JP2008077924A - Photoelectric converter - Google Patents

Photoelectric converter Download PDF

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JP2008077924A
JP2008077924A JP2006254444A JP2006254444A JP2008077924A JP 2008077924 A JP2008077924 A JP 2008077924A JP 2006254444 A JP2006254444 A JP 2006254444A JP 2006254444 A JP2006254444 A JP 2006254444A JP 2008077924 A JP2008077924 A JP 2008077924A
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film
oxide
transparent conductive
photoelectric conversion
dye
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Akira Fujisawa
章 藤沢
Masahiro Hirata
昌宏 平田
Shozo Yanagida
祥三 柳田
Jiangbin Xia
江濱 夏
Shigehiko Masaki
成彦 正木
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Nippon Sheet Glass Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric converter capable of preventing counter electron transfer from a transparent electrode and improving photoelectric conversion efficiency. <P>SOLUTION: A dye sensitized solar cell 100 comprises: two flat, transparent soda lime glass substrates 10a, 10b that are 5 cm square and 3 mm thick; transparent conductive films 20a, 20b that are formed on respective glass substrates 10a, 10b and are made of tin oxide that is as thick as 750 nm while fluorine is added; a niobium oxide (Nb<SB>2</SB>O<SB>5</SB>) film 25 formed on the transparent conductive film 20a; a semiconductor fine particle layer 30 made of titanium oxide formed on the niobium oxide (Nb<SB>2</SB>O<SB>5</SB>) film 25; an electrolyte solution 40 formed on the semiconductor fine particle layer 30; and a counter electrode 50 made of platinum formed between the transparent conductive film 20b and the electrolyte solution 40. The transparent conductive film 20a and the niobium oxide (Nb<SB>2</SB>O<SB>5</SB>) film 25 form a transparent electrode 60. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、光電変換装置に関し、特に、透明電極を備える光電変換装置に関する。   The present invention relates to a photoelectric conversion device, and more particularly to a photoelectric conversion device including a transparent electrode.

近年のエネルギー問題および環境問題を解決する手段として、太陽電池に代表される光電変換装置が注目を集めている。この光電変換装置の中でも、特に、色素増感太陽電池は、製造工程において、高温処理する必要がなかったり、真空装置内の処理を行う必要がなかったり、不足しているシリコン基板を用いる必要がないことから、製造コストが低減された安価な太陽電池として期待が高まっている。この色素増感太陽電池は、ガラス等の透明基板に酸化錫等の透明導電膜を形成した後、酸化チタン等の半導体微粒子を形成し、この半導体微粒子にルテニウム錯体色素を担持させ、白金等を形成した対向電極を貼り合わせることによって製造される（例えば、非特許文献１及び特許文献１参照）。   As means for solving energy problems and environmental problems in recent years, photoelectric conversion devices represented by solar cells have attracted attention. Among the photoelectric conversion devices, in particular, the dye-sensitized solar cell does not need to be subjected to high temperature processing in the manufacturing process, does not need to perform processing in the vacuum device, or needs to use a deficient silicon substrate. Therefore, there is an increasing expectation for an inexpensive solar cell with reduced manufacturing costs. In this dye-sensitized solar cell, a transparent conductive film such as tin oxide is formed on a transparent substrate such as glass, and then semiconductor fine particles such as titanium oxide are formed. It is manufactured by bonding the formed counter electrode (see, for example, Non-Patent Document 1 and Patent Document 1).

上記色素増感太陽電池は、電解質中に溶解した色素分子が光を吸収することにより色素分子の電子が励起され、この励起された電子が酸化チタン電極中に注入されるという原理であり、酸化チタン等の半導体微粒子にルテニウム錯体色素を担持させた後に電解質が注入されることにより製造される。   The dye-sensitized solar cell is based on the principle that dye molecules dissolved in an electrolyte absorb light to excite the electrons of the dye molecules, and the excited electrons are injected into the titanium oxide electrode. It is manufactured by injecting an electrolyte after supporting a ruthenium complex dye on semiconductor fine particles such as titanium.

また、上記色素増感太陽電池において、ガラス基板上に酸化錫膜から成る透明導電膜が透明電極として光が入射する側に設けられている。   In the dye-sensitized solar cell, a transparent conductive film made of a tin oxide film is provided on a glass substrate on the side where light enters as a transparent electrode.

さらに、透明導電膜及び半導体微粒子間に下引き層を形成した光電変換素子が提案されている（例えば、特許文献２参照）。
Brian O’ Regan および Michael Gratzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films", Nature, United Kingdom, Nature Publishing Group, 1991年, vol.353, p.737-740 特開平１−２２０３８０号公報 特開２００１−１４３７７１号公報 Furthermore, a photoelectric conversion element in which an undercoat layer is formed between a transparent conductive film and semiconductor fine particles has been proposed (see, for example, Patent Document 2).
Brian O 'Regan and Michael Gratzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films", Nature, United Kingdom, Nature Publishing Group, 1991, vol.353, p.737-740 Japanese Patent Laid-Open No. 1-220380 JP 2001-143771 A

しかしながら、酸化錫膜のみを透明電極として用いた場合に、光を吸収することにより励起された色素分子の電子が、酸化チタン等の半導体微粒子を通って酸化錫膜に移動した後に、電解質液に接した酸化錫膜の表面から電解質液側に逆電子移動を起こして、得られる電力を低減してしまうという問題があった。   However, when only the tin oxide film is used as the transparent electrode, the electrons of the dye molecules excited by absorbing light move to the tin oxide film through the semiconductor fine particles such as titanium oxide, and then into the electrolyte solution. There has been a problem that reverse electron transfer is caused from the surface of the contacted tin oxide film to the electrolyte solution side to reduce the electric power obtained.

透明導電膜と半導体微粒子との間に下引き層を形成することにより上記問題を解決することもできるが、特許文献２において提案されている光電変換素子によっては十分に高い光電変換効率を得ることができなかった。   Although the above problem can be solved by forming an undercoat layer between the transparent conductive film and the semiconductor fine particles, a sufficiently high photoelectric conversion efficiency can be obtained depending on the photoelectric conversion element proposed in Patent Document 2. I could not.

本発明の目的は、透明電極からの逆電子移動を防ぐと共に光電変換効率を向上することができる光電変換装置を提供することにある。   The objective of this invention is providing the photoelectric conversion apparatus which can improve the photoelectric conversion efficiency while preventing the reverse electron transfer from a transparent electrode.

上述の目的を達成するために、請求項１記載の光電変換装置は、ガラス基板と、前記ガラス基板上に形成された主として酸化錫から成る透明導電膜、及び、前記透明導電膜上に形成され、酸化ニオブ（Ｎｂ２Ｏ５）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム（Ａｌ２Ｏ３）の群から選択される少なくとも１つから成る酸化物膜を有する透明電極とを備える光電変換装置であって、前記酸化物膜は膜厚が０．４〜７０ｎｍであることを特徴とする。 In order to achieve the above object, a photoelectric conversion device according to claim 1 is formed on a glass substrate, a transparent conductive film mainly made of tin oxide formed on the glass substrate, and the transparent conductive film. A transparent electrode having an oxide film made of at least one selected from the group consisting of niobium oxide (Nb 2 O 5 ), magnesium oxide (MgO), and aluminum oxide (Al 2 O 3 ). The oxide film has a thickness of 0.4 to 70 nm.

請求項２記載の光電変換装置は、請求項１記載の光電変換装置において、前記酸化物膜は膜厚が３〜５ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）から成ることを特徴とする。 The photoelectric conversion device according to claim 2 is the photoelectric conversion device according to claim 1, wherein the oxide film is made of niobium oxide (Nb 2 O 5 ) having a thickness of 3 to 5 nm.

請求項３記載の光電変換装置は、請求項２記載の光電変換装置において、光電変換効率が４．４％以上であることを特徴とする。   The photoelectric conversion device according to claim 3 is the photoelectric conversion device according to claim 2, wherein the photoelectric conversion efficiency is 4.4% or more.

請求項４記載の光電変換装置は、請求項１乃至３のいずれか1項に記載の光電変換装置において、前記光電変換装置は色素増感太陽電池であることを特徴とする。   The photoelectric conversion device according to claim 4 is the photoelectric conversion device according to any one of claims 1 to 3, wherein the photoelectric conversion device is a dye-sensitized solar cell.

請求項１記載の光電変換装置によれば、ガラス基板と、ガラス基板上に形成された主として酸化錫から成る透明導電膜、及び、透明導電膜上に形成され、酸化ニオブ（Ｎｂ２Ｏ５）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム（Ａｌ２Ｏ３）の群から選択される少なくとも１つから成る酸化物膜を有する透明電極とを備え、酸化物膜は膜厚が０．４〜７０ｎｍであるので、透明導電膜への電子の移動を妨げることなく、透明導電膜から電解質液側への逆電子移動を防ぐことができ、もって光電変換効率を向上することができる。 According to the photoelectric conversion device of claim 1, a glass substrate, a transparent conductive film mainly made of tin oxide formed on the glass substrate, and niobium oxide (Nb 2 O 5 ) formed on the transparent conductive film. And a transparent electrode having an oxide film made of at least one selected from the group consisting of magnesium oxide (MgO) and aluminum oxide (Al 2 O 3 ), the oxide film having a thickness of 0.4 to 70 nm Therefore, the reverse electron transfer from the transparent conductive film to the electrolyte solution side can be prevented without hindering the movement of electrons to the transparent conductive film, and the photoelectric conversion efficiency can be improved.

請求項２記載の光電変換装置によれば、酸化物膜は膜厚が３〜５ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）から成るので、光電変換効率を４．４％以上に向上することができる。 According to the photoelectric conversion device of claim 2, since the oxide film is made of niobium oxide (Nb 2 O 5 ) having a thickness of 3 to 5 nm, the photoelectric conversion efficiency can be improved to 4.4% or more. .

本明細書において、用語「主として」とは５０重量％以上を占めることを意味する。   In the present specification, the term “mainly” means 50% by weight or more.

以下、本発明の実施の形態に係る光電変換装置を図面を参照しながら詳述する。   Hereinafter, a photoelectric conversion device according to an embodiment of the present invention will be described in detail with reference to the drawings.

図１は、本発明の実施の形態に係る光電変換装置としての色素増感太陽電池の構成を概略的に示す図である。   FIG. 1 is a diagram schematically showing a configuration of a dye-sensitized solar cell as a photoelectric conversion device according to an embodiment of the present invention.

図１において、色素増感太陽電池１００は、大きさ５ｃｍ角、厚さ３ｍｍの板状の透明な２枚のソーダライムガラス基板１０ａ，１０ｂと、各ガラス基板１０ａ，１０ｂの上に形成された厚さ７５０ｎｍのフッ素添加の酸化錫から成る透明導電膜２０ａ，２０ｂと、透明導電膜２０ａ上に形成された酸化ニオブ（Ｎｂ２Ｏ５）膜２５と、酸化ニオブ（Ｎｂ２Ｏ５）膜２５上に形成された酸化チタンから成る半導体微粒子層３０と、半導体微粒子層３０上に形成された電解質液４０と、透明導電膜２０ｂ及び電解質液４０間に形成された白金から成る対向電極５０とを備える。上記透明導電膜２０ａ及び酸化ニオブ（Ｎｂ２Ｏ５）膜２５が透明電極６０を形成する。なお、板ガラス製造ライン上でガラス基板１０ａ，１０ｂを形成すると同時に，ガラスリボンのもつ熱エネルギーを利用して成膜を行うオンラインＣＶＤ法により、ガラス基板１０ａ，１０ｂ上に透明導電膜２０ａ，２０ｂを形成することが好ましい。これにより、大面積のガラスへの生産性よく透明導電膜２０ａ，２０ｂを形成することができる。 In FIG. 1, a dye-sensitized solar cell 100 is formed on two transparent soda-lime glass substrates 10a and 10b each having a size of 5 cm square and a thickness of 3 mm, and the glass substrates 10a and 10b. Transparent conductive films 20a and 20b made of fluorine-added tin oxide having a thickness of 750 nm, a niobium oxide (Nb 2 O 5 ) film 25 formed on the transparent conductive film 20a, and a niobium oxide (Nb 2 O 5 ) film 25 A semiconductor fine particle layer 30 made of titanium oxide formed thereon, an electrolyte solution 40 formed on the semiconductor fine particle layer 30, and a counter electrode 50 made of platinum formed between the transparent conductive film 20b and the electrolyte solution 40. Prepare. The transparent conductive film 20 a and the niobium oxide (Nb 2 O 5 ) film 25 form the transparent electrode 60. The transparent conductive films 20a and 20b are formed on the glass substrates 10a and 10b by the on-line CVD method in which the glass substrates 10a and 10b are formed on the plate glass production line and at the same time the film is formed using the thermal energy of the glass ribbon. It is preferable to form. Thereby, the transparent conductive films 20a and 20b can be formed with high productivity on a large-area glass.

透明導電膜２０ａ上に形成された酸化ニオブ（Ｎｂ２Ｏ５）膜２５の替わりに、酸化マグネシウム（ＭｇＯ）又は酸化アルミニウム（Ａｌ２Ｏ３）から成る被膜を用いてもよい。ここで、酸化ニオブ（Ｎｂ２Ｏ５）膜２５、酸化マグネシウム（ＭｇＯ）膜、又は酸化アルミニウム（Ａｌ２Ｏ３）膜は、膜厚が０．４〜７０ｎｍの範囲内であることが好ましい。即ち、これらの酸化ニオブ（Ｎｂ２Ｏ５）膜２５、酸化マグネシウム（ＭｇＯ）膜、又は酸化アルミニウム（Ａｌ２Ｏ３）膜の膜厚が０．４ｎｍ以上であれば、被膜が十分に形成され、逆電子移動を防止する効果がより確実となる。一方、これらの酸化ニオブ（Ｎｂ２Ｏ５）膜２５、酸化マグネシウム（ＭｇＯ）膜、又は酸化アルミニウム（Ａｌ２Ｏ３）膜の膜厚が７０ｎｍ以下であれば、酸化チタンから成る半導体微粒子層３０を経由してきた電子を、より確実に、フッ素添加の酸化錫から成る透明導電膜２０ａ側に移動することができ、もって電力をより十分に得ることができる。 Instead of the niobium oxide (Nb 2 O 5 ) film 25 formed on the transparent conductive film 20a, a film made of magnesium oxide (MgO) or aluminum oxide (Al 2 O 3 ) may be used. Here, the niobium oxide (Nb 2 O 5 ) film 25, the magnesium oxide (MgO) film, or the aluminum oxide (Al 2 O 3 ) film preferably has a thickness in the range of 0.4 to 70 nm. That is, if the thickness of these niobium oxide (Nb 2 O 5 ) film 25, magnesium oxide (MgO) film, or aluminum oxide (Al 2 O 3 ) film is 0.4 nm or more, a coating film is sufficiently formed. The effect of preventing reverse electron transfer is more certain. On the other hand, when the film thickness of these niobium oxide (Nb 2 O 5 ) film 25, magnesium oxide (MgO) film, or aluminum oxide (Al 2 O 3 ) film is 70 nm or less, the semiconductor fine particle layer 30 made of titanium oxide. The electrons that have passed through can be moved to the transparent conductive film 20a side made of fluorine-added tin oxide more reliably, so that sufficient electric power can be obtained.

上記酸化ニオブ（Ｎｂ２Ｏ５）膜２５、酸化マグネシウム（ＭｇＯ）膜、又は酸化アルミニウム（Ａｌ２Ｏ３）膜の形成方法としては、スパッタリング法、イオンプレーティング法、真空蒸着法、電子ビーム蒸着法、化学的堆積法（ＣＶＤ法）、スプレーパイロリシス法等が挙げられる。 As a method for forming the niobium oxide (Nb 2 O 5 ) film 25, the magnesium oxide (MgO) film, or the aluminum oxide (Al 2 O 3 ) film, a sputtering method, an ion plating method, a vacuum evaporation method, an electron beam evaporation method can be used. Method, chemical deposition method (CVD method), spray pyrolysis method and the like.

フッ素添加の酸化錫から成る透明導電膜２０ａ，２０ｂは、電極として用いることができるという観点から、シート抵抗は１〜５００Ω／□の範囲であることが望ましい。また、透明導電膜２０ａ，２０ｂの膜厚としては１０〜２０００ｎｍの範囲内であることが好ましい。透明導電膜２０ａ，２０ｂの膜厚が１０ｎｍ以上であれば、より十分に低いシート抵抗が得られ、透明導電膜２０ａ，２０ｂの膜厚が２０００ｎｍ以下であれば、透明導電膜２０ａ，２０ｂの光吸収がより十分に低くなって光の透過率が十分に高くなるので、半導体微粒子層３０における半導体微粒子に担持された色素に十分に光が届くようになる。   From the viewpoint that the transparent conductive films 20a and 20b made of fluorine-added tin oxide can be used as electrodes, the sheet resistance is preferably in the range of 1 to 500Ω / □. The film thickness of the transparent conductive films 20a and 20b is preferably in the range of 10 to 2000 nm. If the film thickness of the transparent conductive films 20a and 20b is 10 nm or more, a sufficiently lower sheet resistance can be obtained. If the film thickness of the transparent conductive films 20a and 20b is 2000 nm or less, the light of the transparent conductive films 20a and 20b is obtained. Since the absorption becomes sufficiently lower and the light transmittance becomes sufficiently high, the light can sufficiently reach the dye supported on the semiconductor fine particles in the semiconductor fine particle layer 30.

また、酸化チタンから成る半導体微粒子層３０の厚さとしては１０００〜５００００ｎｍの範囲内であることが好ましい。半導体微粒子層３０の厚さが１０００ｎｍ以上であれば、半導体微粒子に担持された色素の量が十分に多いので、電子が十分に発生する。一方、半導体微粒子層３０の厚みが５００００ｎｍ以下であれば、より生産性が高くなる。   The thickness of the semiconductor fine particle layer 30 made of titanium oxide is preferably in the range of 1000 to 50000 nm. If the thickness of the semiconductor fine particle layer 30 is 1000 nm or more, the amount of the dye supported on the semiconductor fine particles is sufficiently large, so that electrons are sufficiently generated. On the other hand, when the thickness of the semiconductor fine particle layer 30 is 50000 nm or less, the productivity becomes higher.

本実施の形態によれば、ガラス基板１０と、ガラス基板１０上に形成された主として酸化錫から成る透明導電膜２０ａ、及び、透明導電膜２０ａ上に形成された上に形成された酸化ニオブ（Ｎｂ２Ｏ５）膜２５を有する透明電極６０とを備え、酸化ニオブ膜２５は膜厚が０．４〜７０ｎｍであるので、酸化チタンから成る半導体微粒子層３０から透明導電膜２０ａへの電子の移動を妨げることなく、透明導電膜２０ａから電解質液４０側への逆電子移動を防ぐことができ、もって光電変換効率を向上することができる。 According to the present embodiment, the glass substrate 10, the transparent conductive film 20a mainly made of tin oxide formed on the glass substrate 10, and the niobium oxide formed on the transparent conductive film 20a ( Nb 2 O 5 ) film 25 and transparent electrode 60, and niobium oxide film 25 has a thickness of 0.4 to 70 nm. Therefore, electrons from semiconductor fine particle layer 30 made of titanium oxide to transparent conductive film 20 a The reverse electron transfer from the transparent conductive film 20a to the electrolyte solution 40 side can be prevented without hindering the movement, and the photoelectric conversion efficiency can be improved.

本実施の形態では、ガラス基板１０ａ，１０ｂとしてソーダライムガラスを用いているが、これに限定されるものではなく、低アルカリガラス、無アルカリガラス、石英ガラス等を用いてもよい。   In the present embodiment, soda lime glass is used as the glass substrates 10a and 10b, but is not limited to this, and low alkali glass, non-alkali glass, quartz glass, or the like may be used.

本実施の形態では、ガラス基板１０ａの上にフッ素添加の酸化錫から成る透明導電膜２０ａが形成されているが、これに限定されるものではなく、ガラス基板１０ａと透明導電膜２０ａとの間にアルカリバリア膜としての酸化シリコン膜を設けてもよい。この酸化シリコン膜は５〜１００ｎｍの範囲内であることが好ましい。酸化シリコン膜の膜厚が５ｎｍ以上であればアルカリバリア性能がより確実であり、酸化シリコン膜の膜厚が１００ｎｍ以下であれば生産性が良くなる。   In the present embodiment, the transparent conductive film 20a made of fluorine-added tin oxide is formed on the glass substrate 10a. However, the present invention is not limited to this, and the gap between the glass substrate 10a and the transparent conductive film 20a is not limited thereto. Alternatively, a silicon oxide film as an alkali barrier film may be provided. This silicon oxide film is preferably in the range of 5 to 100 nm. When the thickness of the silicon oxide film is 5 nm or more, the alkali barrier performance is more reliable, and when the thickness of the silicon oxide film is 100 nm or less, the productivity is improved.

本実施の形態では、光電変換装置として色素増感太陽電池１００を用いているが、これに限定されるものではなく、アモルファスＳｉ、微結晶Ｓｉ等の薄膜シリコン太陽電池を用いてもよい。   In this embodiment, the dye-sensitized solar cell 100 is used as the photoelectric conversion device, but the present invention is not limited to this, and a thin-film silicon solar cell such as amorphous Si or microcrystalline Si may be used.

以下、本発明の実施例を説明する。   Examples of the present invention will be described below.

（実施例１）
本発明者は、まず、厚さ３ｍｍの板状の透明なソーダライムガラス基板を準備し、このソーダライムガラス基板上に厚さ３０ｎｍの酸化シリコン膜を熱ＣＶＤ法により形成し、この酸化シリコン膜上に厚さ７５０ｎｍのフッ素添加酸化錫膜を熱ＣＶＤ法により形成し、このフッ素添加酸化錫膜上に厚さ３ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）膜をスパッタリング法（Ａｒ及びＯ２がモル比で４：１の混合ガスを使用、圧力０．５Ｐａ、電力５０Ｗ）により形成し、この酸化ニオブ（Ｎｂ２Ｏ５）膜上にＳｏｌａｒｏｎｉｘ製の酸化チタンから成る厚さ５５００ｎｍの酸化チタン微粒子層を形成し、酸化チタン微粒子にＺ−９０７色素を沈着させ、モル比が１：０．５のプロピルメチルイミダゾリウムアイオダイド（ＰＭＩｍＩ）及びエチルメチルイミダゾリウムジシアノアミド （ＥＭＩｍ−ＤＣＡ）、０．５モルのヨウ素（Ｉ２）、０．５モルのｔｅｒｔ-ブチルピリジン（ＴＢＰ）、及び０．１モルのヨウ化リチウムから成る電解質液で構成される層を形成し、この電解質液で構成される層に、ソーダライムガラス基板、ソーダライムガラス基板上に形成された酸化錫膜、及び酸化錫膜の上に形成された白金から成る対向電極を貼り合せて、色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性（開放電圧、短絡電流、曲線因子、変換効率）及びセル面積を図２に実施例１として示す。 (Example 1)
The inventor first prepared a plate-shaped transparent soda lime glass substrate having a thickness of 3 mm, and formed a silicon oxide film having a thickness of 30 nm on the soda lime glass substrate by a thermal CVD method. A fluorine-added tin oxide film having a thickness of 750 nm is formed thereon by a thermal CVD method, and a niobium oxide (Nb 2 O 5 ) film having a thickness of 3 nm is formed on the fluorine-added tin oxide film by a sputtering method (Ar and O 2 are in a molar ratio). A 4: 1 ratio gas mixture, pressure 0.5 Pa, power 50 W), and a titanium oxide fine particle layer having a thickness of 5500 nm made of Solaronix titanium oxide on the niobium oxide (Nb 2 O 5 ) film. Z-907 dye is deposited on titanium oxide fine particles, and propylmethylimidazolium iodide (PMImI) and ethyl having a molar ratio of 1: 0.5 are formed. Chill imidazolium dicyanamide (EMIm-DCA), 0.5 mole of iodine (I 2), 0.5 mol of tert- butylpyridine (TBP), and composed of an electrolyte solution consisting of 0.1 moles of lithium iodide A counter electrode comprising a soda lime glass substrate, a tin oxide film formed on the soda lime glass substrate, and platinum formed on the tin oxide film. Were bonded together to obtain a dye-sensitized solar cell. The output characteristics (open-circuit voltage, short-circuit current, fill factor, conversion efficiency) and cell area of the obtained dye-sensitized solar cell are shown as Example 1 in FIG.

（実施例２）
酸化ニオブ（Ｎｂ２Ｏ５）膜の膜厚を５ｎｍとした以外は実施例１と同じである色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性及びセル面積を図２に実施例２として示す。 (Example 2)
A dye-sensitized solar cell was obtained which was the same as Example 1 except that the thickness of the niobium oxide (Nb 2 O 5 ) film was 5 nm. The output characteristics and cell area of the obtained dye-sensitized solar cell are shown in FIG.

（実施例３）
膜厚３ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）膜の替わりに膜厚７ｎｍの酸化マグネシウム（ＭｇＯ）膜を用いた以外は実施例１と同じである色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性及びセル面積を図２に実施例３として示す。 (Example 3)
A dye-sensitized solar cell was obtained in the same manner as in Example 1 except that a 7 nm-thick magnesium oxide (MgO) film was used instead of the 3 nm-thick niobium oxide (Nb 2 O 5 ) film. The output characteristics and cell area of the obtained dye-sensitized solar cell are shown in FIG.

（実施例４）
膜厚３ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）膜の替わりに膜厚０．４ｎｍの酸化アルミニウム（Ａｌ２Ｏ３）膜を用いた以外は実施例１と同じである色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性及びセル面積を図２に実施例４として示す。 Example 4
A dye-sensitized solar cell is obtained which is the same as that of Example 1 except that a 0.4 nm-thick aluminum oxide (Al 2 O 3 ) film is used instead of the 3 nm-thick niobium oxide (Nb 2 O 5 ) film. It was. The output characteristics and cell area of the obtained dye-sensitized solar cell are shown as Example 4 in FIG.

（比較例１）
酸化ニオブ（Ｎｂ２Ｏ５）膜を形成せずに、フッ素添加酸化錫膜に酸化チタン微粒子層を直接形成した以外は実施例１と同じである色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性及びセル面積を図２に比較例１として示す。 (Comparative Example 1)
A dye-sensitized solar cell was obtained which was the same as in Example 1 except that the titanium oxide fine particle layer was directly formed on the fluorine-added tin oxide film without forming the niobium oxide (Nb 2 O 5 ) film. The output characteristics and cell area of the obtained dye-sensitized solar cell are shown as Comparative Example 1 in FIG.

（比較例２）
酸化ニオブ（Ｎｂ２Ｏ５）膜の膜厚を８０ｎｍとした以外は実施例１と同じである色素増感太陽電池を得た。得られた色素増感太陽電池の出力特性及びセル面積を図２に比較例２として示す。 (Comparative Example 2)
A dye-sensitized solar cell was obtained which was the same as Example 1 except that the thickness of the niobium oxide (Nb 2 O 5 ) film was 80 nm. The output characteristics and cell area of the obtained dye-sensitized solar cell are shown in FIG.

図２より、膜厚が０．４〜７０ｎｍの範囲内である酸化ニオブ（Ｎｂ２Ｏ５）膜、酸化マグネシウム（ＭｇＯ）膜、又は酸化アルミニウム（Ａｌ２Ｏ３）膜を酸化物膜として用いると、開放電圧を６９１ｍＶ以上、短絡電流を８．００ｍＡ以上、光電変換効率を３．７８％以上にすることができることが分かった。特に、膜厚が３〜５ｎｍの範囲内である酸化ニオブ（Ｎｂ２Ｏ５）膜を酸化物膜として用いると、開放電圧を７１０ｍＶ以上、短絡電流を９．２２ｍＡ以上、変換効率を４．４６（％）以上にすることができることが分かった。 As shown in FIG. 2, a niobium oxide (Nb 2 O 5 ) film, a magnesium oxide (MgO) film, or an aluminum oxide (Al 2 O 3 ) film having a thickness in the range of 0.4 to 70 nm is used as the oxide film. It was found that the open circuit voltage can be 691 mV or more, the short circuit current can be 8.00 mA or more, and the photoelectric conversion efficiency can be 3.78% or more. In particular, when a niobium oxide (Nb 2 O 5 ) film having a thickness of 3 to 5 nm is used as the oxide film, the open circuit voltage is 710 mV or more, the short circuit current is 9.22 mA or more, and the conversion efficiency is 4.46. It turned out that it can be made more than (%).

本発明の実施の形態に係る光電変換装置としての色素増感太陽電池の構成を概略的に示す図である。It is a figure which shows schematically the structure of the dye-sensitized solar cell as a photoelectric conversion apparatus which concerns on embodiment of this invention. 本発明の実施例及び比較例に係る色素増感太陽電池の出力特性及びセル面積を示す図である。It is a figure which shows the output characteristic and cell area of the dye-sensitized solar cell which concern on the Example and comparative example of this invention.

符号の説明Explanation of symbols

１０ａ ガラス基板
１０ｂ ガラス基板
２０ａ 透明導電膜
２０ｂ 透明導電膜
２５ 酸化ニオブ（Ｎｂ２Ｏ５）膜
３０ 半導体微粒子層
４０ 電解質液
５０ 対向電極
６０ 透明電極
１００ 色素増感太陽電池 10a glass substrate 10b glass substrate 20a transparent conductive film 20b transparent conductive film 25 niobium oxide (Nb 2 O 5 ) film 30 semiconductor fine particle layer 40 electrolyte solution 50 counter electrode 60 transparent electrode 100 dye-sensitized solar cell

Claims (4)

ガラス基板と、前記ガラス基板上に形成された主として酸化錫から成る透明導電膜、及び、前記透明導電膜上に形成され、酸化ニオブ（Ｎｂ２Ｏ５）、酸化マグネシウム（ＭｇＯ）、酸化アルミニウム（Ａｌ２Ｏ３）の群から選択される少なくとも１つから成る酸化物膜を有する透明電極とを備える光電変換装置であって、前記酸化物膜は膜厚が０．４〜７０ｎｍであることを特徴とする光電変換装置。 A glass substrate, a transparent conductive film mainly made of tin oxide formed on the glass substrate, and niobium oxide (Nb 2 O 5 ), magnesium oxide (MgO), aluminum oxide ( And a transparent electrode having an oxide film made of at least one selected from the group of Al 2 O 3 ), wherein the oxide film has a thickness of 0.4 to 70 nm. A featured photoelectric conversion device. 前記酸化物膜は膜厚が３〜５ｎｍの酸化ニオブ（Ｎｂ２Ｏ５）から成ることを特徴とする請求項１記載の光電変換装置。 2. The photoelectric conversion device according to claim 1, wherein the oxide film is made of niobium oxide (Nb 2 O 5 ) having a thickness of 3 to 5 nm. 光電変換効率が４．４％以上であることを特徴とする請求項２記載の光電変換装置。   The photoelectric conversion device according to claim 2, wherein the photoelectric conversion efficiency is 4.4% or more. 前記光電変換装置は色素増感太陽電池であることを特徴とする請求項１乃至３のいずれか１項に記載の光電変換装置。   The photoelectric conversion device according to any one of claims 1 to 3, wherein the photoelectric conversion device is a dye-sensitized solar cell.
JP2006254444A 2006-09-20 2006-09-20 Photoelectric converter Pending JP2008077924A (en)

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JP2012199228A (en) * 2011-03-09 2012-10-18 Osaka Gas Co Ltd All solid photosensitive solar cell
JP2015118873A (en) * 2013-12-19 2015-06-25 積水化学工業株式会社 Photoelectrode, manufacturing method of the same, and dye-sensitized solar cell
JP6058190B1 (en) * 2016-05-12 2017-01-11 株式会社昭和 Dye-sensitized solar cell with high conversion efficiency
JP6104446B1 (en) * 2016-10-07 2017-03-29 株式会社昭和 Dye-sensitized solar cell module
US10727001B2 (en) 2014-04-16 2020-07-28 Ricoh Company, Ltd. Photoelectric conversion element

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012199228A (en) * 2011-03-09 2012-10-18 Osaka Gas Co Ltd All solid photosensitive solar cell
JP2015118873A (en) * 2013-12-19 2015-06-25 積水化学工業株式会社 Photoelectrode, manufacturing method of the same, and dye-sensitized solar cell
US10727001B2 (en) 2014-04-16 2020-07-28 Ricoh Company, Ltd. Photoelectric conversion element
EP3975278A1 (en) 2014-04-16 2022-03-30 Ricoh Company, Ltd. Photoelectric conversion element
US11069485B2 (en) 2014-04-16 2021-07-20 Ricoh Company, Ltd. Photoelectric conversion element
JP6058190B1 (en) * 2016-05-12 2017-01-11 株式会社昭和 Dye-sensitized solar cell with high conversion efficiency
WO2017195648A1 (en) 2016-05-12 2017-11-16 株式会社昭和 Dye-sensitized solar cell having high conversion efficiency
JP2017204585A (en) * 2016-05-12 2017-11-16 株式会社昭和 Dye-sensitized solar battery having high conversion efficiency
KR20190008063A (en) 2016-05-12 2019-01-23 가부시키가이샤 쇼와 Dye-sensitized solar cell with high conversion efficiency
JP2018060972A (en) * 2016-10-07 2018-04-12 株式会社昭和 Dye sensitization solar cell module
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