JP2006013097A - Organic/inorganic composite solar cell - Google Patents

Organic/inorganic composite solar cell Download PDF

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JP2006013097A
JP2006013097A JP2004187418A JP2004187418A JP2006013097A JP 2006013097 A JP2006013097 A JP 2006013097A JP 2004187418 A JP2004187418 A JP 2004187418A JP 2004187418 A JP2004187418 A JP 2004187418A JP 2006013097 A JP2006013097 A JP 2006013097A
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solar cell
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Osamu Shiino
修 椎野
Shinichiro Sugi
信一郎 杉
Masahito Yoshikawa
雅人 吉川
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Bridgestone Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic composite solar cell which ensures higher conversion efficiency and particularly is capable of improving a short circuit current. <P>SOLUTION: A transparent conductive film 1, an n-type inorganic semiconductor film 2, an n-type organic semiconductor film 3, a p-type organic semiconductor film 4, a p-type inorganic semiconductor film 5, and a metal electrode 6, are stacked in this sequence. A transparent conductive film 7, an n-type inorganic semiconductor film 8, a mixed film 9 of a p-type organic semiconductor and an n-type organic semiconductor, a p-type inorganic semiconductor film 10, and a metal electrode 11, are stacked in this sequence. An n-type transparent conductive film 12, an n-type organic semiconductor film 13, a p-type organic semiconductor film 14, and a p-type transparent conductive film 15, are stacked in this sequence. An n-type transparent conductive film 16, a mixed film 17 of a p-type organic semiconductor and an n-type organic semiconductor, and a p-type transparent conductive film 18, are stacked in this sequence. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は有機半導体と無機半導体の膜を備えた太陽電池に関するものである。   The present invention relates to a solar cell provided with a film of an organic semiconductor and an inorganic semiconductor.

太陽電池は、従来その光電変換効率の高さから、シリコン、ＣｄＳ、ＣｄＴｅ、ＣｄＡｓなどの無機半導体が用いられてきた。これらの変換効率は、例えばシリコンを用いた場合には約１５％にも達する。しかしながら、これら無機半導体を用いた太陽電池では、単結晶作製、ドーピングプロセスなどの多くのプロセスが電池作製に必要であるため、生産コストが非常に高くなるという問題点を有している。   Conventionally, an inorganic semiconductor such as silicon, CdS, CdTe, CdAs has been used for the solar cell because of its high photoelectric conversion efficiency. These conversion efficiencies reach about 15% when silicon is used, for example. However, solar cells using these inorganic semiconductors have a problem that the production cost is very high because many processes such as single crystal production and doping process are necessary for battery production.

有機半導体を用いる太陽電池は、無機半導体を用いた太陽電池に比べ製造工程が容易であり、低コストで大面積化が可能であるという利点を持つところから、この太陽電池に用いられる光電変換素子に関し種々の提案がなされている（下記非特許文献１，２）。
第６４回応用物理学会学術講演会 講演予稿集（２００３年秋 福岡大学）３１ｐ−ＹＬ−１８ 第５０回応用物理学関係連合講演会 講演予稿集（２００３．３ 神奈川大学）２９ａ−Ｂ−５ Photovoltaic conversion elements used for solar cells using organic semiconductors are advantageous in that the manufacturing process is easier than solar cells using inorganic semiconductors and the area can be increased at low cost. Various proposals have been made (Non-Patent Documents 1 and 2 below).
64th JSAP Scientific Lecture Proceedings (Autumn 2003, Fukuoka University) 31p-YL-18 Proceedings of the 50th Joint Conference on Applied Physics (2003.3 Kanagawa University) 29a-B-5

これまでの有機材料を用いた太陽電池は大きく分けて、(1)金属／ｐ型（ｎ型）有機半導体膜／金属（ショットキー型）、(2)金属／ｐ型有機半導体膜／ｎ型有機半導体膜／金属（ｂｉ−ｌａｙｅｒ型）、(3)金属／ｐ型有機半導体とｎ型無機半導体との混合膜／金属、の三種類に分類できる。しかし、これらの太陽電池は開放電圧は高いものの電子の移動度が低いために短絡電流は小さく、太陽電池としての変換効率は低かった。   Conventional solar cells using organic materials can be broadly divided into (1) metal / p-type (n-type) organic semiconductor film / metal (Schottky type) and (2) metal / p-type organic semiconductor film / n-type. There are three types: organic semiconductor film / metal (bi-layer type), and (3) mixed film / metal of metal / p-type organic semiconductor and n-type inorganic semiconductor. However, although these solar cells have a high open circuit voltage, the short circuit current is small because of the low mobility of electrons, and the conversion efficiency as a solar cell is low.

本発明は、変換効率が高く、特に短絡電流を向上することができる有機無機複合太陽電池を提供することを目的とする。   An object of the present invention is to provide an organic-inorganic composite solar cell that has high conversion efficiency and can particularly improve a short-circuit current.

請求項１の有機無機複合太陽電池は、１対の電極間に半導体膜が設けられている太陽電池において、該半導体膜は、ｐ型無機半導体膜／ｐ型有機半導体膜／ｎ型有機半導体膜／ｎ型無機半導体膜の積層体よりなることを特徴とするものである。   2. The organic-inorganic composite solar cell according to claim 1, wherein a semiconductor film is provided between a pair of electrodes, the semiconductor film being p-type inorganic semiconductor film / p-type organic semiconductor film / n-type organic semiconductor film. It is characterized by comprising a stacked body of / n-type inorganic semiconductor films.

請求項２の有機無機複合太陽電池は、１対の電極間に半導体膜が設けられている太陽電池において、該半導体膜は、ｐ型無機半導体膜／ｐ型有機半導体とｎ型有機半導体の混合膜／ｎ型無機半導体膜の積層体よりなることを特徴とするものである。   3. The organic-inorganic composite solar cell according to claim 2, wherein a semiconductor film is provided between a pair of electrodes, and the semiconductor film is a mixture of p-type inorganic semiconductor film / p-type organic semiconductor and n-type organic semiconductor. It consists of a laminated body of a film / n-type inorganic semiconductor film.

請求項３の有機無機複合太陽電池は、請求項１又は２において、ｐ型無機半導体はＣｕ２Ｏ又はＮｉＯであり、ｎ型無機半導体はＺｎＯ、ＴｉＯ２、ＳｎＯ２又はＩｎ２Ｏ３であることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 3 is the organic or inorganic composite solar cell according to claim 1 or 2, wherein the p-type inorganic semiconductor is Cu 2 O or NiO, and the n-type inorganic semiconductor is ZnO, TiO 2 , SnO 2 or In 2 O 3 . It is characterized by this.

請求項４の有機無機複合太陽電池は、請求項１ないし３のいずれか１項において、該電極が金属膜又は透明導電膜よりなることを特徴とするものである。   The organic-inorganic composite solar cell according to claim 4 is characterized in that, in any one of claims 1 to 3, the electrode is made of a metal film or a transparent conductive film.

請求項５の有機無機複合太陽電池は、請求項１において、前記半導体膜は、Ｃｕ２Ｏ／ＭＥＨ−ＰＰＶ／フラーレン類／ＺｎＯの積層体よりなることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 5 is characterized in that, in claim 1, the semiconductor film is made of a laminate of Cu 2 O / MEH-PPV / fullerenes / ZnO.

請求項６の有機無機複合太陽電池は、請求項５において、該有機無機複合太陽電池は、全体として、Ａｌ／Ｃｕ２Ｏ／ＭＥＨ−ＰＰＶ／フラーレン類／ＺｎＯ／ＩＴＯの積層体よりなることを特徴とするものである。 An organic-inorganic composite solar cell according to claim 6 is the organic-inorganic composite solar cell according to claim 5, wherein the organic-inorganic composite solar cell is composed of a laminate of Al / Cu 2 O / MEH-PPV / fullerenes / ZnO / ITO as a whole. It is a feature.

請求項７の有機無機複合太陽電池は、請求項２において、前記半導体膜は、ＮｉＯ／ＭＥＨ−ＰＰＶとフラーレン類との有機混合膜／ＴｉＯ２の積層体よりなることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 7 is characterized in that, in claim 2, the semiconductor film is composed of a laminate of NiO / MEH-PPV and fullerene organic mixed film / TiO 2. .

請求項８の有機無機複合太陽電池は、請求項７において、該有機無機複合太陽電池は、全体として、Ａｌ／ＮｉＯ／ＭＥＨ−ＰＰＶとフラーレン類との有機混合膜／ＴｉＯ２／ＩＴＯの積層体よりなることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 8 is the laminate according to claim 7, wherein the organic-inorganic composite solar cell is an organic mixed film of Al / NiO / MEH-PPV and fullerenes / TiO 2 / ITO as a whole. It is characterized by comprising.

請求項９の有機無機複合太陽電池は、１対の電極間に半導体膜が設けられている太陽電池において、一方の電極がｐ型透明導電膜であり、他方の電極がｎ型透明導電膜であり、全体として、ｐ型透明導電膜／ｐ型有機半導体膜／ｎ型有機半導体膜／ｎ型透明導電膜の積層体よりなることを特徴とするものである。   The organic-inorganic composite solar cell according to claim 9 is a solar cell in which a semiconductor film is provided between a pair of electrodes, one electrode being a p-type transparent conductive film and the other electrode being an n-type transparent conductive film. As a whole, it is characterized by comprising a laminate of p-type transparent conductive film / p-type organic semiconductor film / n-type organic semiconductor film / n-type transparent conductive film.

請求項１０の有機無機複合太陽電池は、１対の電極間に半導体膜が設けられている太陽電池において、一方の電極がｐ型透明導電膜であり、他方の電極がｎ型透明導電膜であり、全体として、ｐ型透明導電膜／ｐ型有機半導体とｎ型有機半導体の混合膜／ｎ型透明導電膜の積層体よりなることを特徴とするものである。   The organic-inorganic composite solar cell according to claim 10 is a solar cell in which a semiconductor film is provided between a pair of electrodes, one electrode being a p-type transparent conductive film and the other electrode being an n-type transparent conductive film. And, as a whole, is composed of a laminate of a p-type transparent conductive film / a mixed film of p-type organic semiconductor and n-type organic semiconductor / n-type transparent conductive film.

請求項１１の有機無機複合太陽電池は、請求項９において、該有機無機複合太陽電池は、全体として、ＣｕＡｌＯ２／ＭＥＨ−ＰＰＶ／フラーレン類／ＩＴＯの積層体よりなることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 11 is characterized in that, in claim 9, the organic-inorganic composite solar cell is composed of a laminate of CuAlO 2 / MEH-PPV / fullerenes / ITO as a whole. is there.

請求項１２の有機無機複合太陽電池は、請求項１０において、該有機無機複合太陽電池は、全体として、ＣｕＡｌＯ２／ＭＥＨ−ＰＰＶとフラーレン類との混合膜／ＩＴＯの積層体よりなることを特徴とするものである。 The organic-inorganic composite solar cell according to claim 12 is characterized in that, in claim 10, the organic-inorganic composite solar cell is composed of a mixed film of CuAlO 2 / MEH-PPV and fullerenes / ITO laminate as a whole. It is what.

請求項１３の有機無機複合太陽電池は、請求項５〜８，１１，１２のいずれか１項において、フラーレン類がフラーレン又はフラーレン誘導体であることを特徴とするものである。   The organic-inorganic composite solar cell according to claim 13 is characterized in that, in any one of claims 5 to 8, 11 and 12, the fullerene is a fullerene or a fullerene derivative.

請求項１４の有機無機複合太陽電池は、請求項１３において、フラーレン誘導体がＰＣＢＭであることを特徴とするものである。   The organic-inorganic composite solar cell of claim 14 is characterized in that, in claim 13, the fullerene derivative is PCBM.

なお、ＭＥＨ−ＰＰＶは下記構造式（化１）で示されるポリ［２−メトキシ−５−（２’−エチルヘキロキシ）−１，４−フェニレンビニレンであり、ＰＣＢＭは、下記構造式（化２）で表わされるものである。   Note that MEH-PPV is poly [2-methoxy-5- (2′-ethylhexyloxy) -1,4-phenylenevinylene represented by the following structural formula (Chemical Formula 1), and PCBM is the following structural formula (Chemical Formula 2). It is represented by

Figure 2006013097
Figure 2006013097

Figure 2006013097
Figure 2006013097

請求項１の有機無機複合太陽電池は、光吸収層をｐ型有機半導体膜とｎ型有機半導体膜との積層体で構成している。また、請求項２の有機無機複合太陽電池は、光吸収層をｐ型有機半導体とｎ型有機半導体との混合膜で構成している。いずれの有機無機複合太陽電池においても、上記の光吸収層の両側をｐ型無機半導体膜及びｎ型無機半導体膜で挟み込んでいるので光照射によって励起された電子を効率良く取り出すことができる。   In the organic-inorganic composite solar cell according to claim 1, the light absorption layer is composed of a laminate of a p-type organic semiconductor film and an n-type organic semiconductor film. In the organic-inorganic composite solar cell according to claim 2, the light absorption layer is composed of a mixed film of a p-type organic semiconductor and an n-type organic semiconductor. In any organic-inorganic composite solar cell, since both sides of the light absorption layer are sandwiched between the p-type inorganic semiconductor film and the n-type inorganic semiconductor film, electrons excited by light irradiation can be efficiently extracted.

請求項９の有機無機複合太陽電池は、光吸収層をｐ型有機半導体膜とｎ型有機半導体膜との積層体で構成している。また、請求項１０の有機無機複合太陽電池は、光吸収層をｐ型有機半導体とｎ型有機半導体との混合膜で構成している。いずれの有機無機複合太陽電池においても、上記の光吸収層の両側をｐ型透明導電膜及びｎ型透明導電膜で挟み込んでいるので光照射によって励起された電子を効率良く取り出すことができる。   In the organic-inorganic composite solar cell according to claim 9, the light absorption layer is formed of a laminate of a p-type organic semiconductor film and an n-type organic semiconductor film. In the organic-inorganic composite solar battery of claim 10, the light absorption layer is composed of a mixed film of a p-type organic semiconductor and an n-type organic semiconductor. In any organic-inorganic composite solar cell, since both sides of the light absorption layer are sandwiched between the p-type transparent conductive film and the n-type transparent conductive film, electrons excited by light irradiation can be efficiently taken out.

なお、請求項３〜８，１１，１２はより具体的な構造を特定したものであり、請求項１３，１４はフラーレン類を特定したものである。   Claims 3 to 8, 11, and 12 specify more specific structures, and claims 13 and 14 specify fullerenes.

以下、図面を参照して本発明についてさらに詳細に説明する。   Hereinafter, the present invention will be described in more detail with reference to the drawings.

図１（ａ）は請求項１の有機無機複合太陽電池の構成を示す模式的な断面図であり、透明導電膜１、ｎ型無機半導体膜２、ｎ型有機半導体膜３、ｐ型有機半導体膜４、ｐ型無機半導体膜５及び金属電極６がこの順に積層されている。   FIG. 1A is a schematic cross-sectional view showing the configuration of the organic-inorganic composite solar cell of claim 1, and includes a transparent conductive film 1, an n-type inorganic semiconductor film 2, an n-type organic semiconductor film 3, and a p-type organic semiconductor. The film 4, the p-type inorganic semiconductor film 5, and the metal electrode 6 are laminated in this order.

図１（ｂ）は請求項２の有機無機複合太陽電池の構成を示す模式的な断面図であり、透明導電膜７、ｎ型無機半導体膜８、ｐ型有機半導体とｎ型有機半導体との混合膜９、ｐ型無機半導体膜１０及び金属電極１１がこの順に積層されている。   FIG. 1B is a schematic cross-sectional view showing the configuration of the organic-inorganic composite solar cell of claim 2, in which a transparent conductive film 7, an n-type inorganic semiconductor film 8, a p-type organic semiconductor, and an n-type organic semiconductor are used. The mixed film 9, the p-type inorganic semiconductor film 10, and the metal electrode 11 are laminated in this order.

図１（ｃ）は請求項９の有機無機複合太陽電池の構成を示す模式的な断面図であり、ｎ型透明導電膜１２、ｎ型有機半導体膜１３、ｐ型有機半導体膜１４及びｐ型透明導電膜１５がこの順に積層されている。   FIG. 1C is a schematic cross-sectional view showing the configuration of the organic-inorganic composite solar cell of claim 9, and the n-type transparent conductive film 12, the n-type organic semiconductor film 13, the p-type organic semiconductor film 14, and the p-type. The transparent conductive film 15 is laminated in this order.

図１（ｄ）は請求項１０の有機無機複合太陽電池の構成を示す模式的な断面図であり、ｎ型透明導電膜１６、ｐ型有機半導体とｎ型有機半導体との混合膜１７及びｐ型透明導電膜１８がこの順に積層されている。   FIG. 1 (d) is a schematic cross-sectional view showing the configuration of the organic-inorganic composite solar cell of claim 10, and includes an n-type transparent conductive film 16, a mixed film 17 of p-type organic semiconductor and n-type organic semiconductor, and p. The type transparent conductive film 18 is laminated in this order.

透明導電膜としては、ＩＴＯ（インジウム・錫酸化物）、ＡＺＯ（アンチモン・亜鉛酸化物）等が好適であり、その膜厚は５〜２００ｎｍ程度が好適である。   As the transparent conductive film, ITO (indium / tin oxide), AZO (antimony / zinc oxide), or the like is preferable, and the film thickness is preferably about 5 to 200 nm.

ｐ型無機半導体膜としては、Ｃｕ２ＯやＮｉＯなどの光透過性を有する無機化合物、特に金属酸化物が好適である。この膜厚は３０〜８００ｎｍ程度が好適である。 As the p-type inorganic semiconductor film, a light-transmitting inorganic compound such as Cu 2 O or NiO, particularly a metal oxide is suitable. This film thickness is preferably about 30 to 800 nm.

ｎ型無機半導体膜としては、ＺｎＯ、ＴｉＯ２、ＳｎＯ２、Ｉｎ２Ｏ３などの光透過性を有する無機化合物、特に金属酸化物が好適である。 As the n-type inorganic semiconductor film, a light-transmitting inorganic compound such as ZnO, TiO 2 , SnO 2 , or In 2 O 3 , particularly a metal oxide is preferable.

ｐ型透明導電膜としては、ＣｕＡｌＯ２等が好適であり、その膜厚は３０ｎｍ〜１μｍ程度が好適である。 As the p-type transparent conductive film, CuAlO 2 or the like is suitable, and the film thickness is preferably about 30 nm to 1 μm.

ｎ型透明導電膜としては、ＩＴＯ、ＡＺＯ等が好適であり、その膜厚は３０ｎｍ〜１μｍ程度が好適である。   As the n-type transparent conductive film, ITO, AZO or the like is suitable, and the film thickness is preferably about 30 nm to 1 μm.

金属電極としては、アルミニウム、白金などが好適であり、その膜厚は３０ｎｍ〜１μｍ程度が好適である。   As the metal electrode, aluminum, platinum or the like is suitable, and the film thickness is preferably about 30 nm to 1 μm.

これらの金属膜や金属酸化物膜はスパッタリングにより形成することができる。   These metal films and metal oxide films can be formed by sputtering.

ｐ型有機半導体膜としては、ＭＥＨ−ＰＰＶが好適であり、特に分子量が１万〜３０万程度のＭＥＨ−ＰＰＶが好適である。ｎ型有機半導体膜としては、フラーレン（Ｃ６０）やフラーレン誘導体が好適である。フラーレン誘導体としては、前記化学構造式で表わされるＰＣＢＭが好適である。これらの有機半導体膜の膜厚は３〜５００ｎｍ程度が好適である。 As the p-type organic semiconductor film, MEH-PPV is preferable, and MEH-PPV having a molecular weight of about 10,000 to 300,000 is particularly preferable. As the n-type organic semiconductor film, fullerene (C 60 ) or a fullerene derivative is suitable. As the fullerene derivative, PCBM represented by the above chemical structural formula is preferable. The thickness of these organic semiconductor films is preferably about 3 to 500 nm.

ｐ型有機半導体とｎ型有機半導体との混合膜における両者の混合割合は、５０：１〜１：５０であることが好ましい。   The mixing ratio of the p-type organic semiconductor and the n-type organic semiconductor in the mixed film is preferably 50: 1 to 1:50.

この有機半導体膜は、クロロベンゼン等の有機溶媒にＭＥＨ−ＰＰＶ、フラーレン類等を溶解ないし分散させ、スピンコート法等によって薄膜化させ、次いで溶媒を蒸発させることにより成膜することができる。   This organic semiconductor film can be formed by dissolving or dispersing MEH-PPV, fullerenes or the like in an organic solvent such as chlorobenzene, thinning the film by a spin coating method, and then evaporating the solvent.

上記の図１（ａ），（ｂ）ではいずれも図の下側から光が照射される。図１（ｃ），（ｄ）では光は上側、下側のいずれから照射されてもよいが、下側の方が好適である。図１（ａ），（ｂ）では最下段の層を透明導電膜１，７としているが、これを金属電極とし、代わりに最上層の層６，１１を透明導電膜とし、図の上側から光が照射される構成としてもよい。   In FIGS. 1A and 1B, light is irradiated from the lower side of the figure. In FIGS. 1C and 1D, light may be emitted from either the upper side or the lower side, but the lower side is preferred. In FIGS. 1A and 1B, the lowermost layer is the transparent conductive films 1 and 7, but this is a metal electrode. Instead, the uppermost layers 6 and 11 are transparent conductive films. It is good also as a structure irradiated with light.

図２（ａ）は図１（ａ）の具体的な構成を示す模式的な断面図であり、透明導電膜としてのＩＴＯ膜１’、ｎ型無機半導体膜としてのＺｎＯ膜２’、ｎ型有機半導体膜としてのフラーレン膜３’、ｐ型有機半導体膜としてのＭＥＨ−ＰＰＶ膜４’、ｐ型無機半導体膜としてのＣｕ２Ｏ膜５’及び金属電極としてのＡｌ膜６’がこの順に積層されている。 FIG. 2A is a schematic cross-sectional view showing a specific configuration of FIG. 1A, in which an ITO film 1 ′ as a transparent conductive film, a ZnO film 2 ′ as an n-type inorganic semiconductor film, and an n-type. A fullerene film 3 ′ as an organic semiconductor film, an MEH-PPV film 4 ′ as a p-type organic semiconductor film, a Cu 2 O film 5 ′ as a p-type inorganic semiconductor film, and an Al film 6 ′ as a metal electrode are stacked in this order. Has been.

図２（ｂ）は図１（ｂ）の具体的な構成を示す模式的な断面図であり、透明導電膜としてのＩＴＯ膜７’、ｎ型無機半導体膜としてのＴｉＯ２膜８’、ｐ型有機半導体とｎ型有機半導体との混合膜としてのＭＥＨ−ＰＰＶとＰＣＢＭとの混合膜９’、ｐ型無機半導体膜としてのＮｉＯ膜１０’及び金属電極としてのＡｌ膜１１’がこの順に積層されている。 FIG. 2B is a schematic cross-sectional view showing a specific configuration of FIG. 1B, in which an ITO film 7 ′ as a transparent conductive film, a TiO 2 film 8 ′ as an n-type inorganic semiconductor film, p A mixed film 9 ′ of MEH-PPV and PCBM as a mixed film of a p-type organic semiconductor and an n-type organic semiconductor, a NiO film 10 ′ as a p-type inorganic semiconductor film, and an Al film 11 ′ as a metal electrode are stacked in this order. Has been.

図２（ｂ）の有機無機複合太陽電池にあっては、光照射によって励起された混合膜９’中の電子がＰＣＢＭに局在するが、隣接するｎ型半導体のＴｉＯ２膜８’に電子が受け渡される。一方、ＭＥＨ−ＰＰＶからはホールがｐ型半導体のＮｉＯ膜１０’に受け渡され、電子・正孔対が効率的に電極７’，１１’に流れていく。 In the organic-inorganic hybrid solar cell of FIG. 2B, electrons in the mixed film 9 ′ excited by light irradiation are localized in PCBM, but electrons are adjoined in the adjacent n-type semiconductor TiO 2 film 8 ′. Is passed. On the other hand, holes are transferred from the MEH-PPV to the NiO film 10 ′ of the p-type semiconductor, and electron / hole pairs efficiently flow to the electrodes 7 ′ and 11 ′.

図２（ｃ）は図１（ｃ）の具体的な構成を示す模式的な断面図であり、ｎ型透明導電膜としてのＩＴＯ膜１２’、ｎ型有機半導体膜としてのフラーレン膜１３’、ｐ型有機半導体膜としてのＭＥＨ−ＰＰＶ膜１４’及びｐ型透明導電膜としてのＣｕＡｌＯ２膜１５’がこの順に積層されている。 FIG. 2C is a schematic cross-sectional view showing a specific configuration of FIG. 1C, in which an ITO film 12 ′ as an n-type transparent conductive film, a fullerene film 13 ′ as an n-type organic semiconductor film, A MEH-PPV film 14 ′ as a p-type organic semiconductor film and a CuAlO 2 film 15 ′ as a p-type transparent conductive film are laminated in this order.

図２（ｄ）は図１（ｄ）の具体的な構成を示す模式的な断面図であり、ｎ型透明導電膜としてのＩＴＯ膜１６’、ｐ型有機半導体とｎ型有機半導体との混合膜としてのＭＥＨ−ＰＰＶとフラーレンとの混合膜１７’及びｐ型透明導電膜としてのＣｕＡｌＯ２膜１８’がこの順に積層されている。 FIG. 2 (d) is a schematic cross-sectional view showing the specific configuration of FIG. 1 (d), in which an ITO film 16 ′ as an n-type transparent conductive film, a mixture of a p-type organic semiconductor and an n-type organic semiconductor. A mixed film 17 ′ of MEH-PPV and fullerene as a film and a CuAlO 2 film 18 ′ as a p-type transparent conductive film are laminated in this order.

実施の形態に係る有機無機複合太陽電池の構造図である。1 is a structural diagram of an organic-inorganic composite solar cell according to an embodiment. 実施の形態に係る有機無機複合太陽電池の具体的な構造図である。It is a specific structural diagram of the organic-inorganic composite solar cell according to the embodiment.

符号の説明Explanation of symbols

１，７ 透明導電膜
２，８ ｎ型無機半導体膜
３，１３ ｎ型有機半導体膜
４，１４ ｐ型有機半導体膜
５，１０ ｐ型無機半導体膜
６，１１ 金属電極
９，１７ ｐ型有機半導体とｎ型有機半導体との混合膜
１２，１６ ｎ型透明導電膜
１５，１８ ｐ型透明導電膜 1,7 Transparent conductive film 2,8 n-type inorganic semiconductor film 3,13 n-type organic semiconductor film 4,14 p-type organic semiconductor film 5,10 p-type inorganic semiconductor film 6,11 metal electrode 9,17 p-type organic semiconductor And n-type organic semiconductor mixed film 12, 16 n-type transparent conductive film 15, 18 p-type transparent conductive film

Claims (14)

１対の電極間に半導体膜が設けられている太陽電池において、
該半導体膜は、ｐ型無機半導体膜／ｐ型有機半導体膜／ｎ型有機半導体膜／ｎ型無機半導体膜の積層体よりなることを特徴とする有機無機複合太陽電池。 In a solar cell in which a semiconductor film is provided between a pair of electrodes,
The organic / inorganic composite solar cell, wherein the semiconductor film is a laminate of p-type inorganic semiconductor film / p-type organic semiconductor film / n-type organic semiconductor film / n-type inorganic semiconductor film. １対の電極間に半導体膜が設けられている太陽電池において、
該半導体膜は、ｐ型無機半導体膜／ｐ型有機半導体とｎ型有機半導体の混合膜／ｎ型無機半導体膜の積層体よりなることを特徴とする有機無機複合太陽電池。 In a solar cell in which a semiconductor film is provided between a pair of electrodes,
The organic / inorganic composite solar cell, wherein the semiconductor film is a laminate of a p-type inorganic semiconductor film / a mixed film of a p-type organic semiconductor and an n-type organic semiconductor / an n-type inorganic semiconductor film. 請求項１又は２において、ｐ型無機半導体はＣｕ２Ｏ又はＮｉＯであり、ｎ型無機半導体はＺｎＯ、ＴｉＯ２、ＳｎＯ２又はＩｎ２Ｏ３であることを特徴とする有機無機複合太陽電池。 3. The organic-inorganic composite solar cell according to claim 1, wherein the p-type inorganic semiconductor is Cu 2 O or NiO, and the n-type inorganic semiconductor is ZnO, TiO 2 , SnO 2 or In 2 O 3 . 請求項１ないし３のいずれか１項において、該電極が金属膜又は透明導電膜よりなることを特徴とする有機無機複合太陽電池。   The organic-inorganic composite solar cell according to any one of claims 1 to 3, wherein the electrode is made of a metal film or a transparent conductive film. 請求項１において、前記半導体膜は、Ｃｕ２Ｏ／ＭＥＨ−ＰＰＶ／フラーレン類／ＺｎＯの積層体よりなることを特徴とする有機無機複合太陽電池。 2. The organic-inorganic composite solar cell according to claim 1, wherein the semiconductor film is formed of a laminate of Cu 2 O / MEH-PPV / fullerenes / ZnO. 請求項５において、該有機無機複合太陽電池は、全体として、Ａｌ／Ｃｕ２Ｏ／ＭＥＨ−ＰＰＶ／フラーレン類／ＺｎＯ／ＩＴＯの積層体よりなることを特徴とする有機無機複合太陽電池。 6. The organic-inorganic composite solar cell according to claim 5, wherein the organic-inorganic composite solar cell is composed of a laminate of Al / Cu 2 O / MEH-PPV / fullerenes / ZnO / ITO as a whole. 請求項２において、前記半導体膜は、ＮｉＯ／ＭＥＨ−ＰＰＶとフラーレン類との有機混合膜／ＴｉＯ２の積層体よりなることを特徴とする有機無機複合太陽電池。 3. The organic / inorganic composite solar cell according to claim 2, wherein the semiconductor film is made of a laminate of NiO / MEH-PPV and fullerenes, ie, an organic mixed film / TiO 2 . 請求項７において、該有機無機複合太陽電池は、全体として、Ａｌ／ＮｉＯ／ＭＥＨ−ＰＰＶとフラーレン類との有機混合膜／ＴｉＯ２／ＩＴＯの積層体よりなることを特徴とする有機無機複合太陽電池。 8. The organic-inorganic composite solar cell according to claim 7, wherein the organic-inorganic composite solar cell is composed of a laminate of an organic mixed film of Al / NiO / MEH-PPV and fullerenes / TiO 2 / ITO as a whole. battery. １対の電極間に半導体膜が設けられている太陽電池において、
一方の電極がｐ型透明導電膜であり、他方の電極がｎ型透明導電膜であり、
全体として、ｐ型透明導電膜／ｐ型有機半導体膜／ｎ型有機半導体膜／ｎ型透明導電膜の積層体よりなることを特徴とする有機無機複合太陽電池。 In a solar cell in which a semiconductor film is provided between a pair of electrodes,
One electrode is a p-type transparent conductive film, the other electrode is an n-type transparent conductive film,
As a whole, an organic-inorganic composite solar cell comprising a laminate of p-type transparent conductive film / p-type organic semiconductor film / n-type organic semiconductor film / n-type transparent conductive film. １対の電極間に半導体膜が設けられている太陽電池において、
一方の電極がｐ型透明導電膜であり、他方の電極がｎ型透明導電膜であり、
全体として、ｐ型透明導電膜／ｐ型有機半導体とｎ型有機半導体の混合膜／ｎ型透明導電膜の積層体よりなることを特徴とする有機無機複合太陽電池。 In a solar cell in which a semiconductor film is provided between a pair of electrodes,
One electrode is a p-type transparent conductive film, the other electrode is an n-type transparent conductive film,
An organic-inorganic composite solar cell comprising a laminate of a p-type transparent conductive film / p-type organic semiconductor and a mixed film of n-type organic semiconductor / n-type transparent conductive film as a whole. 請求項９において、該有機無機複合太陽電池は、全体として、ＣｕＡｌＯ２／ＭＥＨ−ＰＰＶ／フラーレン類／ＩＴＯの積層体よりなることを特徴とする有機無機複合太陽電池。 In claim 9, said organic-inorganic composite solar cells, as a whole, the organic-inorganic composite solar cell characterized by comprising a laminate of CuAlO 2 / MEH-PPV / fullerene / ITO. 請求項１０において、該有機無機複合太陽電池は、全体として、ＣｕＡｌＯ２／ＭＥＨ−ＰＰＶとフラーレン類との混合膜／ＩＴＯの積層体よりなることを特徴とする有機無機複合太陽電池。 11. The organic-inorganic composite solar cell according to claim 10, wherein the organic-inorganic composite solar cell is composed of a laminate of CuAlO 2 / MEH-PPV and fullerenes / ITO as a whole. 請求項５〜８，１１，１２のいずれか１項において、フラーレン類がフラーレン又はフラーレン誘導体であることを特徴とする有機無機複合太陽電池。   The organic-inorganic composite solar cell according to claim 5, wherein the fullerene is a fullerene or a fullerene derivative. 請求項１３において、フラーレン誘導体がＰＣＢＭであることを特徴とする有機無機複合太陽電池。   The organic-inorganic composite solar cell according to claim 13, wherein the fullerene derivative is PCBM.
JP2004187418A 2004-06-25 2004-06-25 Organic/inorganic composite solar cell Pending JP2006013097A (en)

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WO2010050198A1 (en) * 2008-10-30 2010-05-06 出光興産株式会社 Organic solar battery
EP2348556A1 (en) * 2008-10-30 2011-07-27 Idemitsu Kosan Co., Ltd. Organic thin-film solar cell
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