JP2010267534A - Dye-sensitized solar cell - Google Patents

Dye-sensitized solar cell Download PDF

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JP2010267534A
JP2010267534A JP2009118801A JP2009118801A JP2010267534A JP 2010267534 A JP2010267534 A JP 2010267534A JP 2009118801 A JP2009118801 A JP 2009118801A JP 2009118801 A JP2009118801 A JP 2009118801A JP 2010267534 A JP2010267534 A JP 2010267534A
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transport layer
solar cell
thin film
light absorption
dye
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JP5400470B2 (en
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Takashi Ikuno
孝 生野
Naohiko Kato
直彦 加藤
Kazuo Higuchi
和夫 樋口
Yasuhiko Takeda
康彦 竹田
Toshiyuki Sano
利行 佐野
Tatsuo Toyoda
竜生 豊田
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Toyota Central R&D Labs Inc
Aisin Corp
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Aisin Seiki Co Ltd
Toyota Central R&D Labs Inc
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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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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

<P>PROBLEM TO BE SOLVED: To aim at improvement in photoelectric conversion efficiency of a solid dye-sensitized solar cell. <P>SOLUTION: The dye-sensitized solar cell 100 is provided with an electron transport layer 3, a light absorption layer 5, and a hole transport layer 7. The electron transport layer 3 is structured of titanium oxide or zinc oxide, the light absorption layer 5 is structured of either oxide of metal selected from Co and Cu, or fluoride of metal selected from Bi, Sn, Cu and Mo, and the hole transport layer 7 is structured of nickel oxide doped with Li. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、色素増感型太陽電池及びその製造方法に関する。   The present invention relates to a dye-sensitized solar cell and a method for producing the same.

固体金属酸化物等から構成される固体型の色素増感型太陽電池について検討されている（例えば、特許文献１）。固体型の色素増感型太陽電池は、液状電解質の場合に問題となる液漏れを回避可能であるなどの利点を有する。   A solid-type dye-sensitized solar cell composed of a solid metal oxide or the like has been studied (for example, Patent Document 1). The solid-type dye-sensitized solar cell has advantages such as that it is possible to avoid liquid leakage that becomes a problem in the case of a liquid electrolyte.

特開２００６−２１６９５８号公報JP 2006-216958 A

しかし、従来の固体型の色素増感型太陽電池は、液状電解質を用いたものと比較して、光電変換効率の点で必ずしも未だ十分なものではなかった。   However, conventional solid dye-sensitized solar cells have not always been sufficient in terms of photoelectric conversion efficiency as compared with those using a liquid electrolyte.

そこで、本発明の目的は、固体型の色素増感型太陽電池において、光電変換効率の更なる改善を図ることにある。   Accordingly, an object of the present invention is to further improve the photoelectric conversion efficiency in a solid dye-sensitized solar cell.

本発明は、電子輸送層と、光吸収層と、正孔輸送層と、を備え、電子輸送層、光吸収層及び正孔輸送層がこの順に積層されている色素増感型太陽電池に関する。本発明に係る色素増感型太陽電池において、電子輸送層は、酸化チタン又は酸化亜鉛から構成され、光吸収層は、Ｃｏ及びＣｕから選ばれる金属の酸化物、又はＢｉ、Ｓｎ、Ｃｕ及びＭｏから選ばれる金属の硫化物から構成され、正孔輸送層は、Ｌｉによってドープされた酸化ニッケルから構成される。   The present invention relates to a dye-sensitized solar cell including an electron transport layer, a light absorption layer, and a hole transport layer, and the electron transport layer, the light absorption layer, and the hole transport layer are stacked in this order. In the dye-sensitized solar cell according to the present invention, the electron transport layer is composed of titanium oxide or zinc oxide, and the light absorption layer is a metal oxide selected from Co and Cu, or Bi, Sn, Cu, and Mo. The hole transport layer is composed of nickel oxide doped with Li.

本発明に係る色素増感型太陽電池によれば、上記特定の構成を備えることにより、固体型の色素増感型太陽電池において、光電変換効率の更なる改善を図ることが可能である。正孔輸送層を構成する酸化ニッケルをＬｉによってドープすることにより、酸化ニッケルの抵抗率が低下して励起キャリアが取り出され易くなり、さらには、酸化ニッケルの可視光域の光吸収量が増加して量子収率が向上し、その結果、光電変換効率向上の効果が奏されると考えられる。   According to the dye-sensitized solar cell according to the present invention, it is possible to further improve the photoelectric conversion efficiency in the solid-state dye-sensitized solar cell by including the specific configuration. By doping the nickel oxide that constitutes the hole transport layer with Li, the resistivity of the nickel oxide is lowered and the excited carriers are easily extracted, and further, the light absorption amount of the nickel oxide in the visible light region is increased. Thus, it is considered that the quantum yield is improved, and as a result, the effect of improving the photoelectric conversion efficiency is exhibited.

本発明による効果をより一層顕著なものとするために、正孔輸送層が、当該正孔輸送層全体を基準として０．１〜１０原子％のＬｉを含有することが好ましい。   In order to make the effect of the present invention more remarkable, it is preferable that the hole transport layer contains 0.1 to 10 atomic% Li based on the whole hole transport layer.

光吸収層が、電子輸送層、光吸収層及び正孔輸送層の積層方向に波打つ凹凸面に沿って形成されていることが好ましい。これによりキャリアが生成する面積が大きくなって、更なる光電変換率向上の効果が得られる。   The light absorption layer is preferably formed along an uneven surface that undulates in the stacking direction of the electron transport layer, the light absorption layer, and the hole transport layer. Thereby, the area which a carrier produces | generates becomes large and the effect of the further photoelectric conversion rate improvement is acquired.

本発明によれば、固体型の色素増感型太陽電池において、光電変換効率の更なる改善を図ることにある。   According to the present invention, in the solid dye-sensitized solar cell, the photoelectric conversion efficiency is further improved.

色素増感型太陽電池の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of a dye-sensitized solar cell. 色素増感型太陽電池の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of a dye-sensitized solar cell. 色素増感型太陽電池のＩＶ特性を示すグラフである。It is a graph which shows the IV characteristic of a dye-sensitized solar cell. ＬｉＯ薄膜の抵抗率とＬｉ濃度との関係を示すグラフである。It is a graph which shows the relationship between the resistivity of a LiO thin film, and Li density | concentration. 吸光度と波長との関係を示すグラフである。It is a graph which shows the relationship between a light absorbency and a wavelength. Ｌｉによってドープされた酸化ニッケル薄膜のＸＲＤパターンである。It is an XRD pattern of a nickel oxide thin film doped with Li.

以下、本発明の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。   Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

図１は、色素増感型太陽電池の一実施形態を示す断面図である。図１に示す色素増感型太陽電池１００は、透明導電性基板１と、電子輸送層３と、光吸収層５と、正孔輸送層７と、Ａｇ電極１２とから主として構成される。透明導電性基板１は透明基板１０及び透明基板１０上に形成された透明導電膜１１を有している。電子輸送層３、光吸収層５及び正孔輸送層７は、透明導電性基板１の透明導電膜１１上にこの順で積層されている。色素増感型太陽電池１００に対して照射された光は、主として光吸収層５によって吸収される。言い換えると、光吸収層５は増感色素として機能する。光の吸収によってキャリアが生成し、光吸収層５に接する電子輸送層３側に電子が移動し、光吸収層５に接する正孔輸送層７側に正孔が移動して、電流が発生する。   FIG. 1 is a cross-sectional view showing one embodiment of a dye-sensitized solar cell. A dye-sensitized solar cell 100 shown in FIG. 1 is mainly composed of a transparent conductive substrate 1, an electron transport layer 3, a light absorption layer 5, a hole transport layer 7, and an Ag electrode 12. The transparent conductive substrate 1 has a transparent substrate 10 and a transparent conductive film 11 formed on the transparent substrate 10. The electron transport layer 3, the light absorption layer 5, and the hole transport layer 7 are laminated on the transparent conductive film 11 of the transparent conductive substrate 1 in this order. The light irradiated to the dye-sensitized solar cell 100 is mainly absorbed by the light absorption layer 5. In other words, the light absorption layer 5 functions as a sensitizing dye. Carriers are generated by light absorption, electrons move to the electron transport layer 3 side in contact with the light absorption layer 5, holes move to the hole transport layer 7 side in contact with the light absorption layer 5, and current is generated. .

電子輸送層３は、酸化チタン又は酸化亜鉛を主成分として含む薄膜である。好ましくは、電子輸送層３はアナターゼ型の酸化チタンから構成される。   The electron transport layer 3 is a thin film containing titanium oxide or zinc oxide as a main component. Preferably, the electron transport layer 3 is made of anatase type titanium oxide.

光吸収層５は、Ｃｏ及びＣｕから選ばれる金属の酸化物、又はＢｉ、Ｓｎ、Ｃｕ及びＭｏから選ばれる金属の硫化物を主成分として含む薄膜である。好ましくは、光吸収層５は酸化コバルト（Ｃｏ３Ｏ４）の薄膜である。 The light absorption layer 5 is a thin film containing a metal oxide selected from Co and Cu, or a metal sulfide selected from Bi, Sn, Cu and Mo as a main component. Preferably, the light absorption layer 5 is a thin film of cobalt oxide (Co 3 O 4 ).

正孔輸送層７は、正孔輸送層７は、Ｌｉによってドープされた酸化ニッケルを主成分として含む薄膜である。光電変換効率向上の観点から、Ｌｉの含有量は、正孔輸送層７全体を基準として好ましくは０．１〜１０原子％である。Ｌｉの含有量が小さく
なると、正孔輸送層７の抵抗率が低下する傾向があることから、Ｌｉの含有量はより好ましくは１原子％以上である。ただし、Ｌｉの含有量が大きくなると酸化ニッケルの結晶性が低下する傾向があることから、Ｌｉの含有量は３原子％以下がより好ましい。 The hole transport layer 7 is a thin film containing nickel oxide doped with Li as a main component. From the viewpoint of improving the photoelectric conversion efficiency, the Li content is preferably 0.1 to 10 atomic% based on the whole hole transport layer 7. Since the resistivity of the hole transport layer 7 tends to decrease as the Li content decreases, the Li content is more preferably 1 atomic% or more. However, since the crystallinity of nickel oxide tends to decrease as the Li content increases, the Li content is more preferably 3 atomic% or less.

図２の断面図に示されるように、光吸収層５が、電子輸送層３、光吸収層５及び正孔輸送層７の積層方向に波打つ凹凸面に沿って形成されていてもよい。この場合、電子輸送層３の光吸収層５側の面、及び正孔輸送層７の光吸収層５側の面は、光吸収層５に沿う凹凸形状を形成している。   As shown in the sectional view of FIG. 2, the light absorption layer 5 may be formed along an uneven surface that undulates in the stacking direction of the electron transport layer 3, the light absorption layer 5, and the hole transport layer 7. In this case, the surface on the light absorption layer 5 side of the electron transport layer 3 and the surface on the light absorption layer 5 side of the hole transport layer 7 form an uneven shape along the light absorption layer 5.

透明導電性基板１は、ガラス基板等の透明基板１０と、これの受光面とは反対側の面上に設けられた透明導電膜１１とを有する。透明導電性基板１として、通常の色素増感型太陽電池若しくは無機固体型太陽電池に搭載される透明電極、又は液晶パネル等に用いられる透明電極を使用できる。透明導電膜１１は、例えばＩＴＯ膜であり得る。   The transparent conductive substrate 1 includes a transparent substrate 10 such as a glass substrate and a transparent conductive film 11 provided on a surface opposite to the light receiving surface thereof. As the transparent conductive substrate 1, a transparent electrode mounted on a normal dye-sensitized solar cell or an inorganic solid solar cell, or a transparent electrode used for a liquid crystal panel or the like can be used. The transparent conductive film 11 can be, for example, an ITO film.

透明導電性基板１の具体例として、フッ素ドープＳｎＯ２コートガラス、ＩＴＯコート
ガラス、ＺｎＯ：Ａｌコートガラス、及びアンチモンドープ酸化スズ（ＳｎＯ２−Ｓｂ）
がある。 Specific examples of the transparent conductive substrate 1 include fluorine-doped SnO 2 coated glass, ITO coated glass, ZnO: Al coated glass, and antimony-doped tin oxide (SnO 2 —Sb).
There is.

Ａｇ電極１２はＡｇペーストを塗布する方法により形成され、その形状は特に限定されない。他の金属から構成される電極を接続端子として設けてもよい。   The Ag electrode 12 is formed by a method of applying an Ag paste, and the shape thereof is not particularly limited. You may provide the electrode comprised from another metal as a connection terminal.

色素増感型太陽電池１００は、例えば、透明導電性基板１の透明導電膜１１上に、酸化チタン又は酸化亜鉛から構成される薄膜、Ｃｏ及びＣｕから選ばれる金属の酸化物、又はＢｉ、Ｓｎ、Ｃｕ及びＭｏから選ばれる金属の硫化物から構成される薄膜と、Ｌｉによってドープされた酸化ニッケルから構成される薄膜をこの順に形成する工程と、形成された各薄膜を加熱する工程とを備える方法によって製造することができる。   The dye-sensitized solar cell 100 includes, for example, a thin film composed of titanium oxide or zinc oxide, a metal oxide selected from Co and Cu, or Bi, Sn on the transparent conductive film 11 of the transparent conductive substrate 1. And a step of forming a thin film composed of a sulfide of a metal selected from Cu and Mo, a thin film composed of nickel oxide doped with Li in this order, and a step of heating each formed thin film It can be manufactured by a method.

各薄膜は、スパッタ等の通常の薄膜の成膜方法を採用して形成することができる。各薄膜を形成する毎にその薄膜を加熱してもよいし、３つの薄膜を形成した後、それらをまとめて加熱してもよい。薄膜の加熱は、通常、４００〜５００℃、３０分〜３時間行われる。   Each thin film can be formed by employing an ordinary thin film forming method such as sputtering. Each time a thin film is formed, the thin film may be heated, or after forming three thin films, they may be heated together. The thin film is usually heated at 400 to 500 ° C. for 30 minutes to 3 hours.

以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。   Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

透明導電膜ＦＴＯがコーティングされたガラス基板（ＴＣＯガラス基板）を準備し、その透明導電膜上に、ＴｉＯ２薄膜（厚さ２００ｎｍ）、Ｃｏ３Ｏ４薄膜（厚さ１０ｎｍ）、及びＬｉドープＮｉＯ（ＮｉＯ：Ｌｉ）薄膜（厚さ２００ｎｍ）を、スパッタにより順に成膜した。スパッタはＲＦマグネトロンスパッタ装置を用い、室温で成膜を行った。各薄膜のスパッタ条件は下記の通りである。ＮｉＯ：Ｌｉ薄膜におけるＬｉの濃度は２原子％とした。 A glass substrate (TCO glass substrate) coated with a transparent conductive film FTO is prepared, and on the transparent conductive film, a TiO 2 thin film (thickness 200 nm), a Co 3 O 4 thin film (thickness 10 nm), and Li-doped NiO (NiO: Li) thin films (thickness: 200 nm) were sequentially formed by sputtering. Sputtering was performed at room temperature using an RF magnetron sputtering apparatus. The sputtering conditions for each thin film are as follows. The concentration of Li in the NiO: Li thin film was 2 atomic%.

ＴｉＯ２薄膜スパッタ条件
到達真空度：２×１０−６（Ｔｏｒｒ）
ガス：Ａｒ／Ｏ２（８：２）
成膜真空度：４×１０−３（Ｔｏｒｒ）
ターゲット：ＴｉＯ２
投入電力：６００Ｗ TiO 2 thin film sputtering condition reached vacuum: 2 × 10 −6 (Torr)
Gas: Ar / O 2 (8: 2)
Deposition vacuum: 4 × 10 −3 (Torr)
Target: TiO 2
Input power: 600W

Ｃｏ３Ｏ４薄膜スパッタ条件
到達真空度：２×１０−５（Ｔｏｒｒ）
ガス：Ａｒ／Ｏ２（１：１）
成膜真空度：３×１０−３（Ｔｏｒｒ）
ターゲット：Ｃｏ３Ｏ４
投入電力：１５０Ｗ
自己バイアス：−４７０Ｗ
成膜時間：５分 Co 3 O 4 thin film sputtering condition reached vacuum: 2 × 10 −5 (Torr)
Gas: Ar / O 2 (1: 1)
Deposition vacuum: 3 × 10 −3 (Torr)
Target: Co 3 O 4
Input power: 150W
Self bias: -470W
Deposition time: 5 minutes

ターゲット：ＮｉＯ：Ｌｉ薄膜スパッタ条件
到達真空度：２×１０−５（Ｔｏｒｒ）
ガス：Ａｒ／Ｏ２（１：１）
ＮｉＯ：Ｌｉ（２％），ｕｎｄｏｐｅ−ＮｉＯ
投入電力：１５０Ｗ
自己バイアス：−４３０Ｗ
成膜時間：２時間 Target: NiO: Li thin film sputtering condition reached vacuum: 2 × 10 −5 (Torr)
Gas: Ar / O 2 (1: 1)
NiO: Li (2%), undope-NiO
Input power: 150W
Self bias: -430W
Deposition time: 2 hours

成膜後、Ｎ２／Ｏ２（８：２）混合ガス中、大気圧下で、４５０℃、２時間の熱処理を行い、各薄膜の結晶化を進行させた。ＴｉＯ２薄膜はアナターゼ型ＴｉＯ２から構成されることが確認された。次いで、ＮｉＯ：Ｌｉ薄膜上にＡｇペーストを塗布して電極を形成させた。以上の手順により、ＴＣＯガラス基板上にＴｉＯ２薄膜／Ｃｏ２Ｏ４薄膜／ＮｉＯ:Ｌｉ薄膜がこの順で積層された積層構成を有する太陽電池を作製した。 After the film formation, heat treatment was performed at 450 ° C. for 2 hours in an N 2 / O 2 (8: 2) mixed gas at atmospheric pressure to promote crystallization of each thin film. It was confirmed that the TiO 2 thin film is composed of anatase TiO 2 . Next, an Ag paste was applied on the NiO: Li thin film to form an electrode. By the above procedure, a solar cell having a laminated structure in which a TiO 2 thin film / Co 2 O 4 thin film / NiO: Li thin film was laminated in this order on a TCO glass substrate was produced.

さらに、光吸収層であるＣｏ３Ｏ４薄膜を有しない太陽電池のサンプルとして、ＮｉＯ：Ｌｉ薄膜／ＴｉＯ２薄膜をＴＣＯガラス基板上に積層したもの、及びＮｉＯ薄膜（アンドープ）／ＴｉＯ２薄膜をＴＣＯガラス基板上に積層したものを作製した。Ｃｏ３Ｏ４薄膜を成膜しなかったことの他は上記と同様の操作で太陽電池を作製した。 Furthermore, as a sample of a solar cell having no Co 3 O 4 thin film as a light absorption layer, a NiO: Li thin film / TiO 2 thin film laminated on a TCO glass substrate, and a NiO thin film (undoped) / TiO 2 thin film What was laminated | stacked on the TCO glass substrate was produced. A solar cell was fabricated in the same manner as described above except that no Co 3 O 4 thin film was formed.

作製した太陽電池に対して１ｓｕｎの光を照射し、そのときのＩＶ特性を測定した。図３は、各太陽電池のＩＶ特性（電流密度（Ｃｕｒｒｅｎｔ Ｄｅｎｓｉｔｙ）と電圧（Ａｐｐｌｉｅｄ Ｖｏｌｔａｇｅ）との関係）を示すグラフである。ＮｉＯ：Ｌｉ／ＴｉＯ２の開放電圧は０．２１Ｖ、短絡電流密度は８８μＡ／ｃｍ２であり、これらはＮｉＯがＬｉによってドープされていないＮｉＯ／ＴｉＯ２と比較して大きい値である。光吸収層としてＣｏ３Ｏ４薄膜を導入したＮｉＯ：Ｌｉ／Ｃｏ３Ｏ４／ＴｉＯ２の開放電圧は０．３９Ｖ、短絡電流密度は２８９μＡ／ｃｍ２であり、ＮｉＯ：Ｌｉ／ＴｉＯ２と比較してさらに電池特性の向上が認められた。 The produced solar cell was irradiated with 1 sun of light, and the IV characteristics at that time were measured. FIG. 3 is a graph showing IV characteristics (relationship between current density and applied voltage) of each solar cell. The open-circuit voltage of NiO: Li / TiO 2 is 0.21 V, and the short-circuit current density is 88 μA / cm 2, which are higher values than NiO / TiO 2 in which NiO is not doped with Li. NiO: Li / Co 3 O 4 / TiO 2 introduced with a Co 3 O 4 thin film as a light absorption layer has an open-circuit voltage of 0.39 V and a short-circuit current density of 289 μA / cm 2. Compared with NiO: Li / TiO 2 Further improvement in battery characteristics was observed.

さらに、ＬｉでドープされていないＮｉＯ薄膜、及び２原子％又は１０原子％の濃度のＬｉでドープされたＮｉＯ薄膜を石英基板上に作製し、それらに可視光を照射したときの抵抗率を測定した。図４は、ＬｉＯ薄膜の抵抗率（Ｒｅｓｉｓｔｉｖｉｔｙ）とＬｉ濃度（原子％）との関係を示すグラフである。図４に示されるように、２原子％のＬｉをドープすることにより抵抗率が二桁減少し、１０原子％のＬｉをドープすることにより抵抗率が四桁減少した。この抵抗率は太陽電池の等価回路における直列抵抗成分に一部に相当する。直列抵抗成分の増加は太陽電池の特性低下（電流低下、ファイルファクター低下）を招くことが知られている。   Furthermore, NiO thin film not doped with Li and NiO thin film doped with Li at a concentration of 2 atomic% or 10 atomic% are prepared on a quartz substrate, and the resistivity is measured when they are irradiated with visible light. did. FIG. 4 is a graph showing the relationship between the resistivity (Resitivity) of the LiO thin film and the Li concentration (atomic%). As shown in FIG. 4, the resistivity decreased by two orders of magnitude by doping 2 atomic% Li, and the resistivity decreased by four orders of magnitude by doping 10 atomic% Li. This resistivity corresponds to a part of the series resistance component in the equivalent circuit of the solar cell. It is known that an increase in the series resistance component causes a decrease in characteristics of the solar cell (current decrease, file factor decrease).

石英基板上に、ＬｉでドープされていないＮｉＯ薄膜、及び２原子％のＬｉでドープされたＮｉＯ：Ｌｉ薄膜を室温で石英基板上に成膜した。ＬｉでドープされていないＮｉＯ薄膜は４００℃又は７００℃で、ＮｉＯ：Ｌｉ薄膜は４００℃で熱処理した。熱処理後の薄膜の光吸収特性を測定した。図５は、各薄膜の吸光度（Ａｂｓｏｒｐｔｉｏｎ ｃｏｅｆｆｉｃｉｅｎｔ）と波長（Ｗａｖｅｌｅｎｇｔｈ）との関係を示すグラフである。図５に示されるように、Ｌｉをドープすることにより、アンドープの場合と比較してＮｉＯ薄膜の可視光域の吸光度が大きく向上した。   A NiO thin film not doped with Li and a NiO: Li thin film doped with 2 atomic% Li were formed on a quartz substrate at room temperature. The NiO thin film not doped with Li was heat-treated at 400 ° C. or 700 ° C., and the NiO: Li thin film was heat-treated at 400 ° C. The light absorption characteristics of the thin film after heat treatment were measured. FIG. 5 is a graph showing the relationship between the absorbance (absorption coefficient) and wavelength (wavelength) of each thin film. As shown in FIG. 5, by doping with Li, the absorbance in the visible light region of the NiO thin film was greatly improved as compared with the undoped case.

図６は、２原子％のＬｉでドープされたＮｉＯ：Ｌｉ薄膜のＸＲＤパターンを示すグラフである。図６に示されるように、ＬｉがドープされたときであってもＮｉＯ自体の結晶構造が維持されることが確認された。   FIG. 6 is a graph showing an XRD pattern of a NiO: Li thin film doped with 2 atomic% Li. As shown in FIG. 6, it was confirmed that the crystal structure of NiO itself was maintained even when Li was doped.

以上の実験結果から、ＬｉでドープされたＮｉＯ薄膜を採用することにより、固体型の色素増感型太陽電池において優れた電池特性が得られることが確認された。係る電池特性の向上に対しては、Ｌｉのドープによって、ＮｉＯ薄膜の抵抗率減少ばかりでなく、可視光域の吸光度向上が大きく寄与していることが示唆された。   From the above experimental results, it was confirmed that by using a NiO thin film doped with Li, excellent battery characteristics can be obtained in a solid dye-sensitized solar cell. It was suggested that for the improvement of the battery characteristics, not only the decrease in resistivity of the NiO thin film but also the increase in absorbance in the visible light region contributed greatly by doping with Li.

１…透明導電性基板、３…電子輸送層、５…光吸収層、７…正孔輸送層、１０…透明基板、１１…透明導電膜、１２…Ａｇ電極。   DESCRIPTION OF SYMBOLS 1 ... Transparent conductive substrate, 3 ... Electron transport layer, 5 ... Light absorption layer, 7 ... Hole transport layer, 10 ... Transparent substrate, 11 ... Transparent electrically conductive film, 12 ... Ag electrode.

Claims (3)

電子輸送層と、光吸収層と、正孔輸送層と、を備え、
前記電子輸送層、前記光吸収層及び前記正孔輸送層がこの順に積層されており、
前記電子輸送層が、酸化チタン又は酸化亜鉛から構成され、
前記光吸収層が、Ｃｏ及びＣｕから選ばれる金属の酸化物、又はＢｉ、Ｓｎ、Ｃｕ及びＭｏから選ばれる金属の硫化物から構成され、
前記正孔輸送層が、Ｌｉによってドープされた酸化ニッケルから構成される、
色素増感型太陽電池。 An electron transport layer, a light absorption layer, and a hole transport layer;
The electron transport layer, the light absorption layer and the hole transport layer are laminated in this order,
The electron transport layer is composed of titanium oxide or zinc oxide,
The light absorption layer is composed of a metal oxide selected from Co and Cu, or a metal sulfide selected from Bi, Sn, Cu and Mo,
The hole transport layer is composed of nickel oxide doped with Li;
Dye-sensitized solar cell. 前記正孔輸送層が、当該正孔輸送層全体を基準として０．１〜１０原子％のＬｉを含有する、請求項１に記載の色素増感型太陽電池。   The dye-sensitized solar cell according to claim 1, wherein the hole transport layer contains 0.1 to 10 atomic% of Li based on the whole hole transport layer. 前記光吸収層が、前記電子輸送層、前記光吸収層及び前記正孔輸送層の積層方向に波打つ凹凸面に沿って形成されている、請求項１又は２に記載の色素増感型太陽電池。
3. The dye-sensitized solar cell according to claim 1, wherein the light absorption layer is formed along an uneven surface that undulates in the stacking direction of the electron transport layer, the light absorption layer, and the hole transport layer. .
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