JP5642005B2 - PHOTOELECTRIC CONVERSION DEVICE, ITS MANUFACTURING METHOD, AND PHOTOELECTRIC CONVERSION MODULE - Google Patents

PHOTOELECTRIC CONVERSION DEVICE, ITS MANUFACTURING METHOD, AND PHOTOELECTRIC CONVERSION MODULE Download PDF

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JP5642005B2
JP5642005B2 JP2011072383A JP2011072383A JP5642005B2 JP 5642005 B2 JP5642005 B2 JP 5642005B2 JP 2011072383 A JP2011072383 A JP 2011072383A JP 2011072383 A JP2011072383 A JP 2011072383A JP 5642005 B2 JP5642005 B2 JP 5642005B2
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大前　智史
智史 大前
正人 福留
正人 福留
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Description

本発明は、光電変換装置とその製造方法および光電変換モジュ−ルに関する。   The present invention relates to a photoelectric conversion device, a manufacturing method thereof, and a photoelectric conversion module.

従来、太陽電池は、カルコパライト系のＣＩＧＳ等の光吸収層を具備する光電変換装置を構成単位とし、この光電変換装置をガラス等の基板上で複数、直列または並列接続することによって構成されている。   2. Description of the Related Art Conventionally, a solar cell is configured by using a photoelectric conversion device including a light absorption layer such as a chalcopalite-based CIGS as a constituent unit and connecting the photoelectric conversion devices in series or in parallel on a substrate such as glass. .

この光電変換装置は、その受光面すなわち光吸収層の上部にバッファ層が設けられている。バッファ層としては、環境に対する負荷を低減するため、および、光吸収層と好適なヘテロ接合を得るために、溶液析出法（ＣＢＤ法）等によって溶液から化学的に成長させた、硫黄を含んだ亜鉛混晶化合物半導体膜が用いられている。   In this photoelectric conversion device, a buffer layer is provided on the light receiving surface, that is, on the light absorption layer. The buffer layer contained sulfur that was chemically grown from a solution by a solution deposition method (CBD method) or the like in order to reduce the burden on the environment and to obtain a suitable heterojunction with the light absorption layer. A zinc mixed crystal compound semiconductor film is used.

また例えば、このバッファ層の上部には透明電極として酸化亜鉛膜が設けられている（特許文献１参照）。   Further, for example, a zinc oxide film is provided as a transparent electrode on the buffer layer (see Patent Document 1).

特開平０８−３３０６１４号公報Japanese Patent Laid-Open No. 08-330614

しかしながら、特許文献１に示すような光電変換装置およびそれを用いた光電変換モジュ−ルであっても、用途によっては、リ−ク電流に対する信頼性が低く、経年変化によって光電変換効率が低下する場合があった。   However, even with a photoelectric conversion device as shown in Patent Document 1 and a photoelectric conversion module using the photoelectric conversion device, the reliability with respect to the leak current is low depending on the application, and the photoelectric conversion efficiency decreases due to secular change. There was a case.

本発明は、上記従来の問題点に鑑みて完成されたものであり、その目的は、変換効率を高く維持可能な信頼性の高い光電変換装置および光電変換モジュ−ルを提供することである。   The present invention has been completed in view of the above-described conventional problems, and an object thereof is to provide a highly reliable photoelectric conversion device and a photoelectric conversion module that can maintain high conversion efficiency.

本発明の一実施形態の光電変換装置は、光電変換可能な化合物半導体を含む光吸収層と、該光吸収層の一方の表面に設けられたＩｎのカルコゲン化物を含む第１の半導体層と、該第１の半導体層の前記光吸収層と反対側の表面に設けられたＺｎのカルコゲン化物およびＩｎを含む第２の半導体層と、該第２の半導体層の前記光吸収層と反対側の表面に設けられたＩｎを含む透明電極層とを具備しており、前記第２の半導体層は前記第１の半導体層との界面付近においてＩｎの組成比率の極小値を有している。
A photoelectric conversion device according to an embodiment of the present invention includes a light absorption layer including a compound semiconductor capable of photoelectric conversion, a first semiconductor layer including a chalcogenide of In provided on one surface of the light absorption layer, A second semiconductor layer containing Zn chalcogenide and In provided on a surface of the first semiconductor layer opposite to the light absorption layer; and a second semiconductor layer opposite to the light absorption layer. And a transparent electrode layer containing In provided on the surface, wherein the second semiconductor layer has a minimum value of the In composition ratio in the vicinity of the interface with the first semiconductor layer.

さらに、本発明の一実施形態の光電変換モジュ−ルは、上記記載の光電変換装置を複数有し、隣接する前記光電変換装置を電気的に接続したものである。   Furthermore, a photoelectric conversion module according to an embodiment of the present invention includes a plurality of the above-described photoelectric conversion devices, and the adjacent photoelectric conversion devices are electrically connected.

さらに、本発明の一実施形態の光電変換装置の製造方法は、光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、該中間層の表面にＩｎを含む透明導電層を形成する第３工程と、該透明電極層を還元雰囲気中で熱処理して前記透明電極層から前記中間層内にＩｎを拡散させる第４工程とを有する。
Furthermore, a method for manufacturing a photoelectric conversion device according to an embodiment of the present invention includes a first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorption layer containing a compound semiconductor capable of photoelectric conversion, A second step of forming an intermediate layer containing a chalcogenide of Zn on the surface of the first semiconductor layer; a third step of forming a transparent conductive layer containing In on the surface of the intermediate layer; and reducing the transparent electrode layer And a fourth step of diffusing In from the transparent electrode layer into the intermediate layer by heat treatment in an atmosphere.

また、本発明の一実施形態の光電変換装置の製造方法は、光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、該中間層をＩｎを含む溶液に浸漬することで該溶液から前記中間層内にＩｎを拡散させる第３工程とを有する。
According to another embodiment of the present invention, there is provided a method for manufacturing a photoelectric conversion device, the first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorption layer containing a compound semiconductor capable of photoelectric conversion, A second step of forming an intermediate layer containing a chalcogenide of Zn on the surface of the first semiconductor layer; and a step of diffusing In from the solution into the intermediate layer by immersing the intermediate layer in a solution containing In. 3 steps.

本発明によれば、光電変換装置を使用する過程での経年変化における第２の半導体層の導電性の上昇を抑えて、リ−ク電流を低減することで、光電変換効率を高く維持することが可能な高い信頼性を有する光電変換装置および光電変換モジュ−ルを得るものである。   According to the present invention, the photoelectric conversion efficiency can be maintained high by suppressing the increase in conductivity of the second semiconductor layer in the process of using the photoelectric conversion device and reducing the leak current. It is possible to obtain a photoelectric conversion device and a photoelectric conversion module having high reliability capable of satisfying the requirements.

本発明に係る光電変換装置および光電変換モジュ−ルの実施の形態の一例を示す断面図である。It is sectional drawing which shows an example of embodiment of the photoelectric conversion apparatus and photoelectric conversion module which concern on this invention. 本発明に係る光電変換装置および光電変換モジュ−ルの実施の形態の他の例を示す断面図である。It is sectional drawing which shows the other example of embodiment of the photoelectric conversion apparatus and photoelectric conversion module which concern on this invention. 図２の本発明に係る光電変換装置および光電変換モジュ−ルの実施の形態の斜視図である。It is a perspective view of embodiment of the photoelectric conversion apparatus and photoelectric conversion module which concern on this invention of FIG. 本発明の一実施形態の半導体層および光吸収層における熱処理後のＩｎの組成分布を示すグラフである。It is a graph which shows the composition distribution of In after the heat processing in the semiconductor layer and light absorption layer of one Embodiment of this invention.

以下に、本発明の光電変換装置とその製造方法および光電変換モジュ−ルの一実施形態について図面を参照しながら詳細に説明する。   Hereinafter, an embodiment of a photoelectric conversion device, a manufacturing method thereof, and a photoelectric conversion module according to the present invention will be described in detail with reference to the drawings.

（光電変換装置）
光電変換装置１０は、基板１と、第１の電極層２と、光吸収層３と、半導体層４と、第２の電極層５（以下、透明電極層５ともいう）とを含んで構成される。 (Photoelectric conversion device)
The photoelectric conversion device 10 includes a substrate 1, a first electrode layer 2, a light absorption layer 3, a semiconductor layer 4, and a second electrode layer 5 (hereinafter also referred to as a transparent electrode layer 5). Is done.

半導体層４は、光吸収層３側の第１の半導体層４ａと透明電極層５側の第２の半導体層４ｂとから成る。半導体層４は、光吸収層３に対してヘテロ接合を行う層をいう。半導体層４は、光吸収層３上に５ｎｍ〜２００ｎｍ程度の厚みで形成されている。光吸収層３と半導体層４とは異なる導電型であることが好ましく、例えば、光吸収層３がｐ型半導体である場合、半導体層４はｎ型半導体である。好ましくはリ−ク電流を低減するという観点からは、半導体層４は、抵抗率が１Ω・ｃｍ以上の層であるのがよい。また、半導体層４は光吸収層３の吸収効率を高めるため、光吸収層３が吸収する光の波長領域に対して光透過性を有するものが好ましい。   The semiconductor layer 4 includes a first semiconductor layer 4a on the light absorption layer 3 side and a second semiconductor layer 4b on the transparent electrode layer 5 side. The semiconductor layer 4 is a layer that performs a heterojunction with the light absorption layer 3. The semiconductor layer 4 is formed on the light absorption layer 3 with a thickness of about 5 nm to 200 nm. The light absorption layer 3 and the semiconductor layer 4 are preferably of different conductivity types. For example, when the light absorption layer 3 is a p-type semiconductor, the semiconductor layer 4 is an n-type semiconductor. Preferably, from the viewpoint of reducing the leakage current, the semiconductor layer 4 is a layer having a resistivity of 1 Ω · cm or more. Moreover, in order to improve the absorption efficiency of the light absorption layer 3, the semiconductor layer 4 preferably has a light transmission property with respect to the wavelength region of light absorbed by the light absorption layer 3.

図１において、光電変換装置１０は複数並べて形成されている。そして、光電変換装置１０は、光吸収層３の基板１側に第１の電極層２と離間して設けられた第３の電極層６を具備している。そして、光吸収層３に設けられた接続導体７によって、透明電極層５と第３の電極層６とが電気的に接続されている。この第３の電極層６は、隣接する光電変換装置１０の第１の電極層２と一体化されている。この構成により、隣接する光電変換装置１０同士が直列接続されている。なお、一つの光電変換装置１０内において、接続導体７は光吸収層３および半導体層４を貫通するように設けられており、第１の電極層２と透明電極層５とで挟まれた光吸収層３と半導体層４とで光電変換が行なわれる。   In FIG. 1, a plurality of photoelectric conversion devices 10 are formed side by side. The photoelectric conversion device 10 includes a third electrode layer 6 provided on the substrate 1 side of the light absorption layer 3 so as to be separated from the first electrode layer 2. The transparent electrode layer 5 and the third electrode layer 6 are electrically connected by the connection conductor 7 provided in the light absorption layer 3. The third electrode layer 6 is integrated with the first electrode layer 2 of the adjacent photoelectric conversion device 10. With this configuration, adjacent photoelectric conversion devices 10 are connected in series. In one photoelectric conversion device 10, the connection conductor 7 is provided so as to penetrate the light absorption layer 3 and the semiconductor layer 4, and light sandwiched between the first electrode layer 2 and the transparent electrode layer 5. Photoelectric conversion is performed between the absorption layer 3 and the semiconductor layer 4.

基板１は、光電変換装置１０を支持するためのものである。基板１に用いられる材料としては、例えば、ガラス、セラミックス、樹脂および金属等が挙げられる。   The substrate 1 is for supporting the photoelectric conversion device 10. Examples of the material used for the substrate 1 include glass, ceramics, resin, and metal.

第１の電極層２および第３の電極層６は、Ｍｏ、Ａｌ、ＴｉまたはＡｕ等の導電体が用いられ、基板１上にスパッタリング法または蒸着法等で形成される。   The first electrode layer 2 and the third electrode layer 6 are made of a conductor such as Mo, Al, Ti, or Au, and are formed on the substrate 1 by a sputtering method or a vapor deposition method.

透明電極層５は、ＩＴＯ、ＺｎＯ等の０．０５〜３μｍの透明導電膜である。透明電極層５は、スパッタリング法、蒸着法または化学的気相成長（ＣＶＤ）法等で形成される。透明電極層５は、半導体層４よりも抵抗率の低い層であり、光吸収層３で生じた電荷を取り出すためのものである。電荷を良好に取り出すという観点からは、透明電極層５の抵抗率が１Ω・ｃｍ未満でシ−ト抵抗が５０Ω／□以下であるのがよい。   The transparent electrode layer 5 is a 0.05 to 3 μm transparent conductive film such as ITO or ZnO. The transparent electrode layer 5 is formed by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like. The transparent electrode layer 5 is a layer having a resistivity lower than that of the semiconductor layer 4, and is for taking out charges generated in the light absorption layer 3. From the viewpoint of taking out charges well, it is preferable that the resistivity of the transparent electrode layer 5 is less than 1 Ω · cm and the sheet resistance is 50 Ω / □ or less.

透明電極層５は光吸収層３の吸収効率を高めるため、光吸収層３の吸収光に対して光透過性を有するものが好ましい。光透過性を高めると同時に光反射ロス防止効果および光散乱効果を高め、さらに光電変換によって生じた電流を良好に伝送するという観点から、透明電極層５は０．０５〜０．５μｍの厚さとするのが好ましい。また、透明電極層５と半導体層４との界面での光反射ロスを防止する観点からは、透明電極層５と半導体層４の屈折率は等しいのが好ましい。   In order to increase the absorption efficiency of the light absorption layer 3, the transparent electrode layer 5 preferably has a light transmittance with respect to the absorption light of the light absorption layer 3. The transparent electrode layer 5 has a thickness of 0.05 to 0.5 μm from the viewpoint of enhancing the light transmittance and at the same time enhancing the light reflection loss prevention effect and the light scattering effect, and further transmitting the current generated by the photoelectric conversion. It is preferable to do this. Further, from the viewpoint of preventing light reflection loss at the interface between the transparent electrode layer 5 and the semiconductor layer 4, the refractive indexes of the transparent electrode layer 5 and the semiconductor layer 4 are preferably equal.

次に本発明の光電変換装置の実施の形態の他の例を図２、図３に基づき説明する。図２は他の実施形態である光電変換装置２０の断面図であり、図３は光電変換装置２０の斜視図である。図２、図３は、透明電極層５上に集電電極８が形成されている点で図１の光電変換装置１０と異なっている。図２、図３において、図１と同じ構成のものには、同じ符号を付しており、図１と同様、光電変換装置２０が複数接続されて光電変換モジュ−ル２１を構成している。   Next, another example of the embodiment of the photoelectric conversion device of the present invention will be described with reference to FIGS. FIG. 2 is a cross-sectional view of a photoelectric conversion device 20 according to another embodiment, and FIG. 3 is a perspective view of the photoelectric conversion device 20. 2 and 3 are different from the photoelectric conversion device 10 in FIG. 1 in that a collecting electrode 8 is formed on the transparent electrode layer 5. 2 and 3, the same components as those in FIG. 1 are denoted by the same reference numerals, and as in FIG. 1, a plurality of photoelectric conversion devices 20 are connected to constitute a photoelectric conversion module 21. .

本発明の一実施形態の光電変換装置は、光電変換可能な化合物半導体を含む光吸収層と、該光吸収層の一方の表面に設けられたＩｎのカルコゲン化物を含む第１の半導体層と、該第１の半導体層の前記光吸収層と反対側の表面に設けられたＺｎのカルコゲン化物およびＩｎを含む第２の半導体層と、該第２の半導体層の前記光吸収層と反対側の表面に設けられたＩｎを含む透明電極層とを具備しており、前記第２の半導体層は前記第１の半導体層との界面付近においてＩｎの組成比率の極小値を有している。
A photoelectric conversion device according to an embodiment of the present invention includes a light absorption layer including a compound semiconductor capable of photoelectric conversion, a first semiconductor layer including a chalcogenide of In provided on one surface of the light absorption layer, A second semiconductor layer containing Zn chalcogenide and In provided on a surface of the first semiconductor layer opposite to the light absorption layer; and a second semiconductor layer opposite to the light absorption layer. And a transparent electrode layer containing In provided on the surface, wherein the second semiconductor layer has a minimum value of the In composition ratio in the vicinity of the interface with the first semiconductor layer.

図４において、縦軸は光吸収層３および半導体層４の全組成に対するＩｎの原子％、横軸は光吸収層３と第１の半導体層４ａとの界面を原点（０）としたときの距離を示すものであり、光吸収層側を＋、第１の半導体層４ａ側を−としているものである。例えば、第２の半導体層４ｂにおける第１の半導体層４ａとの界面付近（−３０ｎｍ付近、すなわち図４の点線の円で囲まれた部分）では、Ｉｎの組成比率の極小値を有している。   In FIG. 4, the vertical axis is In atomic% with respect to the total composition of the light absorption layer 3 and the semiconductor layer 4, and the horizontal axis is when the interface between the light absorption layer 3 and the first semiconductor layer 4 a is the origin (0). The distance is shown, and the light absorption layer side is +, and the first semiconductor layer 4a side is-. For example, in the vicinity of the interface between the second semiconductor layer 4b and the first semiconductor layer 4a (near −30 nm, that is, the portion surrounded by the dotted circle in FIG. 4), the In composition ratio has a minimum value. Yes.

この極小値の領域で導電性が最も低くなることで、光吸収層３から半導体層４にかけてのリ−ク電流を低減し、光電変換効率の高い信頼性を得るものである。   By having the lowest conductivity in this minimum value region, the leak current from the light absorption layer 3 to the semiconductor layer 4 is reduced, and the reliability with high photoelectric conversion efficiency is obtained.

また、この極小値の領域によって、経年変化による透明電極層５側からのＩｎの拡散が緩衝され、第１の半導体層４ａへの必要以上のＩｎの拡散を抑えることができる。その結果、光吸収層３と第１の半導体層４ａとの良好なｐｎ接合を維持することができ、光電変換効率の高い信頼性を得るものである。   In addition, the region of the minimum value buffers In diffusion from the transparent electrode layer 5 side due to secular change, and can suppress unnecessary diffusion of In to the first semiconductor layer 4a. As a result, it is possible to maintain a good pn junction between the light absorption layer 3 and the first semiconductor layer 4a, and to obtain high reliability with high photoelectric conversion efficiency.

また、第２の半導体層４ｂの透明電極５側においてＩｎが予め含まれていることによって、透明電極層５から第２の半導体層４ｂへのＩｎの拡散を低減することができる。その結果、経年変化による透明電極５からのＩｎの拡散が、第２の半導体層４ｂ中で局所的に進行することによる大きなリ−ク電流の発生を低減できる。   In addition, since In is contained in advance on the transparent electrode 5 side of the second semiconductor layer 4b, diffusion of In from the transparent electrode layer 5 to the second semiconductor layer 4b can be reduced. As a result, it is possible to reduce the generation of a large leak current due to the diffusion of In from the transparent electrode 5 due to aging progressing locally in the second semiconductor layer 4b.

なお透明電極層５から半導体層４にかけて、Ｉｎの組成が断続的に大きく変化している
場合は、透過率や屈折率の急激な変化の要因となり、吸収する光の反射が生じてしまうので、Ｉｎの組成比率は膜厚方向に連続的に漸次変化していることが好ましい。 In addition, when the composition of In changes from the transparent electrode layer 5 to the semiconductor layer 4 intermittently, it causes a sudden change in transmittance and refractive index, resulting in reflection of absorbed light. It is preferable that the composition ratio of In changes gradually and continuously in the film thickness direction.

本発明の一実施形態の光電変換装置は、前記第１の半導体層はＩｎのカルコゲン化物を含み、前記第２の半導体層はＺｎのカルコゲン化物を含んでいる。
The photoelectric conversion device according to an embodiment of the present invention, the first semiconductor layer comprises a chalcogenide of In, the second semiconductor layer that contains a chalcogenide Zn.

Ｉｎのカルコゲン化物としては、例えば、Ｉｎ２Ｓ３、Ｉｎ２Ｓｅ３、Ｉｎ２Ｔｅ３などが挙げられる。このようなＩｎのカルコゲン化物を含む半導体は、高温高湿の環境下における耐久性が高く、劣化しにくい。
 Examples of In chalcogenides include In 2 S 3 , In 2 Se 3 , and In 2 Te 3 . A semiconductor containing such a chalcogenide of In has high durability under a high temperature and high humidity environment and is hardly deteriorated.

また、第２の半導体層４ｂはＺｎのカルコゲン化物を含む半導体であり、Ｚｎのカルコゲン化物とは、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅをいう。Ｚｎの水酸化物やＺｎの酸化物を含んでいてもよい。好ましくは、第２の半導体層４ｂを構成するＺｎの全モル数のうち、６０％以上がＺｎのカルコゲン化物であることが好ましい。このようなＺｎのカルコゲン化物を含む半導体は、光吸収層３とのバンド整合を良好にすることができ、光電変換効率を高めることができる。   The second semiconductor layer 4b is a semiconductor containing a Zn chalcogenide, and the Zn chalcogenide is ZnS, ZnSe, or ZnTe. Zn hydroxide or Zn oxide may be included. Preferably, 60% or more of the total number of moles of Zn constituting the second semiconductor layer 4b is a chalcogenide of Zn. Such a semiconductor containing a chalcogenide of Zn can improve the band matching with the light absorption layer 3 and can increase the photoelectric conversion efficiency.

そして、光吸収層３上に第１の半導体層４ａおよび第２の半導体層４ｂを順次積層した構成とすることで、高温高湿の環境下での高い耐久性と高い光電変換効率を兼ね備えたものとなるとともに、大面積で光電変換装置を作製した場合にも、このような耐久性および光電変換効率が面内位置によってばらつくことを抑制できる。よって、耐久性および光電変換特性にすぐれた光電変換装置の大面積化が可能となる。   The first semiconductor layer 4a and the second semiconductor layer 4b are sequentially stacked on the light absorption layer 3, thereby having both high durability and high photoelectric conversion efficiency in a high temperature and high humidity environment. In addition, even when a photoelectric conversion device is manufactured with a large area, it is possible to prevent such durability and photoelectric conversion efficiency from varying depending on the in-plane position. Therefore, it is possible to increase the area of the photoelectric conversion device having excellent durability and photoelectric conversion characteristics.

さらに第１の半導体層４ａは５〜１００ｎｍであることが好ましい。このような厚みであると、第２の半導体層４ｂが光吸収層３に接近して形成されるため、光吸収層３とのバンド整合を良好にして光吸収層３と半導体層４とで構成される光電変換部の電荷分離機能を高めることができる。   Furthermore, the first semiconductor layer 4a is preferably 5 to 100 nm. With such a thickness, the second semiconductor layer 4 b is formed close to the light absorption layer 3, so that band matching with the light absorption layer 3 is good and the light absorption layer 3 and the semiconductor layer 4 The charge separation function of the configured photoelectric conversion unit can be enhanced.

さらに第２の半導体層４ａは５〜１００ｎｍであることが好ましい。このような厚みであることにより、漏れ電流の低減に寄与し、電圧を向上させ、性能を高めることができる。また、取出し電流の抵抗となる成分を抑えることができ、性能を高めることができる。   Further, the second semiconductor layer 4a is preferably 5 to 100 nm. With such a thickness, it is possible to contribute to a reduction in leakage current, improve voltage, and improve performance. Moreover, the component which becomes resistance of extraction current can be suppressed, and performance can be improved.

さらに、本発明の一実施形態の光電変換装置の好ましい半導体層４の形態としては、第１の半導体層が硫化インジウムを含み、第２の半導体層が硫化亜鉛を含むものが好ましい。これにより、半導体層４間でのバンド整合がより良好となり電荷移動が良好となる。特に光吸収層３がI−III−VI族化合物半導体から成るカルコパイライト系の化合物半導体である場合、光吸収層３、半導体層４のバンド整合が特に良好となり光電変換効率をより高めることができる。好ましくは、第１の半導体層４ａを構成するＩｎの全モル数のうち、６０％以上が硫化インジウムであり、第２の半導体層４ｂを構成するＺｎの全モル数のうち、６０％以上が硫化亜鉛であることが好ましい。これにより、半導体層４全体の高温高湿の環境下における耐久性をより高めることができる。   Furthermore, as a preferable form of the semiconductor layer 4 of the photoelectric conversion device according to one embodiment of the present invention, it is preferable that the first semiconductor layer contains indium sulfide and the second semiconductor layer contains zinc sulfide. As a result, band matching between the semiconductor layers 4 is improved, and charge transfer is improved. In particular, when the light absorption layer 3 is a chalcopyrite compound semiconductor made of an I-III-VI group compound semiconductor, the band matching of the light absorption layer 3 and the semiconductor layer 4 is particularly good, and the photoelectric conversion efficiency can be further increased. . Preferably, 60% or more of the total number of moles of In constituting the first semiconductor layer 4a is indium sulfide, and 60% or more of the total number of moles of Zn constituting the second semiconductor layer 4b. Zinc sulfide is preferred. Thereby, the durability of the entire semiconductor layer 4 in a high-temperature and high-humidity environment can be further enhanced.

さらに、本発明の一実施形態の光電変換装置の光吸収層３は、カルコパイライト系の材料を含むことが好ましく、光を吸収して電荷を生じる機能を有する。光吸収層３は特に限定されないが、１０μｍ以下の薄層でも高い光電変換効率を得ることができるという観点からは、カルコパイライト系の化合物半導体であることが好ましい。カルコパイライト系の化合物半導体としては、例えばI−III−VI族化合物半導体がある。I−III−VI族化合物
半導体とは、Ｉ−Ｂ族元素（１１族元素ともいう）とIII−Ｂ族元素（１３族元素ともいう）とVI−Ｂ族元素（１６族元素ともいう）との化合物半導体である（ＣＩＳ系化合物半導体ともいう）。I−III−VI族化合物半導体としては、例えば、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ２（ＣＩＧＳともいう）、Ｃｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）２（ＣＩＧＳＳともいう）、およびＣｕＩｎＳ２（ＣＩＳともいう）が挙げられる。なお、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ２とは、ＣｕとＩｎとＧａとＳｅとから主に構成された化合物をいう。また、Ｃｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）２とは、ＣｕとＩｎとＧａとＳｅとＳとから主に構成された化合物をいう。 Furthermore, the light absorption layer 3 of the photoelectric conversion device according to one embodiment of the present invention preferably includes a chalcopyrite material and has a function of absorbing light and generating a charge. The light absorption layer 3 is not particularly limited, but is preferably a chalcopyrite compound semiconductor from the viewpoint that high photoelectric conversion efficiency can be obtained even with a thin layer of 10 μm or less. An example of the chalcopyrite compound semiconductor is an I-III-VI group compound semiconductor. The group I-III-VI compound semiconductor is a group IB element (also referred to as a group 11 element), a group III-B element (also referred to as a group 13 element), and a group VI-B element (also referred to as a group 16 element). Compound semiconductor (also referred to as CIS compound semiconductor). Examples of the I-III-VI group compound semiconductor include Cu (In, Ga) Se 2 (also referred to as CIGS), Cu (In, Ga) (Se, S) 2 (also referred to as CIGSS), and CuInS 2 (CIS). Also called). Cu (In, Ga) Se 2 refers to a compound mainly composed of Cu, In, Ga, and Se. Cu (In, Ga) (Se, S) 2 refers to a compound mainly composed of Cu, In, Ga, Se, and S.

また、II−VI族化合物半導体とは、II−Ｂ族元素（１２族元素ともいう）とVI−Ｂ族元素との化合物半導体である。II−VI族化合物半導体としては、例えば、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＣｄＳ，ＣｄＳｅ、ＣｄＴｅ等が挙げられる。   The II-VI group compound semiconductor is a compound semiconductor of a group II-B element (also referred to as a group 12 element) and a group VI-B element. Examples of the II-VI group compound semiconductor include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, and the like.

このような光吸収層３は以下のような方法により形成できる。まず、原料元素（例えばＩ−Ｂ族元素、II−Ｂ族元素、III−Ｂ族元素、VI−Ｂ族元素など）をスパッタリングや蒸着によって膜状に形成し、または原料溶液の塗布によって膜状に形成し、原料元素を含む前駆体を形成する。そしてこの前駆体を加熱することにより半導体から成る光吸収層３を形成できる。あるいは、金属元素（例えばＩ−Ｂ族元素、II−Ｂ族元素、III−Ｂ族元素など）を上記と同様に膜状に形成して前駆体を形成し、この前駆体をVI−Ｂ族元素を含むガス雰囲気下で加熱することによっても形成できる。   Such a light absorption layer 3 can be formed by the following method. First, a raw material element (for example, an IB group element, an II-B group element, a III-B group element, a VI-B group element, etc.) is formed into a film shape by sputtering or vapor deposition, or a film shape is formed by applying a raw material solution. To form a precursor containing raw material elements. And the light absorption layer 3 which consists of a semiconductor can be formed by heating this precursor. Alternatively, a metal element (for example, an IB group element, an II-B group element, an III-B group element, etc.) is formed into a film shape in the same manner as described above to form a precursor, and this precursor is converted into a VI-B group. It can also be formed by heating in a gas atmosphere containing an element.

（光電変換モジュ−ル）
さらに、本発明の一実施形態の光電変換モジュ−ルは、光電変換装置を複数有し、隣接する光電変換装置を電気的に接続したものである。すなわち、光電変換装置１０は、複数個を並べてこれらを電気的に接続し、光電変換モジュ−ル１１とすることができる。隣接する光電変換装置１０同士を容易に直列接続するために、図１に示すように、光電変換装置１０は、光吸収層３の基板１側に第１の電極層２と離間して設けられた第３の電極層６を具備している。そして、光吸収層３に設けられた接続導体７によって、透明電極層５と第３の電極層６とが電気的に接続されている。 (Photoelectric conversion module)
Furthermore, the photoelectric conversion module according to one embodiment of the present invention has a plurality of photoelectric conversion devices and electrically connects adjacent photoelectric conversion devices. That is, a plurality of photoelectric conversion devices 10 can be arranged and electrically connected to form a photoelectric conversion module 11. In order to easily connect adjacent photoelectric conversion devices 10 in series, as shown in FIG. 1, the photoelectric conversion device 10 is provided on the substrate 1 side of the light absorption layer 3 so as to be separated from the first electrode layer 2. The third electrode layer 6 is provided. The transparent electrode layer 5 and the third electrode layer 6 are electrically connected by the connection conductor 7 provided in the light absorption layer 3.

接続導体７は、透明電極層５を形成する際に同時形成して一体化することが好ましい。これにより、工程を簡略化できるとともに透明電極層５との電気的な接続信頼性を高めることができる。接続導体７は、透明電極層５と第３の電極層６とを接続するとともに、隣接する光電変換装置１０の各光吸収層３も分断するように形成されていることにより、隣接する光吸収層３でそれぞれ光電変換を良好に行い、直列接続で電流を取り出すことができる。   The connection conductor 7 is preferably formed and integrated simultaneously when forming the transparent electrode layer 5. Thereby, while being able to simplify a process, the electrical connection reliability with the transparent electrode layer 5 can be improved. The connection conductor 7 connects the transparent electrode layer 5 and the third electrode layer 6, and is formed so as to divide the light absorption layers 3 of the adjacent photoelectric conversion devices 10. Each layer 3 can perform good photoelectric conversion, and current can be taken out in series connection.

（光電変換装置の製造方法）
次に本発明の一実施形態の光電変換装置の製造方法について説明する。 (Manufacturing method of photoelectric conversion device)
Next, the manufacturing method of the photoelectric conversion apparatus of one Embodiment of this invention is demonstrated.

光電変換装置の製造方法には、湿式成膜法が用いられる。この湿式成膜法は、原料溶液を光吸収層３上に塗布しそれを加熱等の処理により化学反応させる方法や、原料を含む溶液中での化学反応により光吸収層３上に析出させる方法である。   A wet film forming method is used as a method for manufacturing the photoelectric conversion device. In this wet film forming method, a raw material solution is applied onto the light absorption layer 3 and chemically reacted by a treatment such as heating, or a method of depositing on the light absorption layer 3 by a chemical reaction in a solution containing the raw material. It is.

このような方法とすることで、光吸収層３表面に半導体層４がある程度拡散して形成され、光吸収層３と半導体層４とのヘテロ接合を欠陥の少ない良好なものとすることができる。   By adopting such a method, the semiconductor layer 4 is diffused to some extent on the surface of the light absorption layer 3, and the heterojunction between the light absorption layer 3 and the semiconductor layer 4 can be made favorable with few defects. .

本発明の一実施形態の光電変換装置の製造方法は、光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、該中間層の表面にＩｎを含む透明導電層を形成する第３工程と、該透明電極層を還元雰囲気中で熱処理して前記透明電極層から前記中間層内にＩｎを拡散させる第４工程とを有する。
The manufacturing method of the photoelectric conversion device of one embodiment of the present invention includes a first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorbing layer containing a compound semiconductor capable of photoelectric conversion, A second step of forming an intermediate layer containing Zn chalcogenide on the surface of the semiconductor layer, a third step of forming a transparent conductive layer containing In on the surface of the intermediate layer, and the transparent electrode layer in a reducing atmosphere. And a fourth step of diffusing In from the transparent electrode layer into the intermediate layer.

この第４工程では、水素等の還元雰囲気下において、好ましくは１５０〜２５０℃、１〜１０時間程度熱処理する。   In the fourth step, heat treatment is preferably performed at 150 to 250 ° C. for about 1 to 10 hours in a reducing atmosphere such as hydrogen.

これによって、透明電極層５から中間層の方向へＩｎが積極的に拡散する一方、第１の半導体層４ａからも中間層の方向へＩｎが積極的に拡散するので、中間層における第１の半導体層４ａとの界面付近において、Ｉｎの組成比率の極小値が形成され、中間層は第２の半導体層４ｂとなる。   Accordingly, In actively diffuses from the transparent electrode layer 5 toward the intermediate layer, while In actively diffuses also from the first semiconductor layer 4a toward the intermediate layer, the first layer in the intermediate layer In the vicinity of the interface with the semiconductor layer 4a, a minimum value of the In composition ratio is formed, and the intermediate layer becomes the second semiconductor layer 4b.

また、本発明の他の実施形態の光電変換装置の製造方法は、光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、該中間層をＩｎを含む溶液に浸漬することで該溶液から前記中間層内にＩｎを拡散させる第３工程とを有する。 Moreover, the manufacturing method of the photoelectric conversion device according to another embodiment of the present invention includes a first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorption layer containing a compound semiconductor capable of photoelectric conversion, A second step of forming an intermediate layer containing a chalcogenide of Zn on the surface of the first semiconductor layer; and immersing the intermediate layer in a solution containing In to diffuse In from the solution into the intermediate layer. A third step.

この第３工程では、中間層をＩｎを含む溶液に浸漬する、好ましくは中間層を乾燥させた後、Ｉｎを含む溶液に圧力をかけて浸漬する。   In the third step, the intermediate layer is immersed in a solution containing In. Preferably, after the intermediate layer is dried, the solution containing In is pressurized and immersed.

これによって、中間層へＩｎを積極的に拡散させることができ、中間層における第１の半導体層４ａとの界面付近において、Ｉｎの組成比率の極小値が形成され、中間層は第２の半導体層４ｂとなる。   As a result, In can be actively diffused into the intermediate layer, a minimum value of the composition ratio of In is formed in the vicinity of the interface with the first semiconductor layer 4a in the intermediate layer, and the intermediate layer is the second semiconductor. Layer 4b is formed.

これらの光電変換装置の製造方法によって、予め第２の半導体層４ｂにＩｎを適切に拡散させておくことができ、経年変化でのＩｎの拡散によるリ−ク電流を低減し、光電変換効率が大きく変化することを低減することができる。   By the manufacturing method of these photoelectric conversion devices, In can be appropriately diffused in advance in the second semiconductor layer 4b, the leak current due to the diffusion of In over time can be reduced, and the photoelectric conversion efficiency can be improved. Large changes can be reduced.

１：基板
２：第１の電極層
３：光吸収層
４：半導体層
４ａ：第１の半導体層
４ｂ：第２の半導体層
５：第２の電極層（透明電極層）
６：第３の電極層
７：接続導体
８：集電電極
９：光電変換体
１０、２０：光電変換装置
１１、２１：光電変換モジュ−ル 1: Substrate 2: First electrode layer 3: Light absorption layer 4: Semiconductor layer 4a: First semiconductor layer 4b: Second semiconductor layer 5: Second electrode layer (transparent electrode layer)
6: third electrode layer 7: connecting conductor 8: current collecting electrode 9: photoelectric conversion body 10, 20: photoelectric conversion device 11, 21: photoelectric conversion module

Claims (6)

光電変換可能な化合物半導体を含む光吸収層と、
該光吸収層の一方の表面に設けられたＩｎのカルコゲン化物を含む第１の半導体層と、
該第１の半導体層の前記光吸収層と反対側の表面に設けられたＺｎのカルコゲン化物およびＩｎを含む第２の半導体層と、
該第２の半導体層の前記光吸収層と反対側の表面に設けられたＩｎを含む透明電極層と
を具備しており、
前記第２の半導体層は前記第１の半導体層との界面付近においてＩｎの組成比率の極小値を有している光電変換装置。 A light absorbing layer comprising a compound semiconductor capable of photoelectric conversion;
A first semiconductor layer containing a chalcogenide of In provided on one surface of the light absorption layer;
A second semiconductor layer containing Zn chalcogenide and In provided on a surface of the first semiconductor layer opposite to the light absorption layer;
A transparent electrode layer containing In provided on the surface of the second semiconductor layer opposite to the light absorption layer;
The photoelectric conversion device, wherein the second semiconductor layer has a minimum value of an In composition ratio in the vicinity of an interface with the first semiconductor layer. 前記第１の半導体層は硫化インジウムを含み、前記第２の半導体層は硫化亜鉛を含む請求項１に記載の光電変換装置。 The photoelectric conversion device according to claim 1, wherein the first semiconductor layer includes indium sulfide, and the second semiconductor layer includes zinc sulfide. 前記光吸収層はカルコパイライト系の材料を含む請求項１または２に記載の光電変換装置。 The light absorbing layer is a photoelectric conversion device according to claim 1 or 2 comprising a material of chalcopyrite. 請求項１〜３のいずれかに記載の光電変換装置を複数有し、隣接する前記光電変換装置を電気的に接続した光電変換モジュ−ル。 A plurality of photoelectric conversion device according to any one of claims 1 to 3 electrically connects the photoelectric conversion module of the photoelectric conversion device adjacent - le. 光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、
該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、
該中間層の表面にＩｎを含む透明導電層を形成する第３工程と、
該透明電極層を還元雰囲気中で熱処理して前記透明電極層から前記中間層内にＩｎを拡散させる第４工程とを有する光電変換装置の製造方法。 A first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorption layer containing a compound semiconductor capable of photoelectric conversion;
A second step of forming an intermediate layer containing a chalcogenide of Zn on the surface of the first semiconductor layer;
A third step of forming a transparent conductive layer containing In on the surface of the intermediate layer;
And a fourth step of diffusing In from the transparent electrode layer into the intermediate layer by heat-treating the transparent electrode layer in a reducing atmosphere. 光電変換可能な化合物半導体を含む光吸収層上にＩｎのカルコゲン化物を含む第１の半導体層を形成する第１工程と、
該第１の半導体層の表面にＺｎのカルコゲン化物を含む中間層を形成する第２工程と、
該中間層をＩｎを含む溶液に浸漬することで該溶液から前記中間層内にＩｎを拡散させる第３工程とを有する光電変換装置の製造方法。 A first step of forming a first semiconductor layer containing a chalcogenide of In on a light absorption layer containing a compound semiconductor capable of photoelectric conversion;
A second step of forming an intermediate layer containing a chalcogenide of Zn on the surface of the first semiconductor layer;
And a third step of diffusing In from the solution into the intermediate layer by immersing the intermediate layer in a solution containing In.
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