JP2007194559A - Compound photoelectric conversion element, and method for manufacturing same - Google Patents

Compound photoelectric conversion element, and method for manufacturing same Download PDF

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JP2007194559A
JP2007194559A JP2006013816A JP2006013816A JP2007194559A JP 2007194559 A JP2007194559 A JP 2007194559A JP 2006013816 A JP2006013816 A JP 2006013816A JP 2006013816 A JP2006013816 A JP 2006013816A JP 2007194559 A JP2007194559 A JP 2007194559A
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photoelectric conversion
semiconductor layer
conversion element
substrate
type
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Hisahiro Ando
寿浩 安藤
Kiyoharu Nakagawa
清晴 中川
Mika Gamo
美香 蒲生
Shusuke Gamo
秀典 蒲生
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National Institute for Materials Science
Toppan Inc
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Toppan Printing Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound photoelectric conversion element exhibiting high conversion efficiency and high carrier transportation efficiency which can be manufactured inexpensively, and to provide a method for manufacturing the compound photoelectric conversion element. <P>SOLUTION: This compound photoelectric conversion element is provided with a substrate, a first electrode formed on the substrate; an n-type semiconductor layer formed on the first electrode, and oriented vertically to the substrate, in which nano carbon materials are included; a p-type organic semiconductor layer formed on the n-type semiconductor layer; and a second electrode formed on the p-type organic semiconductor layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、紫外線、可視光線、近赤外線を含む太陽光、すなわちフォトンの入射により起電力を生ずる太陽電池や光センサ等の光電変換素子であって、特に、無機半導体と有機半導体をそれぞれ異種キャリアの生成層に用いた無機／有機積層（ヘテロ接合）型の複合光電変換素子及びその製造方法に関するものである。   The present invention relates to a photoelectric conversion element such as a solar cell or an optical sensor that generates an electromotive force when sunlight including ultraviolet rays, visible rays, or near-infrared rays, that is, photons, in particular, an inorganic semiconductor and an organic semiconductor are respectively different carriers. The present invention relates to an inorganic / organic multilayer (heterojunction) type composite photoelectric conversion element used for the generation layer and a method for producing the same.

石油資源の枯渇や地球温暖化といったエネルギー問題及び環境問題の解決策の一つとして、光電変換素子の一種である太陽電池が注目されている。このような太陽電池としては、現在、単結晶シリコン、多結晶シルコン、アモルファスシリコンを用いたシリコン型太陽電池が主流であるが、シリコン系太陽電池は、製造コストが高く、また、製造のために消費される電力が大きく、そのため、真にエネルギー問題及び環境問題を解決し得る切り札となるには、未だ課題が多い。   As one of solutions for energy problems and environmental problems such as the depletion of petroleum resources and global warming, a solar cell which is a kind of photoelectric conversion element has attracted attention. Currently, silicon solar cells using single crystal silicon, polycrystalline silcon, and amorphous silicon are the mainstream as such solar cells, but silicon-based solar cells are expensive to manufacture and for production purposes. The power consumed is large, so there are still many issues to become a trump card that can truly solve energy problems and environmental problems.

そこで、シリコンの代わりに、低コストで製造可能な有機化合物を用いる技術が提案され、近年、活発な研究開発が進められている。   Therefore, a technique using an organic compound that can be manufactured at low cost instead of silicon has been proposed, and active research and development has been promoted in recent years.

有機化合物を用いた太陽電池、すなわち有機太陽電池として、ｐ型有機半導体と、仕事関数の小さい金属とのショットキー障壁を利用したものがある。また、ｐ型有機半導体とｎ型有機半導体とのｐｎ接合を利用したｐｎ接合型有機太陽電池も提案されている。   As a solar cell using an organic compound, that is, an organic solar cell, there is one using a Schottky barrier between a p-type organic semiconductor and a metal having a small work function. A pn junction type organic solar cell using a pn junction between a p type organic semiconductor and an n type organic semiconductor has also been proposed.

このようなｐｎ接合型有機太陽電池としては、ｐ型有機半導体である銅フタロシアニンとｎ型有機半導体であるペリレン誘導体とを用いたものが知られている（例えば、非特許文献１参照）。   As such a pn junction type organic solar cell, one using a copper phthalocyanine which is a p-type organic semiconductor and a perylene derivative which is an n-type organic semiconductor is known (for example, see Non-Patent Document 1).

しかしながら、このようなｐｎ接合型有機太陽電池は、エネルギー変換効率が０．０１％以下と非常に低く、また有機半導体でｎ型半導体となる材料が希少であるため、改良のための材料の自由度が少ないという問題がある。   However, such a pn junction type organic solar cell has a very low energy conversion efficiency of 0.01% or less, and a material that becomes an n-type semiconductor as an organic semiconductor is rare. There is a problem that the degree is low.

一方、近年、ｎ型半導体としてフラーレンを用い、ｐ型有機半導体とポリマーブレンドした有機太陽電池が報告され、エネルギー変換効率３％が得られている（例えば、非特許文献２参照）。   On the other hand, in recent years, an organic solar cell using fullerene as an n-type semiconductor and polymer blended with a p-type organic semiconductor has been reported, and an energy conversion efficiency of 3% has been obtained (for example, see Non-Patent Document 2).

しかしながら、フラーレジは未だ工業的な生産プロセスが確立されておらず、高純度の材料の入手が困難であるのが実情である。
Ｃ．Ｗ．Ｔａｎｇ、Ａｐｐｌ，ＰｈｙＥ Ｌｅｔｔ．４８（２）１ ８ ３ （１９８６）。 Ｇ．Ｙｕ，Ｊ．Ｇａｏ，Ｊ．Ｃ．Ｈｕｍｍｅｌｅｎ，Ｆ．Ｗｕｄｌ ａｎｄ Ａ．Ｊ．Ｈｅｅｇｅｒ，ＳＣＩＥＮＣＥ，２７０，１７８９（１９９５）。 However, fullerage has not yet established an industrial production process, and it is difficult to obtain high-purity materials.
C. W. Tang, Appl, PhyE Lett. 48 (2) 1 8 3 (1986). G. Yu, J .; Gao, J .; C. Hummelen, F.M. Wudl and A.W. J. et al. Heeger, SCIENCE, 270, 1789 (1995).

本発明は、以上のような事情の下になされ、高い変換効率及びキャリアの輸送効率を示し、低コストで製造可能な複合光電変換素子及びその製造方法を提供することを目的とする。   The present invention has been made under the circumstances as described above, and an object of the present invention is to provide a composite photoelectric conversion element that exhibits high conversion efficiency and carrier transport efficiency and can be manufactured at low cost, and a method for manufacturing the same.

上記課題を解決するため、本発明は、基体と、この基体上に形成された第１の電極と、この第１の電極上に形成され、前記基体に対し垂直に配向した、ナノカーボン材料を含むｎ型半導体層と、このｎ型半導体層上に形成されたｐ型有機半導体層と、このｐ型有機半導体層上に形成された第２の電極とを具備することを特徴とする複合光電変換素子を提供する。   In order to solve the above problems, the present invention provides a substrate, a first electrode formed on the substrate, and a nanocarbon material formed on the first electrode and oriented perpendicularly to the substrate. A composite photoelectric sensor comprising: an n-type semiconductor layer including the p-type organic semiconductor layer formed on the n-type semiconductor layer; and a second electrode formed on the p-type organic semiconductor layer. A conversion element is provided.

このように、ｎ型半導体層として基体に対し垂直に配向したナノカーボン材料を含む層を用い、ｐ型有機半導体とのｐｎ接合を形成することにより、Ｄｏｎｏｒ／Ａｃｃｅｐｔｏｒ（Ｄ／Ａ）ネットワークを有する、無機／有機複合光電変換素子を得ることができる。   In this way, a layer containing a nanocarbon material oriented perpendicular to the substrate is used as the n-type semiconductor layer, and a pn junction is formed with the p-type organic semiconductor, thereby having a Donor / Acceptor (D / A) network. An inorganic / organic composite photoelectric conversion element can be obtained.

以上のように構成される本発明の複合光電変換素子において、ナノカーボン材料としては、カーボンナノチューブ、カーボンナノホーン、及びカーボンナノフィラメントからなる群から選ばれた少なくとも１種を用いることができる。   In the composite photoelectric conversion device of the present invention configured as described above, as the nanocarbon material, at least one selected from the group consisting of carbon nanotubes, carbon nanohorns, and carbon nanofilaments can be used.

また、本発明は、基体上に第１の電極を形成する工程、前記第１の電極上に、化学的成長法により、ナノカーボン材料を含むｎ型半導体層を形成する工程、前記ｎ型半導体層上に、ｐ型有機半導体層を形成する工程、及び前記ｐ型有機半導体層上に第２の電極を形成する工程を具備することを特徴とする複合光電変換素子の製造方法を提供する。   The present invention also includes a step of forming a first electrode on a substrate, a step of forming an n-type semiconductor layer containing a nanocarbon material on the first electrode by a chemical growth method, and the n-type semiconductor. There is provided a method for producing a composite photoelectric conversion element comprising a step of forming a p-type organic semiconductor layer on a layer and a step of forming a second electrode on the p-type organic semiconductor layer.

以上のように構成される本発明の複合光電変換素子の製造方法において、化学的成長法として、固液平衡化学的成長法を用いることができる。固液平衡化学的成長法によると、ｎ型半導体層として高配向のナノカーボン材料を含む層を低温で得ることができ、またこのようなｎ型半導体層を用いた複合光電変換素子を低コストで製造することができる。   In the method for producing a composite photoelectric conversion element of the present invention configured as described above, a solid-liquid equilibrium chemical growth method can be used as the chemical growth method. According to the solid-liquid equilibrium chemical growth method, a layer containing a highly oriented nanocarbon material can be obtained at a low temperature as an n-type semiconductor layer, and a composite photoelectric conversion element using such an n-type semiconductor layer can be manufactured at low cost. Can be manufactured.

本発明によると、ｎ型無機半導体とｐ型有機半導体とのｐｎ接合を用いて無機／有機複合光電変換素子を構成するに際し、ｎ型無機半導体として、基板に対し垂直方向に配向した高配向のナノカーボン材料を用いることにより、（Ｄ／Ａ）ネットワークの表面積の増加により、高い変換効率及びキャリアの輸送効率を示す光電変換素子を得ることが可能である。特に、高配向のナノカーボン材料の成膜を固液平衡化学的成長法を用いて行うことにより、低温での成膜が可能であり、選択される基板の自由度を大幅に上げることができ、光電変換素子を低コストで製造することができる。   According to the present invention, when an inorganic / organic composite photoelectric conversion element is configured using a pn junction of an n-type inorganic semiconductor and a p-type organic semiconductor, the n-type inorganic semiconductor is a highly oriented material oriented in a direction perpendicular to the substrate. By using the nanocarbon material, it is possible to obtain a photoelectric conversion element exhibiting high conversion efficiency and carrier transport efficiency by increasing the surface area of the (D / A) network. In particular, highly oriented nanocarbon materials can be deposited using solid-liquid equilibrium chemical growth, enabling deposition at low temperatures and greatly increasing the degree of freedom of the selected substrate. The photoelectric conversion element can be manufactured at a low cost.

以下、発明を実施するための最良の形態について説明する。   The best mode for carrying out the invention will be described below.

図１は、本発明の一実施形態に係る複合光電変換素子を示す断面図である。図１において、絶縁基板１１上に、下部電極１２、ナノカーボン材料を含むｎ型半導体層１３、ｐ型有機半導体層１４、及び上部電極１５が順次積層されて、複合光電変換素子が構成される。   FIG. 1 is a cross-sectional view showing a composite photoelectric conversion element according to an embodiment of the present invention. In FIG. 1, a lower electrode 12, an n-type semiconductor layer 13 containing a nanocarbon material, a p-type organic semiconductor layer 14, and an upper electrode 15 are sequentially stacked on an insulating substrate 11 to form a composite photoelectric conversion element. .

図１に示す複合光電変換素子において、絶縁基板１１としては、ガラス基板、シリコン単結晶基板、プラスチック基板、セラミック基板等を用いることができる。特に、後述する固液平衡化学的成長法を用いてナノカーボン材料を含むｎ型半導体層１３を成膜する場合には、低温での成膜が可能であるため、高温に耐えることができないガラス基板、プラスチック基板を用いることが可能である。   In the composite photoelectric conversion element shown in FIG. 1, as the insulating substrate 11, a glass substrate, a silicon single crystal substrate, a plastic substrate, a ceramic substrate, or the like can be used. In particular, when an n-type semiconductor layer 13 containing a nanocarbon material is formed using a solid-liquid equilibrium chemical growth method described later, glass that cannot withstand high temperatures can be formed at low temperatures. A substrate or a plastic substrate can be used.

下部電極１２としては、アルミニウムや銀等の光を反射する金属が使用される。また、ｎ型半導体層１３を構成するナノカーボンとしては、カーボンナノチューブ、カーボンナノホーン、及びカーボンナノフィラメントを挙げることができる。ｎ型半導体層１３の膜厚は、１００ｎｍ〜１０μｍであるのが望ましい。   As the lower electrode 12, a metal that reflects light such as aluminum or silver is used. Examples of the nanocarbon constituting the n-type semiconductor layer 13 include carbon nanotubes, carbon nanohorns, and carbon nanofilaments. The film thickness of the n-type semiconductor layer 13 is desirably 100 nm to 10 μm.

ｐ型有機半導体層１４を構成するｐ型有機半導体としては、ポリチオフェン誘導体等を用いることができる。ｐ型有機半導体層１４の膜厚は、１０ｎｍ〜１０μｍであるのが望ましい。   A polythiophene derivative or the like can be used as the p-type organic semiconductor constituting the p-type organic semiconductor layer 14. The film thickness of the p-type organic semiconductor layer 14 is desirably 10 nm to 10 μm.

上部電極１５としては、ＩＴＯやＳｎＯ２等の透明導電体が用いられる。
ナノカーボンからなるｎ型半導体層は、化学的成長法により成膜することができる。化学的成長法としては、固液平衡化学的成長法（液相ＣＶＤ）または化学的気相成長法（気相ＣＶＤ）を挙げることができる。これらの方法により、高配向のナノカーボン層を上部電極１５上に形成することができる。これらの方法では、特に、低温でナノカーボン層の形成が可能な固液平衡化学的成長法を用いるのが好ましい。固液平衡化学的成長法によるナノカーボンからなるｎ型半導体層の形成プロセスについて、以下に説明する。 As the upper electrode 15, a transparent conductor such as ITO or SnO 2 is used.
The n-type semiconductor layer made of nanocarbon can be formed by a chemical growth method. Examples of the chemical growth method include solid-liquid equilibrium chemical growth method (liquid phase CVD) and chemical vapor deposition method (vapor phase CVD). By these methods, a highly oriented nanocarbon layer can be formed on the upper electrode 15. In these methods, it is particularly preferable to use a solid-liquid equilibrium chemical growth method capable of forming a nanocarbon layer at a low temperature. A process for forming an n-type semiconductor layer made of nanocarbon by a solid-liquid equilibrium chemical growth method will be described below.

固液平衡化学的成長法によるナノカーボンからなるｎ型半導体層の形成は、図２に示す構造を有する固液平衡化学的成長装置を用いて行われる。図２に示す固液平衡化学的成長装置では、有機液体２２を収容する液体槽２１が、蓋２３により密封されて、装置本体を構成する。液体槽２１の外側には、液体槽２１を冷却するための水冷手段２４が設けられている。液体槽２１内の有機液体２２中には、基板２５が浸漬されており、基板２５は、基板ホルダー２６に取り付けられているとともに、一対の電極２７ａ，２７ｂを介して蓋２３に保持されている。基板２５は、一対の電極２７ａ，２７ｂを通して通電される。   The formation of the n-type semiconductor layer made of nanocarbon by the solid-liquid equilibrium chemical growth method is performed using a solid-liquid equilibrium chemical growth apparatus having the structure shown in FIG. In the solid-liquid equilibrium chemical growth apparatus shown in FIG. 2, a liquid tank 21 containing an organic liquid 22 is sealed with a lid 23 to constitute the apparatus main body. Outside the liquid tank 21, water cooling means 24 for cooling the liquid tank 21 is provided. A substrate 25 is immersed in the organic liquid 22 in the liquid tank 21, and the substrate 25 is attached to the substrate holder 26 and is held by the lid 23 via a pair of electrodes 27a and 27b. . The substrate 25 is energized through a pair of electrodes 27a and 27b.

蓋２３には、液体槽２１内から蒸発する有機液体蒸気を冷却凝縮して液体槽２１に戻すための水冷パイプからなる凝縮手段２８と、液体槽２１内に窒素ガスを導入するバルブ２９とが取り付けられている。   The lid 23 has a condensing means 28 comprising a water cooling pipe for cooling and condensing the organic liquid vapor evaporated from the liquid tank 21 and returning it to the liquid tank 21, and a valve 29 for introducing nitrogen gas into the liquid tank 21. It is attached.

次に、以上のように構成される固液平衡化学的成長装置により、基板２５の表面にカーボンナノチューブ層を形成する手順について説明する。   Next, a procedure for forming a carbon nanotube layer on the surface of the substrate 25 using the solid-liquid equilibrium chemical growth apparatus configured as described above will be described.

まず、図２に示すように、基板２５を基板ホルダー２６に取り付け、液体槽２１内の有機液体２２中に浸漬する。有機液体２２としては、メタノール、エタノール、オクタノール等を用いることができる。なお、基板２５の表面には、触媒としての鉄金属膜が形成されている。電極２７ａ，２７ｂを通して基板２５に直流電流を通電する。   First, as shown in FIG. 2, the substrate 25 is attached to the substrate holder 26 and immersed in the organic liquid 22 in the liquid tank 21. As the organic liquid 22, methanol, ethanol, octanol, or the like can be used. Note that an iron metal film as a catalyst is formed on the surface of the substrate 25. A direct current is passed through the substrate 25 through the electrodes 27a and 27b.

通電により、基板２５の温度が６００〜９００℃に昇温すると、基板２５の表面で触媒の存在下での有機液体２２の熱分解反応が生じ、鉄金属膜上にカーボンナノチューブが析出され、カーボンナノチューブ層が形成される。   When the temperature of the substrate 25 is raised to 600 to 900 ° C. by energization, a thermal decomposition reaction of the organic liquid 22 in the presence of the catalyst occurs on the surface of the substrate 25, carbon nanotubes are deposited on the iron metal film, and carbon A nanotube layer is formed.

このようにして成膜されたカーボンナノチューブ層は、高密度、高配向であり、光電変換素子のｎ型半導体層として好適なものである。   The carbon nanotube layer thus formed has high density and high orientation, and is suitable as an n-type semiconductor layer of a photoelectric conversion element.

以下、本発明の光電変換素子の製造に係る実施例を示し、本発明をより具体的に説明する。   EXAMPLES Hereinafter, the Example which concerns on manufacture of the photoelectric conversion element of this invention is shown, and this invention is demonstrated more concretely.

実施例
図１に示す構造を有する光電変換素子を以下のようにして製造した。 Example A photoelectric conversion element having the structure shown in FIG. 1 was produced as follows.

基板１１として、シリコン単結晶基板を用い、このシリコン単結晶基板１１上に、スパッタ法により下部電極としてアルミニウム薄膜１２を形成した。このアルミニウム薄膜１２上に、スバッタ法にて鉄の薄膜を３ｎｍの膜厚に形成した。なお、鉄は、固液平衡化学的成長によりカーボンナノチューブ層を形成するに際し、有機液体の熱分解反応の触媒として働く。   A silicon single crystal substrate was used as the substrate 11, and an aluminum thin film 12 was formed on the silicon single crystal substrate 11 as a lower electrode by sputtering. An iron thin film having a thickness of 3 nm was formed on the aluminum thin film 12 by a sputtering method. Iron forms a carbon nanotube layer by solid-liquid equilibrium chemical growth and serves as a catalyst for thermal decomposition reaction of organic liquid.

次いで、表面に鉄薄膜が形成されたシリコン単結晶基板２５を、図２に示す装置の基板ホルダー２６に取り付け、バルブ２９から窒素ガスを導入しつつ、電極２７ａ，２７ｂを通して基板２５に直流電流を通電し、固液平衡化学的成長法（液相ＣＶＤ）により、有機液体中で高配向カーポンナノチューブ層１３を成膜した。固液平衡化学的成長法による成膜条件は、下記の通りである。   Next, the silicon single crystal substrate 25 on which the iron thin film is formed is attached to the substrate holder 26 of the apparatus shown in FIG. 2, and a direct current is applied to the substrate 25 through the electrodes 27a and 27b while introducing nitrogen gas from the valve 29. A highly oriented carbon nanotube layer 13 was formed in an organic liquid by energization and solid-liquid equilibrium chemical growth (liquid phase CVD). The film forming conditions by the solid-liquid equilibrium chemical growth method are as follows.

有機液体：メタノール
基板温度：９００℃
合成時間：０．５時間
以上の条件で成膜されたカーボンナノチューブの膜厚は約３μｍであり、カーボンナノチューブの長さは約３μｍであり、それぞれのカーボンナノチューブは、基板に対し、垂直に配向していた。 Organic liquid: methanol Substrate temperature: 900 ° C
Synthesis time: 0.5 hours The film thickness of carbon nanotubes formed under the conditions of more than 0.5 hours is about 3 μm, the length of carbon nanotubes is about 3 μm, and each carbon nanotube is oriented perpendicular to the substrate Was.

次に、ポリチオフェン誘導体をペースト化して、これを印刷法によりカーボンナノチューブ層１３上に塗布し、ｐ型有機半導体層１４を形成した。続いて、ｐ型有機半導体層１４上にＩＴＯ膜をスパッタ法により室温下で成膜し、上部電極１５を形成し、図１に示す構造の光電変換素子を得た。   Next, the polythiophene derivative was made into a paste and applied onto the carbon nanotube layer 13 by a printing method to form a p-type organic semiconductor layer 14. Subsequently, an ITO film was formed on the p-type organic semiconductor layer 14 at room temperature by sputtering to form the upper electrode 15 to obtain a photoelectric conversion element having the structure shown in FIG.

このようにして製造された光電変換素子の光電変換特性を評価したところ、５Ｖで６桁以上の高いオンオフ比が得られた。   When the photoelectric conversion characteristics of the photoelectric conversion element thus manufactured were evaluated, a high on / off ratio of 6 digits or more was obtained at 5V.

比較例
基板温度を７００℃としたことを除いて、上記実施例と同様にして、固液平衡化学的成長法によりカーボンナノチューブ層を成膜した。成膜されたカーボンナノチューブは、無配向であった。上記実施例と同様に光電変換素子を製造し、その光電変換特性を評価したところ、５Ｖで２〜３桁という低いオンオフ比しか得られなかった。 Comparative Example A carbon nanotube layer was formed by a solid-liquid equilibrium chemical growth method in the same manner as in the above example except that the substrate temperature was 700 ° C. The formed carbon nanotubes were non-oriented. When the photoelectric conversion element was manufactured similarly to the said Example and the photoelectric conversion characteristic was evaluated, only the low on-off ratio of 2-3 digits was obtained at 5V.

本発明の一実施形態に係る複合光電変換素子を示す断面図である。It is sectional drawing which shows the composite photoelectric conversion element which concerns on one Embodiment of this invention. 本発明の一実施形態に用いた固液平衡化学的成長装置を示す図である。It is a figure which shows the solid-liquid equilibrium chemical growth apparatus used for one Embodiment of this invention.

符号の説明Explanation of symbols

１１・・・ 絶縁基板、１２・・・下部電極、１３・・・ｎ型半導体層、１４・・・ｐ型有機半導体層、１５・・・上部電極、２１・・・液体槽、２２・・・有機液体、２３・・・蓋、２４・・・水冷手段、２５・・・基板、２６・・・基板ホルダー、２７ａ，２７ｂ・・・基板、２８・・・凝縮手段、２９・・・バルブ。   DESCRIPTION OF SYMBOLS 11 ... Insulating substrate, 12 ... Lower electrode, 13 ... N-type semiconductor layer, 14 ... P-type organic semiconductor layer, 15 ... Upper electrode, 21 ... Liquid tank, 22 ... Organic liquid, 23 ... Lid, 24 ... Water cooling means, 25 ... Substrate, 26 ... Substrate holder, 27a, 27b ... Substrate, 28 ... Condensing means, 29 ... Valve .

Claims (5)

基体と、この基体上に形成された第１の電極と、この第１の電極上に形成され、前記基体に対し垂直に配向した、ナノカーボン材料を含むｎ型半導体層と、このｎ型半導体層上に形成されたｐ型有機半導体層と、このｐ型有機半導体層上に形成された第２の電極とを具備することを特徴とする複合光電変換素子。   A base, a first electrode formed on the base, an n-type semiconductor layer formed on the first electrode and oriented perpendicularly to the base and including a nanocarbon material, and the n-type semiconductor A composite photoelectric conversion element comprising a p-type organic semiconductor layer formed on a layer and a second electrode formed on the p-type organic semiconductor layer. 前記ナノカーボン材料は、カーボンナノチューブ、カーボンナノホーン、及びカーボンナノフィラメントからなる群から選ばれた少なくとも１種であることを特徴とする請求項１に記載の複合光電変換素子。   2. The composite photoelectric conversion element according to claim 1, wherein the nanocarbon material is at least one selected from the group consisting of carbon nanotubes, carbon nanohorns, and carbon nanofilaments. 基体上に第１の電極を形成する工程、
前記第１の電極上に、化学的成長法により、ナノカーボン材料を含むｎ型半導体層を形成する工程、
前記ｎ型半導体層上に、ｐ型有機半導体層を形成する工程、及び
前記ｐ型有機半導体層上に第２の電極を形成する工程
を具備することを特徴とする複合光電変換素子の製造方法。 Forming a first electrode on a substrate;
Forming an n-type semiconductor layer containing a nanocarbon material on the first electrode by a chemical growth method;
A method for producing a composite photoelectric conversion element comprising: forming a p-type organic semiconductor layer on the n-type semiconductor layer; and forming a second electrode on the p-type organic semiconductor layer. . 前記ナノカーボン材料は、カーボンナノチューブ、カーボンナノホーン、及びカーボンナノフィラメントからなる群から選ばれた少なくとも１種であることを特徴とする請求項３に記載の複合光電変換素子の製造方法。   The method for producing a composite photoelectric conversion element according to claim 3, wherein the nanocarbon material is at least one selected from the group consisting of carbon nanotubes, carbon nanohorns, and carbon nanofilaments. 前記化学的成長法は、固液平衡化学的成長法であることを特徴とする請求項３または４に記載の複合光電変換素子の製造方法。   The method for manufacturing a composite photoelectric conversion element according to claim 3 or 4, wherein the chemical growth method is a solid-liquid equilibrium chemical growth method.
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