JP2007018951A - Electrode for dye-sensitized solar cell - Google Patents
Electrode for dye-sensitized solar cell Download PDFInfo
- Publication number
- JP2007018951A JP2007018951A JP2005201323A JP2005201323A JP2007018951A JP 2007018951 A JP2007018951 A JP 2007018951A JP 2005201323 A JP2005201323 A JP 2005201323A JP 2005201323 A JP2005201323 A JP 2005201323A JP 2007018951 A JP2007018951 A JP 2007018951A
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- JP
- Japan
- Prior art keywords
- metal oxide
- dye
- transparent conductive
- film
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Images
Classifications
-
- 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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- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
【課題】 支持体としてプラスチック基材を用いながら、十分な量の色素を吸着し高い電荷輸送効率を得ることができ、なおかつ多孔質酸化物膜が良好に基材に積層された、光発電性能の高い色素増感型太陽電池を製造できる、色素増感型太陽電池用電極を提供する。
【解決手段】 エレクトロスピニング法により得られた金属酸化物吐出物を破砕して得られた金属酸化物粒子を、透明導電層を備えたプラスチックフィルムのうえに積層したことを特徴とする、色素増感型太陽電池用電極。
【選択図】 図１PROBLEM TO BE SOLVED: To provide a photovoltaic power generation performance in which a sufficient amount of dye is adsorbed and high charge transport efficiency can be obtained while using a plastic substrate as a support, and a porous oxide film is well laminated on the substrate. A dye-sensitized solar cell electrode capable of producing a high-sensitivity dye-sensitized solar cell is provided.
Disclosed is a dye sensitization characterized by laminating metal oxide particles obtained by crushing a metal oxide discharge obtained by an electrospinning method on a plastic film having a transparent conductive layer. Electrode for sensitive solar cells.
[Selection] Figure 1
Description
本発明は色素増感型太陽電池用電極に関し、詳しくは、プラスチック基材を使用していながら光発電性能の高い色素増感型太陽電池を製造することができる色素増感型太陽電池用電極に関する。 The present invention relates to an electrode for a dye-sensitized solar cell, and more particularly to an electrode for a dye-sensitized solar cell that can produce a dye-sensitized solar cell with high photovoltaic power generation performance while using a plastic substrate. .
色素増感型太陽電池は、色素増感半導体微粒子を用いた光電変換素子が提案されて以来（「ネイチャー（Ｎａｔｕｒｅ）」 第３５３巻、第７３７〜７４０ページ、（１９９１年））、シリコン系太陽電池に替る新たな太陽電池として注目されている。 The dye-sensitized solar cell has been proposed since a photoelectric conversion element using dye-sensitized semiconductor fine particles was proposed (“Nature”, Vol. 353, pages 737-740, (1991)). It is attracting attention as a new solar battery that replaces batteries.
プラスチック基材を用いた色素増感型太陽電池は、柔軟化や軽量化が可能であり、結晶性の金属酸化物微粒子を基材上の透明導電層に固着することで電荷輸送効率の高い太陽電池用電極の開発が検討されている。しかし、透明導電層上に固着された金属酸化物微粒子は、取り扱い時に粉末状で脱離したり電解液中で剥離したりする問題がある。 Dye-sensitized solar cells using plastic substrates can be made flexible and lightweight, and solar cells with high charge transport efficiency can be obtained by fixing crystalline metal oxide particles to the transparent conductive layer on the substrate. Development of battery electrodes is under consideration. However, the metal oxide fine particles fixed on the transparent conductive layer have a problem that they are detached in a powder state or peeled off in the electrolytic solution during handling.
他方、金属酸化物を製造する方法としてエレクトロスピニング法がある。この方法においては、ポリマー等の焼失成分を含む酸化物前駆体を高いアスペクト比で基材上に吐出したのちに高温で熱処理することで金属酸化物を得る。このエレクトロスピニング法を利用して、ガラス基材に金属酸化物の層を設けた色素増感型太陽電池用電極が既に知られている。 On the other hand, there is an electrospinning method as a method for producing a metal oxide. In this method, an oxide precursor containing a burning component such as a polymer is discharged on a substrate with a high aspect ratio and then heat-treated at a high temperature to obtain a metal oxide. An electrode for a dye-sensitized solar cell in which a metal oxide layer is provided on a glass substrate using this electrospinning method is already known.
上述の色素増感型太陽電池用電極においては、金属酸化物前駆体をガラス基板上の透明導電層のうえに高アスペクト比の状態で吐出して堆積したのち、高温で焼成することで金属酸化物層を得ている。この焼成の際に金属酸化物の自己収縮によって金属酸化物が透明導電層から剥離する傾向にあり、単にエレクトロスピニング法によって金属酸化物の層を設けても、十分に高い比表面積と高い電荷輸送効率とを達成することはできない。さらにガラス基材のうえでの金属酸化物の焼成工程自体が４００℃以上で行なわれるため、この技術をプラスチック基材を用いる色素増感型太陽電池用電極に適用するのは困難である。 In the dye-sensitized solar cell electrode described above, the metal oxide precursor is ejected and deposited in a high aspect ratio state on the transparent conductive layer on the glass substrate, and then fired at a high temperature to oxidize the metal. The material layer is obtained. During this firing, the metal oxide tends to peel from the transparent conductive layer due to self-shrinkage of the metal oxide, and even if a metal oxide layer is provided by simply electrospinning, a sufficiently high specific surface area and high charge transport Efficiency cannot be achieved. Further, since the metal oxide firing step itself on the glass substrate is performed at 400 ° C. or higher, it is difficult to apply this technique to a dye-sensitized solar cell electrode using a plastic substrate.
本発明は、プラスチック基材を用いながら、十分な量の色素を吸着し高い電荷輸送効率を得ることができ、なおかつ多孔質酸化物膜が剥離することなく良好な密着性で基材に積層された、光発電性能の高い色素増感型太陽電池を製造できる、色素増感型太陽電池用電極を提供することを目的とする。 In the present invention, while using a plastic substrate, a sufficient amount of dye can be adsorbed to obtain high charge transport efficiency, and the porous oxide film is laminated on the substrate with good adhesion without peeling off. Another object of the present invention is to provide a dye-sensitized solar cell electrode capable of producing a dye-sensitized solar cell with high photovoltaic power generation performance.
すなわち本発明は、エレクトロスピニング法により得られた金属酸化物吐出物を破砕して得られた金属酸化物粒子を、透明導電層を備えるプラスチックフィルムの透明導電層のうえに積層したことを特徴とする、色素増感型太陽電池用電極である。 That is, the present invention is characterized in that metal oxide particles obtained by crushing a metal oxide discharge obtained by an electrospinning method are laminated on a transparent conductive layer of a plastic film provided with a transparent conductive layer. This is an electrode for a dye-sensitized solar cell.
本発明によれば、プラスチック基材を用いながら、十分な量の色素を吸着し高い電荷輸送効率を得ることができ、なおかつ多孔質酸化物膜が剥離することなく良好な密着性で基材に積層された、光発電性能の高い色素増感型太陽電池を製造できる、色素増感型太陽電池用電極を提供することができる。 According to the present invention, while using a plastic substrate, a sufficient amount of dye can be adsorbed and high charge transport efficiency can be obtained, and the porous oxide film can be adhered to the substrate without peeling off. It is possible to provide a dye-sensitized solar cell electrode capable of producing a laminated dye-sensitized solar cell having high photovoltaic power generation performance.
以下、本発明を詳細に説明する。
［金属酸化物粒子］
本発明において、透明導電層を備えたプラスチックフィルムのうえに積層する金属酸化物粒子は、エレクトロスピニング法で得られた金属酸化物吐出物を破砕したものである。
Hereinafter, the present invention will be described in detail.
[Metal oxide particles]
In this invention, the metal oxide particle laminated | stacked on the plastic film provided with the transparent conductive layer is what crushed the metal oxide discharge obtained by the electrospinning method.
金属酸化物吐出物は、金属酸化物前駆体およびこれとの錯体を形成する化合物の混合物と、溶媒と、高アスペクト形成性の溶質とから成る溶液を、エレクトロスピニング法にて捕集基板上に吐出して累積および焼成させてることによって得ることができる。この金属酸化物吐出物は高アスペクト比であり、本発明ではこれを破砕して用いる。 The metal oxide discharge product is a solution comprising a mixture of a metal oxide precursor and a compound that forms a complex with the precursor, a solvent, and a high aspect-forming solute on a collection substrate by electrospinning. It can be obtained by discharging and accumulating and firing. This metal oxide discharge has a high aspect ratio and is used after being crushed in the present invention.
金属酸化物前駆体としては、例えば、チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラノルマルプロポキシド、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンテトラターシャリーブトキシドを用いることができるが、入手のしやすさより、チタンテトライソプロポキシド、チタンテトラノルマルブトキシドが好ましい。 As the metal oxide precursor, for example, titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetratertiary butoxide can be used. Titanium tetraisopropoxide and titanium tetranormal butoxide are preferred for ease of treatment.
金属酸化物前駆体との錯体を形成する化合物としては、例えば、カルボン酸、アミド、エステル、ケトン、ホスフィン、エーテル、アルコール、チオールなどの配位性の化合物を用いることができる。好ましくは、アセチルアセトン、酢酸、テトラヒドロフランを用いる。金属酸化物前駆体との錯体を形成する化合物の添加量は、金属酸化物前駆体に対して、例えば０．５等量以上、好ましくは１〜１０等量である。 As a compound that forms a complex with a metal oxide precursor, for example, a coordination compound such as carboxylic acid, amide, ester, ketone, phosphine, ether, alcohol, thiol, or the like can be used. Preferably, acetylacetone, acetic acid, and tetrahydrofuran are used. The amount of the compound that forms a complex with the metal oxide precursor is, for example, 0.5 equivalents or more, preferably 1 to 10 equivalents, relative to the metal oxide precursor.
溶媒としては、例えばヘキサン等の脂肪族炭化水素；トルエン、テトラリンといった芳香族炭化水素；ｎ−ブタノール、エチレングリコールといったアルコール；テトラヒドロフラン、ジオキサンといったエーテル；ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミド、ｎ−メチルアミノピリジン、水を用いることができるが、各溶質への親和性の点でＮ，Ｎ−ジメチルホルムアミド、水が好ましい。溶媒は単独で用いてもまた複数組み合わせて用いてもよい。溶媒の量としては、金属酸化物前駆体の重量に対して、好ましくは０．５〜３０倍量、さらに好ましくは０．５〜２０倍量である。 Examples of the solvent include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as toluene and tetralin; alcohols such as n-butanol and ethylene glycol; ethers such as tetrahydrofuran and dioxane; dimethyl sulfoxide, N, N-dimethylformamide, and n-methyl. Aminopyridine and water can be used, but N, N-dimethylformamide and water are preferred from the viewpoint of affinity for each solute. The solvents may be used alone or in combination. The amount of the solvent is preferably 0.5 to 30 times, more preferably 0.5 to 20 times the weight of the metal oxide precursor.
高アスペクト比形成性の溶質としては、取り扱いの点や焼成によって除去される必要があることから有機高分子を用いることが好ましい。例えば、ポリエチレンオキシド、ポリビニルアルコール、ポリビニルエステル、ポリビニルエーテル、ポリビニルピリジン、ポリアクリルアミド、エーテルセルロース、ペクチン、澱粉、ポリ塩化ビニル、ポリアクリロニトリル、ポリ乳酸、ポリグリコール酸、ポリ乳酸−ポリグリコール酸共重合体、ポリカプロラクトン、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリスチレン、ポリカーボネート、ポリヘキサメチレンカーボネート、ポリアリレート、ポリビニルイソシアネート、ポリブチルイソシアネート、ポリメチルメタクリレート、ポリエチルメタクリレート、ポリノルマルプロピルメタクリレート、ポリノルマルブチルメタクリレート、ポリメチルアクリレート、ポリエチルアクリレート、ポリブチルアクリレート、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリエチレンナフタレート、ポリパラフェニレンテレフタラミド、ポリパラフェニレンテレフタラミド−３，４′―オキシジフェニレンテレフタラミド共重合体、ポリメタフェニレンイソフタラミド、セルロースジアセテート、セルローストリアセテート、メチルセルロース、プロピルセルロース、ベンジルセルロース、フィブロイン、天然ゴム、ポリビニルアセテート、ポリビニルメチルエーテル、ポリビニルエチルエーテル、ポリビニルノルマルプロピルエーテル、ポリビニルイソプロピルエーテル、ポリビニルノルマルブチルエーテル、ポリビニルイソブチルエーテル、ポリビニルターシャリーブチルエーテル、ポリビニリデンクロリド、ポリ（Ｎ−ビニルピロリドン）、ポリ（Ｎ−ビニルカルバゾル）、ポリ（４−ビニルピリジン）、ポリビニルメチルケトン、ポリメチルイソプロペニルケトン、ポリプロピレンオキシド、ポリシクロペンテンオキシド、ポリスチレンサルホン、ナイロン６、ナイロン６６、ナイロン１１、ナイロン１２、ナイロン６１０、ナイロン６１２、並びにこれらの共重合体を例示することができる。中でも溶媒に対する溶解性の点から、ポリアクリロニトリル、ポリエチレンオキシド、ポリビニルアルコール、ポリビニルアセテート、ポリ（Ｎ−ビニルピロリドン）、ポリ乳酸、ポリ塩化ビニル、セルローストリアセテートが好ましい。 As the high aspect ratio-forming solute, it is preferable to use an organic polymer because it needs to be removed by handling or firing. For example, polyethylene oxide, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl pyridine, polyacrylamide, ether cellulose, pectin, starch, polyvinyl chloride, polyacrylonitrile, polylactic acid, polyglycolic acid, polylactic acid-polyglycolic acid copolymer , Polycaprolactone, polybutylene succinate, polyethylene succinate, polystyrene, polycarbonate, polyhexamethylene carbonate, polyarylate, polyvinyl isocyanate, polybutyl isocyanate, polymethyl methacrylate, polyethyl methacrylate, polynormal propyl methacrylate, polynormal butyl methacrylate, Polymethyl acrylate, polyethyl acrylate, polybutyl acrylate Polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polyparaphenylene terephthalamide, polyparaphenylene terephthalamide-3,4'-oxydiphenylene terephthalamide copolymer, polymetaphenylene isophthalamide, cellulose di Acetate, cellulose triacetate, methyl cellulose, propyl cellulose, benzyl cellulose, fibroin, natural rubber, polyvinyl acetate, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl normal propyl ether, polyvinyl isopropyl ether, polyvinyl normal butyl ether, polyvinyl isobutyl ether, polyvinyl tertiary butyl ether , Polyvinylidene chloride, poly (N-vinylpyrrolide) ), Poly (N-vinylcarbazole), poly (4-vinylpyridine), polyvinylmethylketone, polymethylisopropenylketone, polypropylene oxide, polycyclopentene oxide, polystyrene sulfone, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, and copolymers thereof. Of these, polyacrylonitrile, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, poly (N-vinylpyrrolidone), polylactic acid, polyvinyl chloride, and cellulose triacetate are preferable from the viewpoint of solubility in a solvent.
有機高分子の分子量は、分子量が低い場合は、有機高分子の添加量が大きくなり、焼成によって発生する気体が多くなり、金属酸化物の構造に欠陥が発生する可能性が高くなるので好ましくないことから、適宜設定される。好ましい分子量としては、例えばポリエチレンオキシドのうちポリエチレングリコールの場合、好ましくは１００，０００〜８，０００，０００、より好ましくは１００，０００〜６００，０００である。 The molecular weight of the organic polymer is not preferable when the molecular weight is low, since the amount of organic polymer added increases, the amount of gas generated by firing increases, and the possibility of defects occurring in the structure of the metal oxide increases. Therefore, it is set appropriately. The molecular weight is preferably 100,000 to 8,000,000, more preferably 100,000 to 600,000, for example, in the case of polyethylene glycol among polyethylene oxides.
高アスペクト比形成性の溶質の添加量は、高アスペクト比の形成される濃度範囲で可能な限り少ないことが金属酸化物の緻密性向上の点から好ましく、金属酸化物前駆体の重量に対して好ましくは０．１〜２００重量％、さらに好ましくは１〜１５０重量％である。 The addition amount of the high aspect ratio-forming solute is preferably as small as possible in the concentration range where the high aspect ratio is formed from the viewpoint of improving the denseness of the metal oxide, and is based on the weight of the metal oxide precursor. Preferably it is 0.1-200 weight%, More preferably, it is 1-150 weight%.
金属酸化物吐出物はエレクトロスピニング法によって製造される。エレクトロスピニング法自体は公知の方法であり、高アスペクト比形成性の基質を溶解させた溶液を電極間で形成された静電場中に吐出し、溶液を電極に向けて曳糸し、形成される高アスペクト比形成物を捕集基板上に累積することによって金属酸化物吐出物を得る方法である。金属酸化物吐出物は高アスペクト比形成性の基質を溶解させた溶媒が留去して積層体となっている状態のみならず、前記溶媒が吐出物に含まれている状態においても高アスペクト比を維持している。 The metal oxide discharge is manufactured by an electrospinning method. The electrospinning method itself is a known method, and is formed by discharging a solution in which a high aspect ratio forming substrate is dissolved into an electrostatic field formed between electrodes, and spinning the solution toward the electrodes. In this method, the metal oxide discharge is obtained by accumulating the high aspect ratio formation on the collection substrate. The metal oxide discharge has a high aspect ratio not only in the state in which the solvent in which the substrate having the high aspect ratio forming property is dissolved is distilled to form a laminate, but also in the state where the solvent is contained in the discharge. Is maintained.
通常、エレクトロスピニングは室温で行われるが、溶媒の揮発が不十分な場合など、必要に応じて紡糸雰囲気の温度を制御したり、捕集基板の温度を制御してもよい。 Usually, electrospinning is performed at room temperature, but the temperature of the spinning atmosphere or the temperature of the collection substrate may be controlled as necessary, for example, when the volatilization of the solvent is insufficient.
前述の電極は、金属、無機物、または有機物のいかなるものでも導電性を示しさえすれば用いることができ、また、絶縁物上に導電性を示す金属、無機物、または有機物の薄膜を持つものであっても良い。 The above-described electrode can be used as long as it has conductivity, and any metal, inorganic, or organic material has a thin film of conductive metal, inorganic, or organic material on an insulator. May be.
また、静電場は一対又は複数の電極間で形成されており、いずれの電極に高電圧を印加しても良い。これは、例えば電圧値が異なる高電圧の電極が２つ（例えば１５ｋＶと１０ｋＶ）と、アースにつながった電極の合計３つの電極を用いる場合も含み、または３つを越える数の電極を使う場合も含む。 The electrostatic field is formed between a pair or a plurality of electrodes, and a high voltage may be applied to any of the electrodes. This includes, for example, using two high-voltage electrodes with different voltage values (for example, 15 kV and 10 kV) and a total of three electrodes connected to the ground, or when using more than three electrodes. Including.
エレクトロスピニング法によって吐出を行された高アスペクト比の金属酸化物吐出物は捕集基板である電極上に吐出・堆積される。次にこの金属酸化物吐出物を焼成する。焼成には、一般的な電気炉を用いることができるが、必要に応じて炉内の気体を置換可能な電気炉を用いてもよい。また、焼成温度は、十分な結晶成長及び制御できる条件が好ましい。金属酸化物が酸化チタンの場合、アナターゼ型の結晶成長とルチル型の結晶転位を抑制するために、好ましくは３００〜９００℃、さらに好ましくは５００〜８００℃で焼成するとよい。このようにして得られる高アスペクト比の金属酸化物吐出物は、例えば平均径が５０〜１０００ｎｍであり長さが１００μｍ以上であり、ＢＥＴ比表面積が０．１〜２００ｍ２／ｇである。 The high-aspect-ratio metal oxide ejected by the electrospinning method is ejected and deposited on the electrode which is the collection substrate. Next, this metal oxide discharge is fired. For firing, a general electric furnace can be used, but an electric furnace capable of replacing the gas in the furnace may be used as necessary. In addition, the firing temperature is preferably a condition that allows sufficient crystal growth and control. When the metal oxide is titanium oxide, it is preferably fired at 300 to 900 ° C., more preferably 500 to 800 ° C. in order to suppress anatase type crystal growth and rutile type crystal dislocation. The high aspect ratio metal oxide discharge obtained in this manner has, for example, an average diameter of 50 to 1000 nm, a length of 100 μm or more, and a BET specific surface area of 0.1 to 200 m 2 / g.
本発明では、この金属酸化物吐出物を粉砕して金属酸化物粒子として用いる。金属酸化物粒子のアスペクト比は、良好な電化輸送効率を得るために、好ましくは３〜３００、さらに好ましくは５〜１００であり、金属酸化物粒子の大きさは、短径が好ましくは５０〜１０００ｎｍ、長径が好ましくは０．１〜５００μｍである。 In the present invention, the metal oxide discharge is pulverized and used as metal oxide particles. The aspect ratio of the metal oxide particles is preferably from 3 to 300, more preferably from 5 to 100, in order to obtain good charge transport efficiency, and the size of the metal oxide particles is preferably from 50 to 50 The major axis is preferably 1000 nm and 0.1 to 500 μm.
［多孔質半導体層の形成］
多孔質半導体層を設けるために使う塗液は、エレクトロスピニング法により得られた金属酸化物粒子を分散媒に分散させた分散液である。
[Formation of porous semiconductor layer]
The coating liquid used for providing the porous semiconductor layer is a dispersion liquid in which metal oxide particles obtained by an electrospinning method are dispersed in a dispersion medium.
金属酸化物粒子は、焼成後の金属酸化物吐出物を、例えば乳鉢、乾式ミルで破砕するがことで製造することができる。得られた金属酸化物粒子を分散媒に分散することで塗液が得られる。また塗液中に含まれる分散媒中で分散してもよい。分散媒中で、例えばボールミル、媒体攪拌型ミル、ホモジナイザーなどを利用した物理的分散、超音波処理によって分散するとよい。 The metal oxide particles can be produced by crushing the fired metal oxide discharge with, for example, a mortar or a dry mill. A coating liquid is obtained by dispersing the obtained metal oxide particles in a dispersion medium. Moreover, you may disperse | distribute in the dispersion medium contained in a coating liquid. In a dispersion medium, it is good to disperse | distribute by physical dispersion | distribution using a ball mill, a medium stirring mill, a homogenizer, etc., and ultrasonic treatment, for example.
塗液中のエレクトロスピニング法により得られた金属酸化物粒子の量は、好ましくは０．５〜９０重量％、さらに好ましくは１〜７０重量％、特に好ましくは１〜５０重量％である。０．５重量％未満であると最終的な多孔質半導体層の厚みが薄くなるため好ましくない。９０重量％を超えると粘度が高くなりすぎて塗布するのが困難となり好ましくない。 The amount of the metal oxide particles obtained by the electrospinning method in the coating liquid is preferably 0.5 to 90% by weight, more preferably 1 to 70% by weight, and particularly preferably 1 to 50% by weight. If it is less than 0.5% by weight, the final porous semiconductor layer is undesirably thin. If it exceeds 90% by weight, the viscosity becomes too high and it becomes difficult to apply, which is not preferable.
分散媒としては、水または有機溶媒、有機溶媒として好ましくはアルコールを用いる。分散媒への分散の際には、必要に応じて分散助剤を少量添加してもよい。分散助剤としては、例えば界面活性剤、酸、キレート剤を用いることができる。 As the dispersion medium, water or an organic solvent is used, and alcohol is preferably used as the organic solvent. When dispersing in a dispersion medium, a small amount of a dispersion aid may be added as necessary. As the dispersion aid, for example, a surfactant, an acid, and a chelating agent can be used.
色素の吸着量を増すために、この分散液には、さらに金属酸化物微粒子を配合することが好ましい。この金属酸化物微粒子の粒径は２〜５００ｎｍ、好ましくは３〜２００ｎｍ、さらに好ましくは５〜１５０ｎｍである。金属酸化物微粒子の粒径が２ｎｍ未満であると凝集性が著しく高く取り扱いが困難であるため好ましくない。５００ｎｍを超えると金属酸化物の比表面積が低下色素の吸着量が低下し光電効率の向上が困難であるため好ましくない。この金属酸化物微粒子の塗液中の含有量は、０．１〜５０重量％、好ましくは１〜３０重量％である。０．１重量％未満であると色素の吸着量が少なくなるため発電量が低下して好ましくない。５０重量％を超えると剥離が起こることがあり好ましくない。なお、塗液中の金属酸化物粒子と金属酸化物微粒子との合計濃度は、高い発電量を得ると共に剥離を防止する観点から、好ましくは０．６〜９０重量％である。 In order to increase the amount of dye adsorbed, it is preferable to further add metal oxide fine particles to the dispersion. The particle diameter of the metal oxide fine particles is 2 to 500 nm, preferably 3 to 200 nm, more preferably 5 to 150 nm. If the particle diameter of the metal oxide fine particles is less than 2 nm, the cohesiveness is extremely high and handling is difficult, which is not preferable. If it exceeds 500 nm, the specific surface area of the metal oxide is lowered, the amount of dye adsorbed is lowered, and it is difficult to improve the photoelectric efficiency. The content of the metal oxide fine particles in the coating solution is 0.1 to 50% by weight, preferably 1 to 30% by weight. If it is less than 0.1% by weight, the amount of dye adsorbed decreases, so the amount of power generation decreases, which is not preferable. If it exceeds 50% by weight, peeling may occur, which is not preferable. In addition, the total concentration of the metal oxide particles and the metal oxide fine particles in the coating liquid is preferably 0.6 to 90% by weight from the viewpoint of obtaining a high power generation amount and preventing peeling.
この分散液には、さらに金属酸化物の接着剤を添加してもよい。金属酸化物の接着剤としては例えば金属酸化物前駆体を用いることができる。例えば、チタンテトラメトキシド、チタンテトラエトキシド、チタンテトラノルマルプロポキシド、チタンテトライソプロポキシド、チタンテトラノルマルブトキシド、チタンテトラターシャリーブトキシド、チタン水酸化物を用いることができる。これらは単体で用いてもよく、複数組み合わせて使用してもよい。 A metal oxide adhesive may be further added to the dispersion. As the metal oxide adhesive, for example, a metal oxide precursor can be used. For example, titanium tetramethoxide, titanium tetraethoxide, titanium tetranormal propoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetratertiary butoxide, and titanium hydroxide can be used. These may be used alone or in combination.
透明導電層のうえへの塗液の塗布は、従来から塗布加工に際し慣用されている任意の方法を用いて行うことができる。例えば、ローラ法、ディッブ法、エアーナイフ法、ブレード法、ワイヤーバー法、スライドホッパー法、エクストルージョン法、カーテン法を適用することができる。汎用機によるスピン法やスプレー法を用いてもよく、凸版、オフセットおよびグラビアの３大印刷法をはじめ、凹版、ゴム版、スクリーン印刷のような湿式印刷を用いて塗布してもよい。これらの中から、液粘度やウェット厚さに応じて、好ましい製膜方法を用いることができる。塗液の塗布量は、乾燥時の支持体１ｍ２当り、好ましくは０．５〜２０ｇ／ｍ２、さらに好ましくは５〜１０ｇ／ｍ２である。 Application | coating of the coating liquid on a transparent conductive layer can be performed using the arbitrary methods conventionally conventionally used in the case of a coating process. For example, a roller method, a dip method, an air knife method, a blade method, a wire bar method, a slide hopper method, an extrusion method, and a curtain method can be applied. You may use the spin method and spray method by a general purpose machine, and you may apply using wet printing like an intaglio, a rubber plate, and screen printing, including the three major printing methods of a letterpress, an offset, and a gravure. Among these, a preferable film forming method can be used according to the liquid viscosity and the wet thickness. The coating amount of the coating solution is preferably 0.5 to 20 g / m 2 , more preferably 5 to 10 g / m 2 per 1 m 2 of the support at the time of drying.
透明導電層のうえに塗液を塗設したあと熱処理を行ない、多孔質半導体層を形成する。この熱処理は、乾燥工程で行なってもよく、乾燥後の別工程で行なってもよい。熱処理は、好ましくは１７０〜２５０℃で１〜１２０分間、さらに好ましくは１８０〜２３０℃で１〜９０分間、特に好ましくは１９０〜２２０℃で１〜６０分間の条件で行なう。この熱処理を行うことで、透明導電層を支持するフィルムの加熱による変形を防ぎながら多孔質半導体層の抵抗上昇を小さくすることができる。最終的な多孔質半導体層の厚さは、好ましくは１〜３０μｍ、さらに好ましくは２〜１０μｍであり、特に透明度を高める場合には２〜６μｍが最も好ましい。 A coating liquid is applied on the transparent conductive layer and then heat treatment is performed to form a porous semiconductor layer. This heat treatment may be performed in a drying process or in a separate process after drying. The heat treatment is preferably performed under the conditions of 170 to 250 ° C. for 1 to 120 minutes, more preferably 180 to 230 ° C. for 1 to 90 minutes, particularly preferably 190 to 220 ° C. for 1 to 60 minutes. By performing this heat treatment, an increase in resistance of the porous semiconductor layer can be reduced while preventing deformation of the film supporting the transparent conductive layer due to heating. The final thickness of the porous semiconductor layer is preferably 1 to 30 μm, more preferably 2 to 10 μm, and 2 to 6 μm is most preferable when increasing the transparency.
なお、多孔質半導体層を構成することになる金属酸化物粒子に対して粒子が強く吸収する紫外光などを照射したり、マイクロ波を照射して微粒子層を加熱することにより、粒子の間の物理的接合を強める処理を行ってもよい。 In addition, by irradiating the metal oxide particles constituting the porous semiconductor layer with ultraviolet light or the like that the particles strongly absorb, or by irradiating microwaves to heat the fine particle layer, You may perform the process which strengthens physical joining.
エレクトロスピニング法により得られた金属酸化物吐出物を破砕して得られた金属酸化物粒子からなる多孔質半導体層の形成は、電着によって金属酸化物粒子の薄膜を透明導電層のうえに担持する方法を用いて行なってもよい。すなわち、半導体微粒子を適当な低伝導度の溶媒、例えば純水、アルコールやアセトニトリル、ＴＨＦなどの極性有機溶媒、ヘキサン、クロロホルムなどの非極性有機溶媒、あるいはこれらの混合溶媒に添加し、凝集のないよう均一に分散し、電着すべき導電性樹脂シート電極と対極とを一定の間隔で平行に対向させ、この間隙に上記の分散液を注入し、両電極間に直流電圧を印加する。このようにして、分散液の濃度と電極間隔を選択することにより、基板電極に一定かつ均一な厚みの電着膜である多孔質半導体層を形成してもよい。 Formation of a porous semiconductor layer composed of metal oxide particles obtained by crushing metal oxide discharge obtained by electrospinning method is carried by supporting a thin film of metal oxide particles on a transparent conductive layer by electrodeposition You may carry out using the method to do. That is, the semiconductor fine particles are added to an appropriate low-conductivity solvent such as pure water, polar organic solvents such as alcohol, acetonitrile and THF, nonpolar organic solvents such as hexane and chloroform, or a mixed solvent thereof, so that there is no aggregation. The conductive resin sheet electrode to be electrodeposited and the counter electrode are made to face each other in parallel at a constant interval, the dispersion liquid is injected into the gap, and a DC voltage is applied between the electrodes. In this way, a porous semiconductor layer that is an electrodeposition film having a constant and uniform thickness may be formed on the substrate electrode by selecting the concentration of the dispersion and the electrode interval.
なお、多孔質半導体を担持する透明導電層が対極と電気的に短絡することを防止するな
どの目的のため、予め透明導電層の上に下塗り層を設けておくこともできる。この下塗り層としては、ＴｉＯ２、ＳｎＯ２、ＺｎＯ、Ｎｂ２Ｏ５、特にＴｉＯ２が好ましい。この下塗り層は、例えばＥｌｅｃｔｒｏｃｈｉｍ、Ａｃｔａ４０、６４３〜６５２（１９９５）に記載されているスプレーパイロリシス法の他、スパッタ法などにより設けることができる。この下塗り層の膜厚は、好ましくは５〜１０００ｎｍ、さらに好ましくは１０〜５００ｎｍである。
For the purpose of preventing the transparent conductive layer carrying the porous semiconductor from being electrically short-circuited with the counter electrode, an undercoat layer may be provided on the transparent conductive layer in advance. As the undercoat layer, TiO 2 , SnO 2 , ZnO, Nb 2 O 5 , particularly TiO 2 is preferable. This undercoat layer can be provided by, for example, a sputtering method in addition to the spray pyrolysis method described in Electrochim, Acta 40, 643 to 652 (1995). The thickness of the undercoat layer is preferably 5 to 1000 nm, more preferably 10 to 500 nm.
［プラスチックフィルム］
本発明において、透明導電層を支える支持体としてプラスチックフィルムを用いる。プラスチックフィルムとしては、ポリエステルフィルムが好ましく、このポリエステルフィルムを構成するポリエステルは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから合成される線状飽和ポリエステルである。
[Plastic film]
In the present invention, a plastic film is used as a support for supporting the transparent conductive layer. The plastic film is preferably a polyester film, and the polyester constituting the polyester film is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
かかるポリエステルの具体例として、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−ナフタレート等を例示することができる。これらの共重合体またはこれと小割合の他樹脂とのブレンドであってもよい。これらのポリエステルのうち、ポリエチレンテレフタレート、ポリエチレン−２，６−ナフタレートが力学的物性や光学物性等のバランスが良いので好ましい。 Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. It may be a blend of these copolymers or a small proportion of other resins. Among these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable because of a good balance between mechanical properties and optical properties.
特にポリエチレン−２，６−ナフタレートは機械的強度の大きさ、熱収縮率の小ささ、加熱時のオリゴマー発生量の少なさなどの点でポリエチレンテレフタレートに勝っているので最も好ましい。 In particular, polyethylene-2,6-naphthalate is most preferable because it is superior to polyethylene terephthalate in terms of mechanical strength, small thermal shrinkage, and a small amount of oligomer generated during heating.
ポリエチレンテレフタレートとしては、エチレンテレフタレート単位を好ましくは９０モル％以上、さらに好ましくは９５％以上、特に好ましくは９７％以上有するものを用いるとよい。ポリエチレン−２，６−ナフタレートとしては、ポリエチレン−２，６−ナフタレート単位を好ましくは９０モル％以上、さらに好ましくは９５％以上、特に好ましくは９７％以上有するものを用いるとよい。ポリエステルは、ホモポリマーでも、第三成分を共重合したコポリマーでもよいが、ホモポリマーが好ましい。 As the polyethylene terephthalate, those having an ethylene terephthalate unit of preferably 90 mol% or more, more preferably 95% or more, particularly preferably 97% or more may be used. As the polyethylene-2,6-naphthalate, one having a polyethylene-2,6-naphthalate unit of preferably 90 mol% or more, more preferably 95% or more, particularly preferably 97% or more may be used. The polyester may be a homopolymer or a copolymer obtained by copolymerizing the third component, but a homopolymer is preferred.
ポリエステルの固有粘度は、好ましくは０．４０ｄｌ／ｇ以上、さらに好ましくは０．４０〜０．９０ｄｌ／ｇである。固有粘度が０．４０ｄｌ／ｇ未満では工程切断が多発することがあり好ましくなく、０．９０ｄｌ／ｇを超えると溶融粘度が高いため溶融押出しが困難になり、重合時間が長く不経済であり好ましくない。 The intrinsic viscosity of the polyester is preferably 0.40 dl / g or more, more preferably 0.40 to 0.90 dl / g. If the intrinsic viscosity is less than 0.40 dl / g, process cutting may occur frequently, which is not preferable, and if it exceeds 0.90 dl / g, melt extrusion becomes difficult because of high melt viscosity, and the polymerization time is long and uneconomical. Absent.
ポリエステルは従来公知の方法で得ることができる。例えば、ジカルボン酸とグリコールの反応で直接低重合度ポリエステルを得る方法で得ることができる。また、ジカルボン酸の低級アルキルエステルとグリコールとをエステル交換反応触媒を用いて反応させた後、重合反応触媒の存在下で重合反応を行う方法で得ることができる。エステル交換反応触媒としては、従来公知のもの、例えばナトリウム、カリウム、マグネシウム、カルシウム、亜鉛、ストロンチウム、チタン、ジルコニウム、マンガン、コバルトを含む化合物を用いることができる。重合反応触媒としては、従来公知のもの、例えば三酸化アンチモン、五酸化アンチモンのようなアンチモン化合物、二酸化ゲルマニウムで代表されるようなゲルマニウム化合物、テトラエチルチタネート、テトラプロピルチタネート、テトラフェニルチタネートまたはこれらの部分加水分解物、蓚酸チタニルアンモニウム、蓚酸チタニルカリウム、チタントリスアセチルアセトネートのようなチタン化合物を用いることができる。エステル交換反応を経由して重合を行う場合は、重合反応前にエステル交換触媒を失活させる目的でトリメチルホスフェート、トリエチルホスフェート、トリ−ｎ−ブチルホスフェート、正リン酸等のリン化合物が通常は添加されるが、リン元素としてのポリエステル中の含有量が２０〜１００ｐｐｍであることが熱安定性の点から好ましい。なお、ポリエステルは、溶融重合後これをチップ化し、加熱減圧下または窒素などの不活性気流中において更に固相重合を施してもよい。 Polyester can be obtained by a conventionally known method. For example, it can be obtained by a method of directly obtaining a low-polymerization degree polyester by reaction of dicarboxylic acid and glycol. Alternatively, it can be obtained by a method in which a lower alkyl ester of dicarboxylic acid and glycol are reacted with each other using a transesterification catalyst and then a polymerization reaction is performed in the presence of a polymerization reaction catalyst. As the transesterification reaction catalyst, conventionally known compounds such as sodium, potassium, magnesium, calcium, zinc, strontium, titanium, zirconium, manganese, and cobalt can be used. Examples of the polymerization reaction catalyst include conventionally known ones, for example, antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl titanate, tetraphenyl titanate or a portion thereof. Titanium compounds such as hydrolysates, titanyl ammonium oxalate, potassium titanyl oxalate, and titanium trisacetylacetonate can be used. When polymerization is performed via a transesterification reaction, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, or normal phosphoric acid is usually added to deactivate the transesterification catalyst before the polymerization reaction. However, the content in the polyester as the phosphorus element is preferably 20 to 100 ppm from the viewpoint of thermal stability. The polyester may be converted into chips after melt polymerization, and further subjected to solid phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen.
ポリエステルフィルムは、実質的に粒子を含有しないことが好ましい。粒子を含有していると高透明性が損なわれたり、表面が粗面化し透明導電層の加工が困難になることがある。フィルムのヘーズ値は、好ましくは１．５％以下、さらに好ましくは１．０％以下、特に好ましくは０．５％以下である。 The polyester film preferably contains substantially no particles. If the particles are contained, high transparency may be impaired, or the surface may be roughened, making it difficult to process the transparent conductive layer. The haze value of the film is preferably 1.5% or less, more preferably 1.0% or less, and particularly preferably 0.5% or less.
ポリエステルフィルムは、波長３７０ｎｍにおける光線透過率が３％以下、４００ｎｍでの光線透過率が７０％以上であることが好ましい。なお、光線透過率は（株）島津製作所製分光光度計ＭＰＣ３１００を用いて測定した数値である。この光線透過率は、２，６−ナフタレンジカルボン酸のような紫外線を吸収するモノマーを構成成分とするポリエステルを用いることにより、また紫外線吸収剤をポリエステルに含有させることにより得ることができる。 The polyester film preferably has a light transmittance at a wavelength of 370 nm of 3% or less and a light transmittance at 400 nm of 70% or more. The light transmittance is a numerical value measured using a spectrophotometer MPC3100 manufactured by Shimadzu Corporation. This light transmittance can be obtained by using a polyester containing a monomer that absorbs ultraviolet rays, such as 2,6-naphthalenedicarboxylic acid, and by incorporating an ultraviolet absorber in the polyester.
紫外線吸収剤を用いる場合、例えば２，２’−ｐ−フェニレンビス（３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−メチル−３，１−ベンゾオキサジン−４−オン）、２，２’−ｐ−フェニレンビス（６−クロロ−３，１−ベンゾオキサジン−４−オン）、２，２’−（４，４’−ジフェニレン）ビス（３，１−ベンゾオキサジン−４−オン）および２，２’−（２，６−ナフチレン）ビス（３，１−ベンゾオキサジン−４−オン）などの環状イミノエステル化合物を用いることができる。 When an ultraviolet absorber is used, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-p-phenylenebis (6-methyl-3,1-benzoxazine) -4-one), 2,2'-p-phenylenebis (6-chloro-3,1-benzoxazin-4-one), 2,2 '-(4,4'-diphenylene) bis (3,1 Cyclic imino ester compounds such as -benzoxazin-4-one) and 2,2 '-(2,6-naphthylene) bis (3,1-benzoxazin-4-one) can be used.
ポリエステルフィルムは、３次元中心線平均粗さが、両面共に好ましくは０．０００１〜０．０２μｍ、さらに好ましくは０．０００１〜０．０１５μｍ、特に好ましくは０．０００１〜０．０１０μｍである。特に、少なくとも片面の３次元中心線平均粗さが０．０００１〜０．００５μｍであると、透明導電層の加工がしやすくなるので好ましい。少なくとも片面の最も好ましい表面粗さは、０．０００５〜０．００４μｍである。
ポリエステルフィルムの厚みは、好ましくは１０〜５００μｍ、さらに好ましくは２０〜４００μｍ、特に好ましくは５０〜３００μｍである。
The polyester film has a three-dimensional centerline average roughness of preferably 0.0001 to 0.02 μm on both sides, more preferably 0.0001 to 0.015 μm, and particularly preferably 0.0001 to 0.010 μm. In particular, it is preferable that the three-dimensional center line average roughness of at least one surface is 0.0001 to 0.005 μm because the transparent conductive layer can be easily processed. The most preferable surface roughness of at least one surface is 0.0005 to 0.004 μm.
The thickness of the polyester film is preferably 10 to 500 μm, more preferably 20 to 400 μm, and particularly preferably 50 to 300 μm.
次に、ポリエステルフィルムの好ましい製造方法について説明する。なおガラス転位温度をＴｇと略記する。ポリエステルフィルムは、ポリエステルをフィルム状に溶融押出し、キャスティングドラムで冷却固化させて未延伸フィルムとし、この未延伸フィルムをＴｇ〜（Ｔｇ＋６０）℃で長手方向に１回もしくは２回以上合計の倍率が３倍〜６倍になるよう延伸し、その後Ｔｇ〜（Ｔｇ＋６０）℃で幅方向に倍率が３〜５倍になるように延伸し、必要に応じて更にＴｍ１８０℃〜２５５℃で１〜６０秒間熱処理を行うことにより得ることができる。ポリエステルフィルムの長手方向と幅方向における熱収縮率の差、および長手方向の熱収縮を小さくするためには、特開平５７−５７６２８号公報に示されるような、熱処理工程で縦方向に収縮せしめる方法や、特開平１−２７５０３１号公報に示されるような、フィルムを懸垂状態で弛緩熱処理する方法などを用いることができる。 Next, the preferable manufacturing method of a polyester film is demonstrated. The glass transition temperature is abbreviated as Tg. The polyester film is obtained by melt-extruding polyester into a film and cooling and solidifying it with a casting drum to form an unstretched film. This unstretched film is once or twice or more in the longitudinal direction at Tg to (Tg + 60) ° C. Stretched to double to 6 times, and then stretched so that the magnification is 3 to 5 times in the width direction at Tg to (Tg + 60) ° C., and further heat treated at Tm 180 ° C. to 255 ° C. for 1 to 60 seconds as necessary. Can be obtained. In order to reduce the difference in thermal shrinkage between the longitudinal direction and the width direction of the polyester film and the thermal shrinkage in the longitudinal direction, a method of shrinking in the longitudinal direction in a heat treatment step as disclosed in JP-A-57-57628 Alternatively, a method of relaxing heat treatment of a film in a suspended state as disclosed in JP-A-1-275031 can be used.
［透明導電層］
透明導電層としては、例えば導電性の金属酸化物（フッ素ドープ酸化スズ、インジウム−スズ複合酸化物（ＩＴＯ）、インジウム−亜鉛複合酸化物（ＩＺＯ）、金属の薄膜（例えば白金、金、銀、銅、アルミニウムなど）、炭素材料を用いることができる。この透明導電層は２種以上を積層したり、複合化させたものでもよい。これらのなかでもＩＴＯおよびＩＺＯは、光線透過率が高く低抵抗であるため、特に好ましい。
[Transparent conductive layer]
Examples of the transparent conductive layer include conductive metal oxides (fluorine-doped tin oxide, indium-tin composite oxide (ITO), indium-zinc composite oxide (IZO), metal thin films (for example, platinum, gold, silver, Copper, aluminum, etc.) and carbon materials can be used.This transparent conductive layer may be a laminate or composite of two or more. Among these, ITO and IZO have a high light transmittance and a low light transmittance. Since it is resistance, it is especially preferable.
透明導電層の表面抵抗は、好ましくは１００Ω／□以下、さらに好ましくは４０Ω／□以下である。１００Ω／□を超えると電池内抵抗が大きくなりすぎて光発電効率が低下するため好ましくない。 The surface resistance of the transparent conductive layer is preferably 100Ω / □ or less, more preferably 40Ω / □ or less. If it exceeds 100Ω / □, the resistance in the battery becomes too large, and the photovoltaic power generation efficiency is lowered.
透明導電層の厚みは、好ましくは１００〜５００ｎｍである。１００ｎｍ未満であると十分に表面抵抗値を低くすることができず、５００ｎｍを超えると光線透過率が低下するとともに、透明導電層がわれやすくなり好ましくない。 The thickness of the transparent conductive layer is preferably 100 to 500 nm. If it is less than 100 nm, the surface resistance value cannot be lowered sufficiently, and if it exceeds 500 nm, the light transmittance is lowered and the transparent conductive layer is easily broken, which is not preferable.
透明導電層の表面張力は、好ましくは４０ｍＮ／ｍ以上、さらに好ましくは６５ｍＮ／ｍ以上である。表面張力が４０ｍＮ／ｍ未満であると、透明導電層と多孔質半導体の密着性が劣ることがあり、６５ｍＮ／ｍ以上であると溶媒の主成分が水である水性塗液の塗布による多孔質半導体層の形成が容易になりより好ましい。 The surface tension of the transparent conductive layer is preferably 40 mN / m or more, more preferably 65 mN / m or more. When the surface tension is less than 40 mN / m, the adhesion between the transparent conductive layer and the porous semiconductor may be inferior, and when it is 65 mN / m or more, the porous material is coated with an aqueous coating liquid whose main component is water. The semiconductor layer can be easily formed, which is more preferable.
上記性質を備える透明導電層は、例えばＩＴＯやＩＺＯを用いて透明導電層を形成し、下記のいずれかの方法で加工を施すことにより得ることができる。
（１）酸性もしくはアルカリ性溶液で透明導電層表面を活性化する方法
（２）紫外線や電子線を透明導電層表面に照射して活性化する方法
（３）コロナ処理やプラズマ処理を施して透明導電層表面を活性化する方法
中でもプラズマ処理により表面を活性化する方法は、高い表面張力が得られるため特に好ましい。
A transparent conductive layer having the above properties can be obtained by forming a transparent conductive layer using, for example, ITO or IZO and processing it by any of the following methods.
(1) Method of activating the surface of the transparent conductive layer with an acidic or alkaline solution (2) Method of activating by irradiating the surface of the transparent conductive layer with ultraviolet rays or an electron beam (3) Transparent conductivity by applying corona treatment or plasma treatment Method for activating layer surface Among these, the method for activating the surface by plasma treatment is particularly preferred because high surface tension can be obtained.
［易接着層］
ポリエステルフィルムと透明導電層との密着性を向上させるために、ポリエステルフィルムと透明導電層の間に易接着層を設けることが好ましい。易接着層の厚みは好ましくは１０〜２００ｎｍ、さらに好ましくは２０〜１５０ｎｍである。易接着層の厚みが１０ｎｍ未満であると密着性を向上させる効果が乏しく、２００ｎｍを超えると易接着層の凝集破壊が発生しやすくなり密着性が低下することがあり好ましくない。
[Easily adhesive layer]
In order to improve the adhesion between the polyester film and the transparent conductive layer, it is preferable to provide an easy adhesion layer between the polyester film and the transparent conductive layer. The thickness of the easy adhesion layer is preferably 10 to 200 nm, more preferably 20 to 150 nm. If the thickness of the easy-adhesion layer is less than 10 nm, the effect of improving the adhesion is poor, and if it exceeds 200 nm, cohesive failure of the easy-adhesion layer tends to occur and the adhesion may be lowered.
易接着層を設ける場合、ポリエステルフィルムの製造過程で塗工により設けること好ましく、さらには配向結晶化が完了する前のポリエステルフィルムに塗布することが好ましい。ここで、結晶配向が完了する前のポリエステルフィルムとは、未延伸フィルム、未延伸フィルムを縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、さらには縦方向および横方向の二方向に低倍率延伸配向せしめたもの（最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム）を含むものである。なかでも、未延伸フィルムまたは一方向に配向せしめた一軸延伸フィルムに、上記組成物の水性塗液を塗布し、そのまま縦延伸および／または横延伸と熱固定とを施すのが好ましい。 When providing an easy-adhesion layer, it is preferable to provide by coating in the manufacturing process of a polyester film, and it is preferable to apply | coat to the polyester film before orientation crystallization is completed further. Here, the polyester film before the crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And a film that has been stretched and oriented at a low magnification (a biaxially stretched film before being finally re-stretched in the machine direction or the transverse direction to complete oriented crystallization). In particular, it is preferable to apply the aqueous coating liquid of the above composition to an unstretched film or a uniaxially stretched film oriented in one direction, and perform longitudinal stretching and / or lateral stretching and heat setting as it is.
易接着層は、ポリエステルフィルムと透明導電層の双方に優れた接着性を有する素材からなることが好ましく、例えばポリエステル樹脂、アクリル樹脂、ウレタンアクリル樹脂、シリコンアクリル樹脂、メラミン樹脂、ポリシロキサン樹脂を用いることができる。これらの樹脂は単独で用いても良く、２種以上の混合物として用いてもよい。 The easy adhesion layer is preferably made of a material having excellent adhesion to both the polyester film and the transparent conductive layer. For example, a polyester resin, an acrylic resin, a urethane acrylic resin, a silicon acrylic resin, a melamine resin, or a polysiloxane resin is used. be able to. These resins may be used alone or as a mixture of two or more.
［ハードコート層］
ポリエステルフィルムと透明導電層との密着性、特に密着の耐久性を向上させるために、易接着層と透明導電層との間にハードコート層を設けてもよい。ハードコート層の厚みは好ましくは０．０１〜２０μｍ、さらに好ましくは１〜１０μｍである。
[Hard coat layer]
In order to improve the adhesion between the polyester film and the transparent conductive layer, particularly the durability of the adhesion, a hard coat layer may be provided between the easy adhesion layer and the transparent conductive layer. The thickness of the hard coat layer is preferably 0.01 to 20 μm, more preferably 1 to 10 μm.
ハードコート層を設ける場合、易接着層を設けたポリエステルフィルム上に塗工により設けることが好ましい。ハードコート層は、易接着層と透明導電層の双方に優れた密着性を有する素材からなることが好ましく、例えばアクリル系樹脂、ウレタン系樹脂、シリコン系樹脂、ＵＶ硬化系樹脂、エポキシ系樹脂といった樹脂成分やこれらと無機粒子の混合物を用いることができる。無機粒子としては、例えばアルミナ、シリカ、マイカの粒子を用いることができる。 When providing a hard-coat layer, it is preferable to provide by coating on the polyester film which provided the easily bonding layer. The hard coat layer is preferably made of a material having excellent adhesion to both the easy adhesion layer and the transparent conductive layer, such as an acrylic resin, a urethane resin, a silicon resin, a UV curable resin, and an epoxy resin. A resin component or a mixture of these and inorganic particles can be used. As the inorganic particles, for example, alumina, silica, and mica particles can be used.
［反射防止層］
本発明においては、光線透過率を上げて光発電効率を高めることを目的として、透明導電層とは反対側の面に反射防止層を設けてもよい。
反射防止層を設ける方法としては、ポリエステルフィルムの屈折率とは異なる屈折率を有する素材を単層もしくは２層以上に積層形成する方法が好ましい。単層構造の場合は、基材フィルムよりも小さな屈折率を有する素材を使用するのがよく、また２層以上の多層構造とする場合は、積層フィルムと隣接する層はポリエステルフィルムよりも大さな屈折率を有する素材とし、その上に積層される層には、これよりも小さな屈折率を有する素材を選択することが好ましい。
[Antireflection layer]
In the present invention, an antireflection layer may be provided on the surface opposite to the transparent conductive layer for the purpose of increasing the light transmittance and enhancing the photovoltaic power generation efficiency.
As a method for providing the antireflection layer, a method in which a material having a refractive index different from the refractive index of the polyester film is laminated in a single layer or two or more layers is preferable. In the case of a single layer structure, it is better to use a material having a refractive index smaller than that of the base film, and in the case of a multilayer structure of two or more layers, the layer adjacent to the laminated film is larger than the polyester film. It is preferable to select a material having a refractive index smaller than that of a material having a high refractive index and a layer laminated thereon.
この反射防止層を構成する素材としては、有機材料、無機材料の如何を問わず上記屈折率の関係を満足するものであればよいが、好ましくは、ＣａＦ２，ＭｇＦ２，ＮａＡｌＦ４，ＳｉＯ２，ＴｈＦ４，ＺｒＯ２，Ｎｄ２Ｏ３，ＳｎＯ２，ＴｉＯ２，Ｃｅ、Ｏ２，ＺｎＳ，Ｉｎ２Ｏ３からなる群から選ばれる誘電体を用いる。 The material constituting the antireflection layer may be any material that satisfies the above-described refractive index relationship, regardless of whether it is an organic material or an inorganic material, but preferably CaF 2 , MgF 2 , NaAlF 4 , SiO 2. , ThF 4 , ZrO 2 , Nd 2 O 3 , SnO 2 , TiO 2 , Ce, O 2 , ZnS, and In 2 O 3 are used.
反射防止層を積層する方法としては、例えば真空蒸着法、スパッタリング法、ＣＶＤ法、イオンプレーテイング法などのドライコーティング法を用いることができ、また例えばグラビア方式、リバース方式、ダイ方式などのウェットコーティング法を用いることができる。
反射防止層の積層に先立って、コロナ放電処理、プラズマ処理、スパッタエッチング処理、電子線照射処理、紫外線照射処理、プライマ処理、易接着処理などの前処理を施してもよい。
As a method of laminating the antireflection layer, for example, a dry coating method such as a vacuum deposition method, a sputtering method, a CVD method, or an ion plating method can be used, and a wet coating such as a gravure method, a reverse method, or a die method is used. Can be used.
Prior to the lamination of the antireflection layer, pretreatment such as corona discharge treatment, plasma treatment, sputter etching treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, primer treatment, and easy adhesion treatment may be performed.
［色素増感型太陽電池の作成］
本発明の電極を用いて色素増感型太陽電池を作成するには、公知の方法を用いることができる。具体的は例えば下記の方法で作成することができる。
（１）本発明の電極の多孔質半導体層に色素を吸着させる。ルテニウムビピリジン系錯体（ルテニウム錯体）に代表される有機金属錯体色素、シアニン系色素、クマリン系色素、キサンテン系色素、ポルフィリン系色素など、可視光領域および赤外光領域の光を吸収する特性を有する色素を、アルコールやトルエンなどの溶媒に溶解させて色素溶液を作成し、多孔質半導体層を浸漬するか、多孔質半導体層に噴霧または塗布する。（電極Ａ）
（２）対極としては、本発明の電極の透明導電層側に、薄い白金層をスパッタ法により形成したものを用いる。（電極Ｂ）
（３）上記電極Ａと電極Ｂを、熱圧着性のポリエチレンフィルム製フレーム型スペーサー（厚さ２０μｍ）を挿入して重ね合わせ、スペーサー部を１２０℃に加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。
（４）シートのコーナー部にあらかじめ設けた電解液注入用の小孔を通して、ヨウ化リチウムとヨウ素（モル比３：２）ならびにスペーサーとして平均粒径２０μｍのナイロンビーズを３重量％含む電解質水溶液を注入する。内部の脱気を十分に行い、最終的に小孔をエポキシ樹脂接着剤で封じる。
[Creation of dye-sensitized solar cell]
In order to produce a dye-sensitized solar cell using the electrode of the present invention, a known method can be used. Specifically, for example, it can be created by the following method.
(1) A dye is adsorbed on the porous semiconductor layer of the electrode of the present invention. It has the property of absorbing light in the visible and infrared regions, such as organometallic complex dyes represented by ruthenium bipyridine complexes (ruthenium complexes), cyanine dyes, coumarin dyes, xanthene dyes, porphyrin dyes, etc. A dye solution is prepared by dissolving a dye in a solvent such as alcohol or toluene, and the porous semiconductor layer is immersed, or sprayed or applied to the porous semiconductor layer. (Electrode A)
(2) As the counter electrode, a thin platinum layer formed by sputtering on the transparent conductive layer side of the electrode of the present invention is used. (Electrode B)
(3) The electrode A and the electrode B are overlapped by inserting a thermocompression-bondable polyethylene film frame spacer (thickness 20 μm), the spacer portion is heated to 120 ° C., and both electrodes are pressure-bonded. Further, the edge portion is sealed with an epoxy resin adhesive.
(4) An electrolyte aqueous solution containing lithium iodide and iodine (molar ratio 3: 2) and 3% by weight of nylon beads having an average particle diameter of 20 μm as spacers is passed through a small hole for injecting electrolyte provided in advance in the corner of the sheet. inject. Thoroughly deaerate the inside and finally seal the small holes with an epoxy resin adhesive.
次に、実施例により本発明をさらに詳細に説明する。また以下の各実施例、比較例における評価項目は以下のとおりの手法にて実施した。
（１）金属酸化物粒子および金属酸化物微粒子の平均径および平均長さ
金属酸化物粒子または金属酸化物微粒子の表面を走査型電子顕微鏡（株式会社日立製作所製Ｓ−２４００）により撮影（倍率２０００倍）して得た写真図から無作為に２０箇所を選んでフィラメントの径及び長さを測定し、平均値を求めて、平均径及び平均長さとした。
Next, the present invention will be described in more detail with reference to examples. The evaluation items in the following examples and comparative examples were carried out by the following methods.
(1) Average diameter and average length of metal oxide particles and metal oxide fine particles The surface of metal oxide particles or metal oxide fine particles was photographed with a scanning electron microscope (S-2400, manufactured by Hitachi, Ltd.) (magnification 2000) 20 times were selected at random from the photograph obtained by measuring the diameter and length of the filament, and the average value was obtained to obtain the average diameter and average length.
（２）ＢＥＴ比表面積の測定方法
金属酸化物粒子または金属酸化物微粒子の比表面積測定を、窒素ガスを用いたＢＥＴ法により測定した。
(2) Method for measuring BET specific surface area The specific surface area of metal oxide particles or metal oxide fine particles was measured by the BET method using nitrogen gas.
（３）Ｘ線回折の測定
金属酸化物吐出物を、Ｘ線回折装置（株式会社リガク社製）を使用し、Ｘ線源にＣｕのＫα線を用い、多層膜コンフォーカルミラーにより単色化してＸ線回折図形を得た。
(3) Measurement of X-ray diffraction Using a X-ray diffractometer (manufactured by Rigaku Co., Ltd.) and a Cu Kα ray as the X-ray source, the metal oxide discharge is monochromated by a multilayer film confocal mirror. An X-ray diffraction pattern was obtained.
（４）固有粘度
固有粘度（［η］ｄｌ／ｇ）は、３５℃のｏ−クロロフェノール溶液で測定した。
(4) Intrinsic viscosity Intrinsic viscosity ([η] dl / g) was measured with an o-chlorophenol solution at 35 ° C.
（５）フィルム厚み
マイクロメーター（アンリツ（株）製のＫ−４０２Ｂ型）を用いて、フィルムの連続製膜方向および幅方向に各々１０ｃｍ間隔で測定を行い、全部で３００ヶ所のフィルム厚みを測定した。得られた３００ヶ所のフィルム厚みの平均値を算出してフィルム厚みとした。
(5) Film thickness Using a micrometer (K-402B type manufactured by Anritsu Co., Ltd.), measurements are made at 10 cm intervals in the continuous film forming direction and the width direction of the film, and a total of 300 film thicknesses are measured. did. The average value of the film thicknesses of the obtained 300 locations was calculated and used as the film thickness.
（６）塗布層の厚み
フィルムの小片をエポキシ樹脂（リファインテック（株）製エポマウント）中に包埋し、Ｒｅｉｃｈｅｒｔ−Ｊｕｎｇ社製Ｍｉｃｒｏｔｏｍｅ２０５０を用いて包埋樹脂ごと５０ｎｍ厚さにスライスし、透過型電子顕微鏡（トプコンＬＥＭ−２０００）にて加速電圧１００ＫＶ、倍率１０万倍にて観察し、塗膜層の厚みを測定した。
(6) Thickness of coating layer A small piece of film was embedded in an epoxy resin (Epomount manufactured by Refine Tech Co., Ltd.), sliced to a thickness of 50 nm together with the embedded resin using Microtome 2050 manufactured by Reichert-Jung, and transmitted. The thickness of the coating layer was measured with a scanning electron microscope (Topcon LEM-2000) at an acceleration voltage of 100 KV and a magnification of 100,000.
（７）表面抵抗値
４探針式表面抵抗率測定装置（三菱化学（株）製、ロレスタＧＰ）を用いて任意の５点を測定し、その平均値を代表値として用いた。
(7) Surface resistance value Any five points were measured using a 4-probe type surface resistivity measuring device (Made by Mitsubishi Chemical Co., Ltd., Loresta GP), and the average value was used as a representative value.
（８）表面張力
表面張力が既知である水、およびヨウ化メテレンの透明導電性薄膜に対する接触角：θｗ、θｙを接触角計（協和界面科学社製「ＣＡ−Ｘ型」）を使用し、２５℃、５０％ＲＨの条件で測定した。これらの測定値を用い、以下の様にして透明導電性薄膜の表面張力γｓを算出した。
透明導電性薄膜の表面張力γｓは、分散性成分γｓｄと極性成分γｓｐとの和である。即ち、
γｓ＝γｓｄ＋γｓｐ （式１）
また、Ｙｏｕｎｇの式より、
γｓ＝γｓｗ＋γｗ・ｃｏｓθｗ （式２）
γｓ＝γｓｙ＋γｙ・ｃｏｓθｙ （式３）
ここで、γｓｗは透明導電性薄膜と水との間に働く張力、γｓｗは透明導電性薄膜とヨウ化メチレンとの間に働く張力、γｗは水の表面張力、γｙはヨウ化メチレンの表面張力である。
また、Ｆｏｗｋｅｓの式より、
γｓｗ＝γｓ＋γｗ−２×（γｓｄ・γｗｄ）１／２−２×（γｓｐ・γｗｐ）１／２ （式４）
γｓｙ＝γｓ＋γｙ−２×（γｓｄ・γｙｄ）１／２−２×（γｓｐ・γｙｐ）１／２ （式５）
である。
ここで、γｗｄは水の表面張力の分散性成分、γｗｐは水の表面張力の極性成分、γｙｄはヨウ化メテレンの表面張力の分散性成分、γｙｐはヨウ化メチレンの表面張力の極性成分である。
(8) Surface tension Contact angles: θ w and θ y of water and methylene iodide with known surface tension to the transparent conductive thin film are used using a contact angle meter (“CA-X type” manufactured by Kyowa Interface Science Co., Ltd.). And measured under conditions of 25 ° C. and 50% RH. Using these measured values, the surface tension γ s of the transparent conductive thin film was calculated as follows.
The surface tension γ s of the transparent conductive thin film is the sum of the dispersive component γ sd and the polar component γ sp . That is,
γ s = γ sd + γ sp (Formula 1)
From the Young equation,
γ s = γ sw + γ w · cos θ w (Formula 2)
γ s = γ sy + γ y · cos θ y (Formula 3)
Here, γ sw is a tension acting between the transparent conductive thin film and water, γ sw is a tension acting between the transparent conductive thin film and methylene iodide, γ w is a surface tension of water, and γ y is iodide. This is the surface tension of methylene.
From the Fowkes equation,
γ sw = γ s + γ w −2 × (γ sd · γ wd ) 1/2 −2 × (γ sp · γ wp ) 1/2 (Formula 4)
γ sy = γ s + γ y −2 × (γ sd · γ yd ) 1/2 −2 × (γ sp · γ yp ) 1/2 (Formula 5)
It is.
Here, γ wd is a dispersive component of the surface tension of water, γ wp is a polar component of the surface tension of water, γ yd is a dispersive component of the surface tension of methyl iodide, and γ yp is a surface tension of methylene iodide. It is a polar component.
式１〜５の連立方程式を解くことにより、透明導電性薄膜の表層張力γｓ＝γｓｄ＋γｓｐを算出できる。この時、水の表面張力（γｗ）：７２．８ｍＮ／ｍ、よう化メチレンの表面張力（γｙ）：５０．５ｍＮ／ｍ、水の表面張力の分散性成分（γｗｄ）：２１．８ｍＮ／ｍ、水の表面張力の極性成分（γｗｐ）：５１．０ｍＮ／ｍ、ヨウ化メチレンの表面張力の分散性成分（γｙｄ）：４９．５ｍＮ／ｍ、ヨウ化メテレンの表面張力の極性成分（γｙｐ）：１．３ｍＮ／ｍを用いた。 By solving the simultaneous equations of Formulas 1 to 5, the surface tension γ s = γ sd + γ sp of the transparent conductive thin film can be calculated. At this time, the surface tension of water (γ w ): 72.8 mN / m, the surface tension of methylene iodide (γ y ): 50.5 mN / m, the dispersive component of the surface tension of water (γ wd ): 21. 8 mN / m, polar component of surface tension of water (γ wp ): 51.0 mN / m, dispersive component of surface tension of methylene iodide (γ yd ): 49.5 mN / m, surface tension of methylene iodide Polar component (γ yp ): 1.3 mN / m was used.
（９）Ｉ−Ｖ特性（光電流−電圧特性）
１００ｍｍ２大の色素増感型太陽電池を形成し、下記の方法で光発電効率を算出した。ぺクセルテクノロジーズ社製ソーラーシュミレーター（ＰＥＣ−Ｌ１０）を用い入射光強度が１００ｍＷ／ｃｍ２の模擬太陽光を、気温２５℃、湿度５０％の雰囲気で測定した。電流電圧測定装置（ＰＥＣＫ ２４００）を用いて、システムに印加するＤＣ電圧を１０ｍＶ／ｓｅｃの定速でスキャンし、素子の出力する光電流を計測することにより、光電流−電圧特性を測定し、光発電効率を算出した。
(9) IV characteristics (photocurrent-voltage characteristics)
A 100 mm 2 large dye-sensitized solar cell was formed, and the photovoltaic power generation efficiency was calculated by the following method. Simulated sunlight with an incident light intensity of 100 mW / cm 2 was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 50% using a solar simulator (PEC-L10) manufactured by Pexel Technologies. Using a current-voltage measuring device (PECK 2400), the DC voltage applied to the system is scanned at a constant speed of 10 mV / sec, the photocurrent output from the device is measured, and the photocurrent-voltage characteristic is measured. Photovoltaic efficiency was calculated.
［実施例１］
＜ポリエステルフィルムの作成＞
固有粘度が０．６３で、実質的に粒子を含有しないポリエチレン−２，６−ナフタレンジカルボキシレートのペレットを１７０℃で６時間乾燥後、押出機ホッパーに供給し、溶融温度３０５℃で溶融し、平均目開きが１７μｍのステンレス鋼細線フィルターで濾過し、３ｍｍのスリット状ダイを通して表面温度６０℃の回転冷却ドラム上で押出し、急冷して未延伸フィルムを得た。このようにして得られた未延伸フィルムを１２０℃にて予熱し、さらに低速、高速のロール間で１５ｍｍ上方より８５０℃のＩＲヒーターにて加熱して縦方向に３．１倍に延伸した。この縦延伸後のフィルムの片面に下記の塗剤Ａを乾燥後の塗膜厚みが０．２５μｍになるようにロールコーターで塗工し易接層を形成した。
[Example 1]
<Creation of polyester film>
Polyethylene-2,6-naphthalene dicarboxylate pellets having an intrinsic viscosity of 0.63 and containing substantially no particles are dried at 170 ° C. for 6 hours, then fed to an extruder hopper, and melted at a melting temperature of 305 ° C. Then, it was filtered through a stainless steel fine wire filter having an average opening of 17 μm, extruded through a 3 mm slit die on a rotary cooling drum having a surface temperature of 60 ° C., and rapidly cooled to obtain an unstretched film. The unstretched film thus obtained was preheated at 120 ° C., and further heated by an IR heater at 850 ° C. from above 15 mm between low-speed and high-speed rolls and stretched 3.1 times in the longitudinal direction. The following coating agent A was applied on one side of the film after the longitudinal stretching with a roll coater so that the coating thickness after drying was 0.25 μm, thereby forming an easy-contact layer.
続いてテンターに供給し、１４０℃にて横方向に．３．３倍に延伸した。得られた二軸配向フィルムを２４５℃の温度で５秒間熱固定し、固有粘度が０．５８ｄｌ／ｇ、厚み１２５μｍのポリエステルフィルムを得た。その後、このフィルムを懸垂状態で、弛緩率０．７％、温度２０５℃で熱弛緩させた。 Subsequently, it was supplied to the tenter and laterally at 140 ° C. 3. Stretched 3 times. The obtained biaxially oriented film was heat-fixed at a temperature of 245 ° C. for 5 seconds to obtain a polyester film having an intrinsic viscosity of 0.58 dl / g and a thickness of 125 μm. Thereafter, this film was heat-relaxed in a suspended state at a relaxation rate of 0.7% and a temperature of 205 ° C.
＜塗剤Ａの調製＞
２，６−ナフタレンジカルボン酸ジメチル６６部、イソフタル酸ジメチル４７部、５−ナトリウムスルホイソフタル酸ジメチル８部、エチレングリコール５４部、ジエチレングリコール６２部を反応器に仕込み、これにテトラブトキシチタン０．０５部を添加して窒素雰囲気下で温度を２３０℃にコントロールして加熱し、生成するメタノールを留去させてエステル交換反応を行った。次いで反応系の温度を徐々に２５５℃まで上昇させ系内を１ｍｍＨｇの減圧にして重縮合反応を行い、ポリエステルを得た。このポリエステル２５部をテトラヒドロフラン７５部に溶解させ、得られた溶液に１００００回転／分の高速攪拌下で水７５部を滴下して乳白色の分散体を得、次いでこの分散体を２０ｍｍＨｇの減圧下で蒸留し、テトラヒドロフランを留去し、固形分が２５重量％のポリエステルの水分散体を得た。
<Preparation of coating agent A>
66 parts of
次に、四つ口フラスコに、界面活性剤としてラウリルスルホン酸ナトリウム３部、およびイオン交換水１８１部を仕込んで窒素気流中で６０℃まで昇温させ、次いで重合開始剤として過硫酸アンモニウム０．５部、亜硝酸水素ナトリウム０．２部を添加し、更にモノマー類である、メタクリル酸メチル３０．１部、２−イソプロペニル−２−オキサゾリン２１．９部、ポリエチレンオキシド（ｎ＝１０）メタクリル酸３９．４部、アクリルアミド８．６部の混合物を３時間にわたり、液温が６０〜７０℃になるよう調整しながら滴下した。滴下終了後も同温度範囲に２時間保持しつつ、攪拌下に反応を継続させ、次いで冷却して固形分が３５％重量のアクリルの水分散体を得た。 Next, 3 parts of sodium lauryl sulfonate as a surfactant and 181 parts of ion-exchanged water are charged into a four-necked flask and the temperature is raised to 60 ° C. in a nitrogen stream, and then 0.5% ammonium persulfate is used as a polymerization initiator. Part, 0.2 part of sodium hydrogen nitrite is added, and further monomers 30.1 parts of methyl methacrylate, 21.9 parts of 2-isopropenyl-2-oxazoline, polyethylene oxide (n = 10) methacrylic acid A mixture of 39.4 parts and 8.6 parts of acrylamide was added dropwise over 3 hours while adjusting the liquid temperature to 60 to 70 ° C. After completion of dropping, the reaction was continued with stirring while maintaining the same temperature range for 2 hours, and then cooled to obtain an acrylic aqueous dispersion having a solid content of 35% by weight.
一方で、シリカフィラー（平均粒径：１００ｎｍ）（日産化学株式会社製 商品名スノーテックスＺＬ）を０．２重量％、濡れ剤として、ポリオキシエチレン（ｎ＝７）ラウリルエーテル（三洋化成株式会社製 商品名ナロアクティーＮ−７０）の０．３重量％添加した水溶液を作成した。
上記のポリエステルの水分散体８重量部、アクリルの水分散体７重量部と水溶液８５重量部を混合して、易着層の形成に用いる塗剤Ａを作成した。
On the other hand, 0.2% by weight of silica filler (average particle size: 100 nm) (trade name Snowtex ZL manufactured by Nissan Chemical Co., Ltd.), polyoxyethylene (n = 7) lauryl ether (Sanyo Chemical Co., Ltd.) as a wetting agent An aqueous solution containing 0.3% by weight of the trade name NAROACTY N-70) was prepared.
8 parts by weight of the above-mentioned polyester aqueous dispersion, 7 parts by weight of the acrylic water dispersion and 85 parts by weight of the aqueous solution were mixed to prepare a coating agent A used for forming an easy-adhesion layer.
＜ハードコートの形成＞
得られたポリエステルフィルムを用い、この易接層側にＵＶ硬化性ハードコート剤（ＪＳＲ製 デソライトＲ７５０１）を厚さ約５μｍになるよう塗布し、ＵＶ硬化させてハードコート層を形成した。
<Formation of hard coat>
Using the obtained polyester film, a UV curable hard coat agent (Desolite R7501 manufactured by JSR) was applied to the easy-contact layer side so as to have a thickness of about 5 μm, and UV cured to form a hard coat layer.
＜透明導電層の形成＞
ハードコート層が形成された片面に、主として酸化インジウムからなり酸化亜鉛が１０重量％添加されたＩＺＯターゲットを用いた直流マグネトロンスパッタリング法により、膜厚２６０ｎｍのＩＺＯからなる透明導電層を形成した。透明導電層のスパッタリング法による形成は、プラズマの放電前にチャンバー内を５×１０−４Ｐａまで排気した後、チャンバー内にアルゴンと酸素を導入して圧力を０．３Ｐａとし、ＩＺＯターゲットに２Ｗ／ｃｍ２の電力密度で電力を印加して行った。酸素分圧は３．７ｍＰａであった。透明導電層の表面抵抗値は１５Ω／□であった。
<Formation of transparent conductive layer>
A transparent conductive layer made of IZO having a film thickness of 260 nm was formed on one surface on which the hard coat layer was formed by a direct current magnetron sputtering method using an IZO target made of indium oxide and added with 10% by weight of zinc oxide. Formation of the transparent conductive layer by sputtering is performed by evacuating the chamber to 5 × 10 −4 Pa before plasma discharge, introducing argon and oxygen into the chamber to a pressure of 0.3 Pa, and applying 2 W to the IZO target. Electric power was applied at a power density of /
次いで、常圧プラズマ表面処理装置（積水化学工業製ＡＰ−Ｔ０３−Ｌ）を用いて、窒素気流下（６０Ｌ／分）、１ｍ／分にて透明導電層表面にプラズマ処理を施した。このとき、表面抵抗値１６Ω／□、表面張力は７１．５ｍＮ／ｍであった。 Next, using a normal pressure plasma surface treatment apparatus (AP-T03-L manufactured by Sekisui Chemical Co., Ltd.), the surface of the transparent conductive layer was subjected to plasma treatment at 1 m / min under a nitrogen stream (60 L / min). At this time, the surface resistance value was 16Ω / □, and the surface tension was 71.5 mN / m.
＜反射防止層の形成＞
積層フィルムの透明導電層を形成した面とは反対側の面に、厚さ７５ｎｍで屈折率１．８９のＹ２Ｏ３層、その上に厚さ１２０ｎｍで屈折率２．３のＴｉＯ２層、更にその上に厚さ９０ｎｍで屈折率１．４６のＳｉＯ２を、夫々高周波スパッタリング法によって製膜し、反射防止処理層とした。各静電体薄膜を製膜するに際し、いずれも真空度は１×１０−３Ｔｏｒｒとし、ガスとしてＡｒ：５５ｓｃｃｍ、Ｏ２：５ｓｃｃｍを流した。また、基板は製膜行程中、加熱もしくは冷却をすることなく室温のままとした。このようにして、透明導電層と反射防止層を備える積層フィルムを得た。
<Formation of antireflection layer>
A Y 2 O 3 layer having a thickness of 75 nm and a refractive index of 1.89 is formed on the surface of the laminated film opposite to the surface on which the transparent conductive layer is formed, and a TiO 2 layer having a refractive index of 2.3 and a thickness of 120 nm is formed thereon. Further, a SiO 2 film having a thickness of 90 nm and a refractive index of 1.46 was formed thereon by a high frequency sputtering method to form an antireflection treatment layer. In forming each electrostatic thin film, the degree of vacuum was 1 × 10 −3 Torr, and Ar: 55 sccm and O 2 : 5 sccm were flowed as gases. The substrate was kept at room temperature without heating or cooling during the film forming process. Thus, the laminated film provided with a transparent conductive layer and an antireflection layer was obtained.
＜エレクトロスピニング法による金属酸化物の調製＞
ポリアクリロニトリル（和光純薬工業株式会社製）１重量部、Ｎ，Ｎ−ジメチルホルムアミド（和光純薬工業株式会社製、特級）９重量部よりなる溶液に、チタンテトラノルマルブトキシド（和光純薬工業株式会社製、一級）１重量部とアセチルアセトン（和光純薬工業株式会社製、特級）１重量部よりなる溶液を混合し紡糸溶液を調製した。この紡糸溶液からエレクトロスピニング法による吐出装置を用いて、金属酸化物を繊維構造体状に吐出した。噴出ノズル１の内径は０．８ｍｍ、電圧は１５ｋＶ、噴出ノズル１から電極４までの距離は１５ｃｍであった。用いたエレクトロスピニング法による吐出装置の詳細を図１に示す。得られた繊維構造体状の金属酸化物を空気雰囲気下で電気炉を用いて６００℃まで１０時間で昇温し、その後６００℃で２時間保持することにより高アスペクト比の金属酸化物吐出物を作製した。この高アスペクト比の金属酸化物を電子顕微鏡で観察したところ、繊維径は６００ｎｍであり、繊維長１００μｍ以上であった。また、ＢＥＴ比表面積は７３ｍ２／ｇであった。得られた金属酸化物吐出物のＸ線回折結果では、２θ＝２５．３°に鋭いピークが認められ、酸化チタンのアナターゼ型結晶が形成されていることが確認された。
<Preparation of metal oxide by electrospinning method>
In a solution comprising 1 part by weight of polyacrylonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and 9 parts by weight of N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., special grade), titanium tetranormal butoxide (stock of Wako Pure Chemical Industries, Ltd.) A spinning solution was prepared by mixing a solution consisting of 1 part by weight of company-made, first grade and 1 part by weight of acetylacetone (made by Wako Pure Chemical Industries, Ltd., special grade). The metal oxide was discharged from the spinning solution into a fibrous structure using a discharge device by electrospinning. The inner diameter of the ejection nozzle 1 was 0.8 mm, the voltage was 15 kV, and the distance from the ejection nozzle 1 to the electrode 4 was 15 cm. FIG. 1 shows the details of the discharge device using the electrospinning method used. The resulting metal oxide in the form of a fiber structure is heated to 600 ° C. for 10 hours in an air atmosphere using an electric furnace, and then held at 600 ° C. for 2 hours, thereby discharging a metal oxide having a high aspect ratio. Was made. When this high aspect ratio metal oxide was observed with an electron microscope, the fiber diameter was 600 nm, and the fiber length was 100 μm or more. Moreover, the BET specific surface area was 73 m < 2 > / g. In the X-ray diffraction result of the obtained metal oxide discharge product, a sharp peak was observed at 2θ = 25.3 °, and it was confirmed that an anatase type crystal of titanium oxide was formed.
＜多孔質半導体層の形成＞
前述のエレクトロスピニング法による金属酸化物１０.０重量部、テトライソプロポキシチタン（和光純薬製）７．５重量部、エタノール（和光純薬製）８２．５重量部からなる分散液を作成し４０．０Ｈｚの超音波照射下３０分処理した。当初フィルム状であった金属酸化物が溶液中に良好に分散した。こうして超音波処理により破砕された金属酸化物粒子の平均アスペクト比は７．２であり、大きさは、平均短径が６００ｎｍ、平均長径は４．３μｍであった。この塗液を直ちにバーコーターにて塗布し、大気中１８０℃で５分間の熱処理を行って厚み５μｍになるように多孔質二酸化チタン層を形成した。熱処理後多孔質半導体層の剥離や脆さは観察されず、基材と密着性の良い色素増感型太陽電池の電極が得られた。
<Formation of porous semiconductor layer>
A dispersion comprising 10.0 parts by weight of the metal oxide by the electrospinning method described above, 7.5 parts by weight of tetraisopropoxytitanium (manufactured by Wako Pure Chemical Industries) and 82.5 parts by weight of ethanol (manufactured by Wako Pure Chemical Industries) was prepared. The treatment was performed for 30 minutes under 40.0 Hz ultrasonic irradiation. The metal oxide, which was originally in the form of a film, was well dispersed in the solution. The average aspect ratio of the metal oxide particles thus crushed by ultrasonic treatment was 7.2, and the average minor axis was 600 nm and the average major axis was 4.3 μm. This coating solution was immediately applied with a bar coater and heat-treated at 180 ° C. for 5 minutes in the atmosphere to form a porous titanium dioxide layer having a thickness of 5 μm. After the heat treatment, no peeling or brittleness of the porous semiconductor layer was observed, and an electrode of a dye-sensitized solar cell having good adhesion to the substrate was obtained.
＜色素増感型太陽電池の作成＞
この電極をルテニウム錯体（Ｒｕ５３５ｂｉｓＴＢＡ、Ｓｏｌａｒｏｎｉｘ製）の３００μＭエタノール溶液中に２４時間浸漬し、光作用電極表面にルテニウム錯体を吸着させた。
他方、前記＜反射防止層の形成＞で得た透明導電層と反射防止層を備える積層フィルムの透明導電層のうえにスパッタリング法によりＰｔ膜を堆積して対向電極を作成した。
<Creation of dye-sensitized solar cell>
This electrode was immersed in a 300 μM ethanol solution of a ruthenium complex (Ru535bisTBA, Solaronix) for 24 hours to adsorb the ruthenium complex on the surface of the photoactive electrode.
On the other hand, a Pt film was deposited by sputtering on the transparent conductive layer of the laminated film provided with the transparent conductive layer and the antireflection layer obtained in <Preparation of antireflection layer> to prepare a counter electrode.
電極と対向電極を、熱圧着性のポリエチレンフィルム製フレーム型スペーサー（厚さ２０μｍ）を介して重ね合わせ、スペーサー部を１２０℃に加熱し、両電極を圧着する。さらに、そのエッジ部をエポキシ樹脂接着剤でシールする。電解質溶液（０．５Ｍのヨウ化リチウムと０．０５Ｍのヨウ素と０．５Ｍのｔｅｒｔ−ブチルピリジンを含む３−メトキシプロピオニトリル溶液）を注入した後、エポキシ系接着剤でシールした。 The electrode and the counter electrode are overlapped via a thermocompression-bondable polyethylene film frame spacer (thickness 20 μm), the spacer portion is heated to 120 ° C., and both electrodes are pressure-bonded. Further, the edge portion is sealed with an epoxy resin adhesive. An electrolyte solution (3-methoxypropionitrile solution containing 0.5 M lithium iodide, 0.05 M iodine and 0.5 M tert-butylpyridine) was injected, and then sealed with an epoxy adhesive.
完成した色素増感型太陽電池のＩ−Ｖ特性の測定（有効面積１００ｍｍ２）を行った結果、開放電圧、短絡電流密度、曲線因子はそれぞれ、０．７Ｖ、５．９ｍＡ／ｃｍ２、０．５であり、その結果、光発電効率は２．０％であった。 As a result of measuring the IV characteristics (effective area 100 mm 2 ) of the completed dye-sensitized solar cell, the open circuit voltage, short circuit current density, and fill factor were 0.7 V, 5.9 mA / cm 2 , and 0, respectively. As a result, the photovoltaic power generation efficiency was 2.0%.
［実施例２］
多孔質半導体層形成時にエレクトロスピニング法による金属酸化物粒子５．０重量部、テイカ株式会社製光触媒用酸化チタンＡＭＴ−１００（平均粒子径：６ｎｍ アナターゼ相）を５．０重量部、テトライソプロポキシチタン７．５重量部、エタノール８２．５重量部とした以外は同様の手法を用いた。熱処理後多孔質半導体層の剥離や脆さは観察されず、基材と密着性の良い色素増感型太陽電池の電極を作成した。こうして得られた電極を用いて実施例１と同様の手法で色素増感型太陽電池を作成しＩ−Ｖ特性の測定（有効面積１００ｎｍ２）を行った結果開放電圧、短絡電流密度、曲線因子はそれぞれ、０．７Ｖ、６．７ｍＡ／ｃｍ２、０．６であり、その結果、光発電効率は２．８％であった。
[Example 2]
At the time of forming the porous semiconductor layer, 5.0 parts by weight of metal oxide particles by electrospinning method, 5.0 parts by weight of titanium oxide AMT-100 (average particle diameter: 6 nm anatase phase) for photocatalyst manufactured by Teika Co., Ltd., tetraisopropoxy A similar method was used except that 7.5 parts by weight of titanium and 82.5 parts by weight of ethanol were used. After the heat treatment, no peeling or brittleness of the porous semiconductor layer was observed, and an electrode of a dye-sensitized solar cell having good adhesion to the substrate was prepared. Using the electrode thus obtained, a dye-sensitized solar cell was prepared in the same manner as in Example 1, and the IV characteristics were measured (effective area 100 nm 2 ). As a result, the open circuit voltage, short circuit current density, and fill factor Were 0.7 V, 6.7 mA / cm 2 , and 0.6, respectively. As a result, the photovoltaic generation efficiency was 2.8%.
［比較例１］
多孔質半導体層形成時にエレクトロスピニング法による金属酸化物を用いず、テイカ株式会社製光触媒用酸化チタンＡＭＴ−１００（平均粒子径：６ｎｍ アナターゼ相）のみを１０．０重量部、テトライソプロポキシチタン７．５重量部、エタノール８２．５重量部とした以外は同様の手法を用いた。熱処理後多孔質半導体層は非常に脆く剥離が観察された。この電極を用いて実施例１と同様の手法で色素増感型太陽電池を作成しＩ−Ｖ特性の測定（有効面積１００ｎｍ２）を行った結果開放電圧、短絡電流密度、曲線因子はそれぞれ、０．５Ｖ、３．１ｍＡ／ｃｍ２、０．４であり、その結果、光発電効率は０．６％であった。
[Comparative Example 1]
10.0 parts by weight of tetraisopropoxytitanium 7 by using only titanium oxide AMT-100 (average particle size: 6 nm anatase phase) for photocatalyst manufactured by Teika Co., Ltd. without using metal oxide by electrospinning method when forming the porous semiconductor layer The same method was used except that the amount was 0.5 parts by weight and 82.5 parts by weight of ethanol. After the heat treatment, the porous semiconductor layer was very brittle and peeling was observed. Using this electrode, a dye-sensitized solar cell was prepared in the same manner as in Example 1 and measured for IV characteristics (effective area 100 nm 2 ). As a result, the open circuit voltage, short circuit current density, and fill factor were It was 0.5 V, 3.1 mA / cm 2 , 0.4, and as a result, the photovoltaic efficiency was 0.6%.
本発明の色素増感型太陽電池用電極は、色素増感型太陽電池の電極として好適に利用することができる。 The electrode for dye-sensitized solar cells of the present invention can be suitably used as an electrode for dye-sensitized solar cells.
１ 溶液噴出ノズル
２ 溶液
３ 溶液保持槽
４ 電極
５ 高電圧発生器
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008181685A (en) * | 2007-01-23 | 2008-08-07 | Teijin Dupont Films Japan Ltd | Electrode for dye-sensitized solar cell and method for producing the same |
| JP2008186659A (en) * | 2007-01-29 | 2008-08-14 | Teijin Dupont Films Japan Ltd | Dye-sensitized solar cell electrode |
| JP2009037779A (en) * | 2007-07-31 | 2009-02-19 | Seiko Epson Corp | Photoelectric conversion element, method for manufacturing electron transport layer, method for manufacturing photoelectric conversion element, and electronic device |
| WO2011083688A1 (en) * | 2010-01-08 | 2011-07-14 | 日立造船株式会社 | Method for manufacturing dye-sensitized solar cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093590A (en) * | 1999-09-22 | 2001-04-06 | Canon Inc | Photoelectric conversion device and method of manufacturing the same |
| JP2001358348A (en) * | 2000-06-16 | 2001-12-26 | Canon Inc | Photoelectric conversion device and method of manufacturing the same |
| JP2002050413A (en) * | 2000-08-03 | 2002-02-15 | Japan Gore Tex Inc | Photoelectrode and solar cell using the same |
| JP2007009398A (en) * | 2005-06-16 | 2007-01-18 | Korea Inst Of Science & Technology | Titanium oxide nanorods and method for producing the same |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093590A (en) * | 1999-09-22 | 2001-04-06 | Canon Inc | Photoelectric conversion device and method of manufacturing the same |
| JP2001358348A (en) * | 2000-06-16 | 2001-12-26 | Canon Inc | Photoelectric conversion device and method of manufacturing the same |
| JP2002050413A (en) * | 2000-08-03 | 2002-02-15 | Japan Gore Tex Inc | Photoelectrode and solar cell using the same |
| JP2007009398A (en) * | 2005-06-16 | 2007-01-18 | Korea Inst Of Science & Technology | Titanium oxide nanorods and method for producing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008181685A (en) * | 2007-01-23 | 2008-08-07 | Teijin Dupont Films Japan Ltd | Electrode for dye-sensitized solar cell and method for producing the same |
| JP2008186659A (en) * | 2007-01-29 | 2008-08-14 | Teijin Dupont Films Japan Ltd | Dye-sensitized solar cell electrode |
| JP2009037779A (en) * | 2007-07-31 | 2009-02-19 | Seiko Epson Corp | Photoelectric conversion element, method for manufacturing electron transport layer, method for manufacturing photoelectric conversion element, and electronic device |
| WO2011083688A1 (en) * | 2010-01-08 | 2011-07-14 | 日立造船株式会社 | Method for manufacturing dye-sensitized solar cell |
| JP2011142027A (en) * | 2010-01-08 | 2011-07-21 | Hitachi Zosen Corp | Method of manufacturing dye-sensitized solar cell |
| CN102687337A (en) * | 2010-01-08 | 2012-09-19 | 日立造船株式会社 | Method for manufacturing dye-sensitized solar cell |
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