルボン酸金属塩の製造方法は、モノカルボン酸のアルカリ金属塩、アンモニウム塩、有機アミン塩などの水溶液と、水溶性無機金属化合物とを水中などで反応させる複分解法や、モノカルボン酸と無機金属化合物とを高温条件で反応させる直接法、無機金属化合物を酢酸やシュウ酸にて有機酸金属塩とした後に、有機酸金属塩にモノカルボン酸を加えて高温条件で反応させてモノカルボン酸金属塩にする方法、金属アルコキシドにモノカルボン酸を加え高温でアルコールを脱離させながらモノカルボン酸金属塩にする方法などが挙げられる。
The thickness of the undercoat layer of the metal oxide film may be any thickness, but is preferably from 3 to 700 nm, and particularly preferably from 15 to 300 nm, from which a homogeneous film can be easily prepared.
The method for producing a monocarboxylic acid metal salt used in the present invention includes a metathesis method in which an aqueous solution of an alkali metal salt, ammonium salt, organic amine salt or the like of a monocarboxylic acid and a water-soluble inorganic metal compound are reacted in water, Direct method of reacting carboxylic acid and inorganic metal compound under high temperature condition, after converting inorganic metal compound to organic acid metal salt with acetic acid or oxalic acid, adding monocarboxylic acid to organic acid metal salt and reacting under high temperature condition And a method of forming a monocarboxylic acid metal salt, a method of adding a monocarboxylic acid to a metal alkoxide, and a method of converting it to a monocarboxylic acid metal salt while desorbing alcohol at high temperature.
本発明に用いるモノカルボン酸金属塩を溶解させる溶媒は、モノカルボン酸金属塩が溶解するものであればいずれでも良い。例えば、エタノール等のアルコール系溶媒、トルエン等の芳香族炭化水素系溶媒、ヘキサン等の炭化水素系溶媒、クロロホルム等の含ハロゲン系溶媒、アセトン等のケトン系溶媒、ジエチルエーテル等のエーテル系溶媒、ジメチルホルムアミド等のアミド系溶媒、酢酸エチル等のエステル系溶媒、酢酸等のカルボン酸系溶媒などが好適に用いられ、単独で用いても混合して用いてもよい。これらの溶媒のなかでより好適なものは炭化水素系溶媒、アルコール系溶媒、エステル系溶媒、エーテル系溶媒、ケトン系溶媒であり、さらに好適なものは、基板へのぬれ性や環境負荷の点から、エタノール等の極性の高いアルコール系溶媒である。また、金属酸化物透明導電層と親和性が高いプロピレングリコールモノメチルエーテルアセテートなどのエステル系溶媒と、エタノール、プロパノール、ブタノールなどのアルコール系溶媒とを併用することもできる。また、本発明を損なわない範囲で水を含んでも良い。 The solvent for dissolving the monocarboxylic acid metal salt used in the present invention may be any solvent that dissolves the monocarboxylic acid metal salt. For example, alcohol solvents such as ethanol, aromatic hydrocarbon solvents such as toluene, hydrocarbon solvents such as hexane, halogen-containing solvents such as chloroform, ketone solvents such as acetone, ether solvents such as diethyl ether, Amide solvents such as dimethylformamide, ester solvents such as ethyl acetate, carboxylic acid solvents such as acetic acid, and the like are preferably used, and may be used alone or in combination. Among these solvents, hydrocarbon solvents, alcohol solvents, ester solvents, ether solvents, and ketone solvents are more preferable, and more preferable are the wettability to the substrate and environmental load. Therefore, it is a highly polar alcohol solvent such as ethanol. Further, an ester solvent such as propylene glycol monomethyl ether acetate having high affinity with the metal oxide transparent conductive layer and an alcohol solvent such as ethanol, propanol, and butanol can be used in combination. Moreover, you may contain water in the range which does not impair this invention.
モノカルボン酸金属塩の溶媒に対する濃度は均一に金属酸化物透明導電層に塗布できる濃度が好ましい。なかでも濃度は、良好な塗布面を得るために適度な粘度となる２５重量％以下が好ましく、金属酸化物透明導電層の表面に対してより均質な下引き層が形成できる０．１重量％〜１０重量％がより好ましく、０．１重量％〜５重量％がさらに好ましい。
また、塗布液を調製する際には、本発明の効果を損なわない範囲で、増粘剤、消泡剤、レベリング剤などの各種添加剤を用いてもよい。増粘剤は、エチルセルロース、ニトロセルロースなどが挙げられる。消泡剤、レベリング剤はアニオン型活性剤、ノニオン型活性剤、カチオン型活性剤などが挙げられる。
The concentration of the monocarboxylic acid metal salt with respect to the solvent is preferably a concentration that can be uniformly applied to the metal oxide transparent conductive layer. In particular, the concentration is preferably 25% by weight or less which gives an appropriate viscosity to obtain a good coated surface, and 0.1% by weight which can form a more uniform undercoat layer on the surface of the metal oxide transparent conductive layer. Is more preferably from 10 to 10% by weight, and further preferably from 0.1 to 5% by weight.
Moreover, when preparing a coating liquid, you may use various additives, such as a thickener, an antifoamer, and a leveling agent, in the range which does not impair the effect of this invention. Examples of the thickener include ethyl cellulose and nitrocellulose. Examples of antifoaming agents and leveling agents include anionic active agents, nonionic active agents, and cationic active agents.
金属酸化物透明導電層の表面にモノカルボン酸金属塩溶液を塗布する方法としては、刷毛塗り法、浸漬法、スピンコート法、スプレー法、スクリーン印刷法、ロールコート法、インクジェット方式によるパターン形成など、既知のいずれの方法を用いてもよい。そして、加熱したホットプレートなどを用いて塗布膜を加熱し、モノカルボン酸金属塩が均一に金属酸化物透明導電層の表面に残存するように溶媒を除去する。塗布膜の加熱温度は、使用している溶媒の沸点付近が好ましく、例えば溶媒としてエタノールを用いる場合は７０℃〜１３０℃が好ましい。そして、溶媒を除去した後に焼成することにより、金属酸化物透明導電層上に金属酸化物膜の下引き層を形成する。 Examples of methods for applying a monocarboxylic acid metal salt solution to the surface of the metal oxide transparent conductive layer include brush coating, dipping, spin coating, spraying, screen printing, roll coating, and ink jet patterning. Any known method may be used. And a coating film is heated using the heated hotplate etc., and a solvent is removed so that monocarboxylic acid metal salt may remain on the surface of a metal oxide transparent conductive layer uniformly. The heating temperature of the coating film is preferably near the boiling point of the solvent used. For example, when ethanol is used as the solvent, it is preferably 70 ° C to 130 ° C. And by baking after removing a solvent, the undercoating layer of a metal oxide film is formed on a metal oxide transparent conductive layer.
金属酸化物透明導電層上に金属酸化物膜の下引き層を形成する際の焼成方法としては、ヒータープレートや焼成炉などを用いた全面焼成方法や、紫外線、マイクロウェーブを照射することによる局所焼成方法など既知の方法を用いることができ、これらの方法を併用しても良い。また、全面焼成の際の焼成温度は、塗布したモノカルボン酸金属塩から生成するモノカルボン酸由来の分解物を表面から除去でき、均質な金属酸化物膜の下引き層が得られる温度を適宜選択すれば良い。そのなかで、モノカルボン酸由来の分解物がより飛散しやすく、より均質な金属酸化物膜の下引き層を得るためには、２５０℃〜６００℃の温度範囲で焼成する事が好適である。 As a baking method when forming the undercoat layer of the metal oxide film on the metal oxide transparent conductive layer, a whole surface baking method using a heater plate, a baking furnace or the like, or a local method by irradiating ultraviolet rays or microwaves. Known methods such as a firing method can be used, and these methods may be used in combination. In addition, the firing temperature at the time of the entire surface firing is suitably a temperature at which a decomposition product derived from a monocarboxylic acid generated from the applied monocarboxylic acid metal salt can be removed from the surface, and a homogeneous metal oxide film undercoat layer is obtained. Just choose. Among them, the decomposition product derived from monocarboxylic acid is more likely to be scattered, and in order to obtain a more uniform undercoat layer of the metal oxide film, it is preferable to fire at a temperature range of 250 ° C. to 600 ° C. .
色素増感型太陽電池の受光電極を作成する際には、金属酸化物膜の下引き層の表面に半導体粒子層を形成し、半導体粒子層の表面に色素を吸着させる。半導体粒子層を形成する際に用いられる半導体粒子としては、色素増感型太陽電池に用いられることが知られているいずれの半導体粒子を用いても良い。半導体粒子としては、例えば、酸化チタンや酸化ニオブが好適に用いられる。また本発明に用いられる半導体粒子は、色素を吸着できる面積をより広くするために数ナノメートルから数マイクロメートルサイズの半導体粒子が好ましい。半導体粒子は、２種類以上の粒子サイズ分布の異なる粒子を混合して用いてもよい。下引き層の表面に半導体粒子層を形成する方法としては、半導体粒子の分散液またはコロイド溶液をスクリーン印刷法、スピン法、スプレー法、ローラ法、ディップ法などにより塗布し、塗布膜を加熱、焼成処理することが好ましい。半導体粒子層は単層や半導体の種類が異なる多層のいずれを用いても良い。 When preparing a light-receiving electrode of a dye-sensitized solar cell, a semiconductor particle layer is formed on the surface of the undercoat layer of the metal oxide film, and the dye is adsorbed on the surface of the semiconductor particle layer. As the semiconductor particles used when forming the semiconductor particle layer, any semiconductor particles known to be used in dye-sensitized solar cells may be used. As the semiconductor particles, for example, titanium oxide or niobium oxide is preferably used. Further, the semiconductor particles used in the present invention are preferably semiconductor particles having a size of several nanometers to several micrometers in order to increase the area capable of adsorbing the dye. The semiconductor particles may be used by mixing two or more kinds of particles having different particle size distributions. As a method of forming a semiconductor particle layer on the surface of the undercoat layer, a dispersion or colloidal solution of semiconductor particles is applied by a screen printing method, a spin method, a spray method, a roller method, a dip method, and the coating film is heated. Baking treatment is preferred. The semiconductor particle layer may be either a single layer or a multilayer having different types of semiconductors.
また、半導体粒子層の表面に吸着させる色素は、色素増感型太陽電池用色素として用いることが知られているいずれの色素を用いても良い。中でも、ルテニウム錯体色素などの錯体色素またはメチン色素が好ましい。さらに、光電変換の波長域をできるだけ広くし、かつ光電変換効率を上げるため、二種類以上の色素を混合してもよい。そして、目的とする光源の波長域と強度分布に合わせるように、混合する色素とその割合を選ぶことができる。半導体粒子層に色素を吸着させる方法としては、これまで知られている方法を用いることができるが、例えば、半導体粒子層を有する基板を色素溶液中に浸漬するか、または、乾燥した半導体粒子層の表面に色素溶液をスプレー法などで塗布して吸着させる方法などが好適に用いられる。その際に使用する溶媒は、色素の溶解性と吸着方法に応じて適宜選択する。色素の半導体粒子層１ｍ２あたりに対する吸着量は０．０１〜１００ミリモルが好ましい。 Moreover, as the dye adsorbed on the surface of the semiconductor particle layer, any dye known to be used as a dye for dye-sensitized solar cells may be used. Among these, a complex dye such as a ruthenium complex dye or a methine dye is preferable. Furthermore, in order to make the wavelength range of photoelectric conversion as wide as possible and increase the photoelectric conversion efficiency, two or more kinds of dyes may be mixed. And the pigment | dye to mix and its ratio can be selected so that it may match with the wavelength range and intensity distribution of the target light source. As a method of adsorbing the dye to the semiconductor particle layer, a method known so far can be used. For example, a substrate having a semiconductor particle layer is immersed in a dye solution or dried. A method in which a dye solution is applied to the surface of the substrate by a spray method or the like is adsorbed. The solvent used at that time is appropriately selected according to the solubility of the dye and the adsorption method. The adsorption amount of dye per 1 m 2 of semiconductor particle layer is preferably 0.01 to 100 mmol.
次に実施例によって本発明を更に詳細に説明する。
（実施例１）
（１）下引き層の形成
金属酸化物透明導電層として、フッ素をドープした酸化スズ導電層（ＦＴＯ）を有した１５ｍｍ×２０ｍｍ角のガラス基板（日本板硝子株式会社製、シート抵抗１０Ω／□）を用いた。基板の金属酸化物透明導電層上１５ｍｍ×５ｍｍ角の範囲にメンディングテープを貼付け、残りの金属酸化物透明導電層表面１５ｍｍ×１５ｍｍ角の範囲に１．０質量％カプロン酸スズ−エタノール溶液（Ａ−１）をスピンコート法で塗布した。そして、この基板を８０℃に調整したホットプレート上に置き溶媒を除去した後、メンディングテープを剥がしてマッフル炉にて５００℃で３０分間焼成して酸化スズの下引き層を形成した。
（２）半導体粒子層の調製
（１）の操作により得られた１５ｍｍ×１５ｍｍの下引き層上の中央に、市販のナノサイズ酸化チタンペースト（ＳＯＬＡＲＯＮＩＸ ＳＡ社製 ＮａｎｏｘｉｄｅＴ／ＳＰ）を、スクリーン印刷にて４ｍｍ×４ｍｍ角の範囲で塗布し、電気炉にて５００℃で３０分間加熱して製膜した。実施例１の光増感型太陽電池における受光面積は１６ｍｍ２となり、加熱後の酸化チタン膜層の厚みは約１７μｍであった。
（３）色素の吸着
増感色素（ＳＯＬＡＲＯＮＩＸ ＳＡ社製 Ｒｕｔｈｅｎｉｕｍ５３５−ｂｉｓＴＢＡ）を、エタノールに溶解し、濃度５×１０−４Ｍに調製した。この色素溶液に（２）で調製した基板を２０時間浸して色素を吸着させた後、電極表面をアセトニトリルで洗浄して乾燥させ、受光電極を得た。
Next, the present invention will be described in more detail by way of examples.
Example 1
(1) Formation of undercoat layer 15 mm × 20 mm square glass substrate having a tin oxide conductive layer (FTO) doped with fluorine as a metal oxide transparent conductive layer (Nippon Sheet Glass Co., Ltd., sheet resistance 10Ω / □) Was used. A mending tape is affixed to a 15 mm × 5 mm square area on the metal oxide transparent conductive layer on the substrate, and a 1.0 mass% tin caproate-ethanol solution (15% × 15 mm square surface on the remaining metal oxide transparent conductive layer surface ( A-1) was applied by spin coating. Then, this substrate was placed on a hot plate adjusted to 80 ° C. to remove the solvent, and then the mending tape was peeled off and baked at 500 ° C. for 30 minutes in a muffle furnace to form an undercoat layer of tin oxide.
(2) Preparation of semiconductor particle layer In the center of the undercoat layer of 15 mm × 15 mm obtained by the operation of (1), a commercially available nano-sized titanium oxide paste (Nanoxide T / SP manufactured by SOLARONIX SA) is used for screen printing. 4 mm × 4 mm square, and heated in an electric furnace at 500 ° C. for 30 minutes to form a film. The light receiving area in the photosensitized solar cell of Example 1 was 16 mm 2 , and the thickness of the titanium oxide film layer after heating was about 17 μm.
(3) Adsorption of dye Sensitizing dye (Ruthenium 535-bisTBA manufactured by SOLARONIX SA) was dissolved in ethanol to prepare a concentration of 5 × 10 −4 M. The substrate prepared in (2) was immersed in this dye solution for 20 hours to adsorb the dye, and then the electrode surface was washed with acetonitrile and dried to obtain a light-receiving electrode.
（４）電解質溶液の調整
下記処方にて電解質溶液を調製した。
ヨウ化リチウム ０．０６７ｇ
ヨウ素 ０．０６３５ｇ
４−ｔーブチルピリジン ０．３３７５ｇ
１−プロピル−２，３−ジメチル−ヨウ化イミダゾリウム ０．７９７５ｇ
アセトニトリル ５ｍＬ
（５）色素増感型太陽電池セルの組み立て
図１のように色素増感型太陽電池セルの試験サンプルを組み立てた。対電極にはスパッタリング法により製膜した白金を持つフッ素ドープ酸化スズ層を用いた。
（６）光電変換効率（η）の測定方法
色素増感型太陽電池の出力特性は、ＪＩＳ Ｃ８９１３：１９９８ のシリコン結晶系太陽電池セルの出力測定方法に準拠した方法で測定した。３００Ｗソーラーシュミレーター（山下電装株式会社製 ＹＳＳ−８０）にＡＭ１．５Ｇ相当のエアマスフィルターを組み合わせ、２次基準 Ｓｉ 太陽電池で１００ｍＷ／ｃｍ２の光量に調整して測定用光源とし、色素増感型太陽電池セルの試験サンプルに光照射をしながらポテンショスタット（北斗電工株式会社製，ＨＳＶ−１００）を使用してＩ‐Ｖカーブ特性を測定し、Ｉ‐Ｖカーブ特性測定から得られた開放電圧（Ｖｏｃ）、短絡電流（Ｉｓｃ）、フィルファクター（ＦＦ）を導出した。そして、短絡電流密度（Ｊｓｃ）、および光電変換効率（η）を以下の式１、２を用いて算出した。結果を表２に示す。
(4) Preparation of electrolyte solution An electrolyte solution was prepared according to the following formulation.
Lithium iodide 0.067g
Iodine 0.0635g
4-tert-butylpyridine 0.3375 g
1-propyl-2,3-dimethyl-imidazolium iodide 0.7975 g
Acetonitrile 5mL
(5) Assembly of dye-sensitized solar cell A test sample of the dye-sensitized solar cell was assembled as shown in FIG. For the counter electrode, a fluorine-doped tin oxide layer having platinum formed by sputtering was used.
(6) Measuring method of photoelectric conversion efficiency (η) The output characteristics of the dye-sensitized solar cell were measured by a method based on the output measuring method of the silicon crystal solar cell of JIS C8913: 1998. A 300W solar simulator (YSS-80 manufactured by Yamashita Denso Co., Ltd.) is combined with an air mass filter equivalent to AM1.5G and adjusted to a light intensity of 100 mW / cm 2 with a secondary standard Si solar cell to obtain a light source for measurement. Open-circuit voltage obtained by measuring IV curve characteristics using a potentiostat (HSV-100, manufactured by Hokuto Denko Co., Ltd.) while irradiating a test sample of a solar battery cell with light. (Voc), short circuit current (Isc), and fill factor (FF) were derived. And the short circuit current density (Jsc) and the photoelectric conversion efficiency ((eta)) were computed using the following
（実施例２、比較例２）
実施例１における（１）の工程、即ち金属酸化物透明導電層の上に金属酸化物膜の下引き層を形成する工程を表１に示す塗布液（Ａ−２、Ａ−６）を用いて行った。そして、（２）の操作により下引き層の上に厚み１７μｍの半導体粒子層を形成し、以後、実施例１と同様に（３）〜（５）の操作により色素増感型太陽電池を作成した。そして、（６）の操作により光電変換効率（η）を求めた。結果を表２に示す。
(Example 2, comparative example 2)
The coating liquid (A-2, A-6) shown in Table 1 is used as the step (1) in Example 1, that is, the step of forming the undercoat layer of the metal oxide film on the metal oxide transparent conductive layer. I went. Then, a semiconductor particle layer having a thickness of 17 μm is formed on the undercoat layer by the operation of (2), and thereafter dye-sensitized solar cells are prepared by the operations of (3) to (5) in the same manner as in Example 1. did. And the photoelectric conversion efficiency ((eta)) was calculated | required by operation of (6). The results are shown in Table 2.
（比較例１）
実施例１における（１）の工程、即ち金属酸化物透明導電層の上に金属酸化物膜の下引き層を形成する工程を行わなかった。そして、（２）の操作により金属酸化物透明導電層の上に厚み１７μｍの半導体粒子層を形成し、以後、実施例１と同様に（３）〜（５）の操作により色素増感型太陽電池を作成した。そして、（６）の操作により光電変換効率（η）を求めた。結果を表２に示す。
(Comparative Example 1)
The step (1) in Example 1, that is, the step of forming the undercoat layer of the metal oxide film on the metal oxide transparent conductive layer was not performed. Then, a semiconductor particle layer having a thickness of 17 μm is formed on the metal oxide transparent conductive layer by the operation (2). Thereafter, the dye-sensitized solar cell is operated by the operations (3) to (5) in the same manner as in Example 1. A battery was created. And the photoelectric conversion efficiency ((eta)) was calculated | required by operation of (6). The results are shown in Table 2.
（実施例３〜５）
実施例１における（１）の工程、即ち金属酸化物透明導電層の上に下引き層を形成する工程を表１に示す塗布液（Ａ−３、Ａ−４、Ａ−５）を用いて行った。そして、（２）の操作により金属酸化物膜の下引き層の上に厚み１０μｍの半導体粒子層を形成し、以後、実施例１と同様に（３）〜（５）の操作により色素増感型太陽電池を作成した。そして、（６）の操作により光電変換効率（η）を求めた。結果を表３に示す。
（比較例３）
実施例１における（１）の工程、即ち金属酸化物透明導電層の上に金属酸化物膜の下引き層を形成する工程を行わなかった。そして、（２）の操作により金属酸化物透明導電層の上に厚み１０μｍの半導体粒子層を形成し、以後、実施例1と同様に（３）〜（５）の操作により色素増感型太陽電池を作成した。そして、（６）の操作により光電変換効率（η）を求めた。結果を表３に示す。
(Examples 3 to 5)
The coating liquid (A-3, A-4, A-5) shown in Table 1 is used for the step (1) in Example 1, that is, the step of forming the undercoat layer on the metal oxide transparent conductive layer. went. Then, a semiconductor particle layer having a thickness of 10 μm is formed on the undercoat layer of the metal oxide film by the operation of (2), and thereafter dye sensitization is performed by the operations of (3) to (5) as in Example 1. Type solar cell was created. And the photoelectric conversion efficiency ((eta)) was calculated | required by operation of (6). The results are shown in Table 3.
(Comparative Example 3)
The step (1) in Example 1, that is, the step of forming the undercoat layer of the metal oxide film on the metal oxide transparent conductive layer was not performed. Then, a semiconductor particle layer having a thickness of 10 μm is formed on the metal oxide transparent conductive layer by the operation (2). Thereafter, the dye-sensitized solar cell is operated by the operations (3) to (5) in the same manner as in Example 1. A battery was created. And the photoelectric conversion efficiency ((eta)) was calculated | required by operation of (6). The results are shown in Table 3.
表２に記載した実施例１〜２、比較例１〜２の色素増感型太陽電池用電極の半導体粒子層の厚みは１７μｍであった。表２の結果から、本発明のモノカルボン酸金属塩を使用した実施例１〜２は、金属酸化物膜の下引き層を有さない比較例１に対して、開放電圧（Ｖｏｃ）と、短絡電流密度（Ｊｓｃ）が共に高くなり、光電変換効率（η）が高かった。対して、モノカルボン酸金属塩の代わりに塩化錫−エタノール溶液を使用した比較例２は、開放電圧（Ｖｏｃ）は高くなるが、短絡電流密度（Ｊｓｃ）が低くなり、光電変換効率（η）は、金属酸化物膜の下引き層を有さない比較例１と同程度であった。
表３に記載した実施例３〜５、比較例３の色素増感型太陽電池用電極の半導体粒子層の厚みは１０μｍであった。表３の結果から、本発明のモノカルボン酸金属塩を使用した実施例３〜５は、金属酸化物膜の下引き層を有さない比較例３に対して、開放電圧（Ｖｏｃ）と、短絡電流密度（Ｊｓｃ）が共に高くなり、光電変換効率（η）が高かった。
The thickness of the semiconductor particle layer of the electrodes for dye-sensitized solar cells of Examples 1-2 and Comparative Examples 1-2 described in Table 2 was 17 μm. From the results of Table 2, Examples 1-2 using the monocarboxylic acid metal salt of the present invention have an open circuit voltage (Voc) compared to Comparative Example 1 having no metal oxide film undercoat layer, Both the short circuit current density (Jsc) was high and the photoelectric conversion efficiency (η) was high. On the other hand, Comparative Example 2 using a tin chloride-ethanol solution instead of the monocarboxylic acid metal salt increases the open-circuit voltage (Voc) but decreases the short-circuit current density (Jsc), and the photoelectric conversion efficiency (η) Was comparable to Comparative Example 1 having no undercoat layer of the metal oxide film.
The thickness of the semiconductor particle layer of the electrodes for dye-sensitized solar cells of Examples 3 to 5 and Comparative Example 3 described in Table 3 was 10 μm. From the results of Table 3, Examples 3 to 5 using the monocarboxylic acid metal salt of the present invention have an open circuit voltage (Voc) compared to Comparative Example 3 having no metal oxide film undercoat layer, Both the short circuit current density (Jsc) was high and the photoelectric conversion efficiency (η) was high.
１ 基板
２ 金属酸化物透明導電層
３ 下引き層
４ 半導体粒子層
５ 色素
６ 電解質層
７ 対電極
８ 基板
２〜５ 受光電極
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