JPWO2011118716A1 - Photoelectric conversion device - Google Patents
Photoelectric conversion device Download PDFInfo
- Publication number
- JPWO2011118716A1 JPWO2011118716A1 JP2012507064A JP2012507064A JPWO2011118716A1 JP WO2011118716 A1 JPWO2011118716 A1 JP WO2011118716A1 JP 2012507064 A JP2012507064 A JP 2012507064A JP 2012507064 A JP2012507064 A JP 2012507064A JP WO2011118716 A1 JPWO2011118716 A1 JP WO2011118716A1
- Authority
- JP
- Japan
- Prior art keywords
- photoelectric conversion
- layer
- conversion device
- linear
- semiconductor layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
変換効率が向上された光電変換装置を提供することを図る。この目的を達成するために、光電変換装置は、一主面に線状の窪み部が延在し且つ第１の導電型を有している第１半導体層と、該第１半導体層の一主面の上に配されている第２の導電型を有する第２半導体層と、を備えている。A photoelectric conversion device with improved conversion efficiency is provided. In order to achieve this object, a photoelectric conversion device includes a first semiconductor layer in which a linear depression extends on one main surface and has a first conductivity type, and one of the first semiconductor layers. And a second semiconductor layer having a second conductivity type disposed on the main surface.
Description
本発明は、光電変換装置、および光電変換装置の製造方法に関する。 The present invention relates to a photoelectric conversion device and a method for manufacturing the photoelectric conversion device.
太陽電池として、主にＩ−III−VI族化合物半導体から成る光吸収層を具備した光電変換装置を用いたものがある（例えば、特許文献１参照）。Ｉ−III−VI族化合物半導体は、ＣＩＧＳ等といったカルコパイライト系の化合物半導体である。ＣＩＧＳは、光吸収係数が高く、光電変換装置の薄膜化、大面積化および製造コストの低減に適している。 As a solar cell, there is one using a photoelectric conversion device including a light absorption layer mainly composed of an I-III-VI group compound semiconductor (for example, see Patent Document 1). The I-III-VI group compound semiconductor is a chalcopyrite compound semiconductor such as CIGS. CIGS has a high light absorption coefficient and is suitable for reducing the thickness and area of the photoelectric conversion device and reducing the manufacturing cost.
この光電変換装置では、複数の光電変換セルが、平面的に並設されている。各光電変換セルでは、ガラス等の基板の上に、主に金属電極等から成る下部電極と、光吸収層およびバッファ層等を主に含む半導体層から成る光電変換層と、主に透明電極および金属電極等から成る上部電極とが、この順に積層されている。また、複数の光電変換セルは、隣り合う一方の光電変換セルの上部電極と他方の光電変換セルの下部電極とが接続導体によって電気的に接続されることで、電気的に直列に接続されている。 In this photoelectric conversion device, a plurality of photoelectric conversion cells are arranged side by side in a plane. In each photoelectric conversion cell, on a substrate such as glass, a lower electrode mainly made of a metal electrode, a photoelectric conversion layer mainly made of a semiconductor layer mainly including a light absorption layer and a buffer layer, a mainly transparent electrode and An upper electrode made of a metal electrode or the like is laminated in this order. In addition, the plurality of photoelectric conversion cells are electrically connected in series by electrically connecting the upper electrode of one adjacent photoelectric conversion cell and the lower electrode of the other photoelectric conversion cell by a connecting conductor. Yes.
カルコパイライト系の光電変換装置では、例えば、製造工程における熱処理時の膨張と収縮ならびに屋外での使用時における外力の付与に起因する応力の発生等によって、光吸収層にクラックが生じる虞がある。このクラックの発生は、光電変換装置における変換効率の低下を招く。そして、この問題は、カルコパイライト系の光電変換装置以外の光電変換装置にも生じ得る。 In a chalcopyrite photoelectric conversion device, cracks may occur in the light absorption layer due to, for example, expansion and contraction during heat treatment in the manufacturing process and generation of stress due to application of external force during outdoor use. Generation | occurrence | production of this crack causes the fall of the conversion efficiency in a photoelectric conversion apparatus. This problem may also occur in photoelectric conversion devices other than chalcopyrite type photoelectric conversion devices.
そこで、変換効率が向上された光電変換装置が望まれている。 Therefore, a photoelectric conversion device with improved conversion efficiency is desired.
上記課題を解決するために、第１の態様に係る光電変換装置は、一主面に線状の窪み部が延在し且つ第１の導電型を有している第１半導体層と、前記一主面の上に配されている第２の導電型を有する第２半導体層と、を備える。 In order to solve the above-described problem, a photoelectric conversion device according to a first aspect includes a first semiconductor layer in which a linear depression extends on one main surface and has a first conductivity type, And a second semiconductor layer having a second conductivity type disposed on one main surface.
また、第２の態様に係る光電変換装置の製造方法は、原料溶液および化合物半導体の微粒子を含有する微粒子含有溶液を準備する工程と、前記微粒子含有溶液を電極層の上に塗布して皮膜を形成する工程と、前記皮膜に対して熱処理を施すことで、一主面に線状の窪み部が延在している半導体層を形成する工程と、を備え、前記原料溶液に、ルイス塩基性有機化合物、カルコゲン元素を含有する有機化合物および金属元素を含ませ、前記化合物半導体の微粒子に、前記金属元素を含ませる。 In addition, a method for manufacturing a photoelectric conversion device according to the second aspect includes a step of preparing a raw material solution and a fine particle-containing solution containing fine particles of a compound semiconductor, and applying the fine particle-containing solution onto an electrode layer to form a film. And a step of forming a semiconductor layer in which a linear depression extends on one main surface by subjecting the film to a heat treatment. An organic compound, an organic compound containing a chalcogen element, and a metal element are included, and the metal element is included in the fine particles of the compound semiconductor.
本発明の上記態様によれば、変換効率が向上された光電変換装置が実現される。 According to the above aspect of the present invention, a photoelectric conversion device with improved conversion efficiency is realized.
以下、本発明の一実施形態を図面に基づいて説明する。なお、図面においては同様な構成および機能を有する部分については同一符号が付されており、下記説明では重複説明が省略される。また、図面は模式的に示されたものであり、各図における各種構造のサイズおよび位置関係等は正確に図示されたものではない。なお、図１から図１４には、光電変換セル１０の配列方向（図１の図面視左右方向）をＸ軸方向とする右手系のＸＹＺ座標系が付されている。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In the drawings, parts having similar configurations and functions are denoted by the same reference numerals, and redundant description is omitted in the following description. Further, the drawings are schematically shown, and the sizes, positional relationships, and the like of various structures in the drawings are not accurately illustrated. 1 to 14 are provided with a right-handed XYZ coordinate system in which the arrangement direction of photoelectric conversion cells 10 (the horizontal direction in the drawing in FIG. 1) is the X-axis direction.
＜(1)光電変換装置の構成＞
光電変換装置２１は、基板１と、該基板１の上に平面的に並べられた複数の光電変換セル１０とを備えている。図１では、図示の都合上、２つの光電変換セル１０の一部のみが示されている。但し、実際の光電変換装置２１には、図面の左右方向に、多数の光電変換セル１０が平面的に配列され得る。<(1) Configuration of photoelectric conversion device>
The photoelectric conversion device 21 includes a substrate 1 and a plurality of photoelectric conversion cells 10 arranged in a plane on the substrate 1. In FIG. 1, only a part of the two photoelectric conversion cells 10 is shown for convenience of illustration. However, in the actual photoelectric conversion device 21, a large number of photoelectric conversion cells 10 can be arranged in a plane in the left-right direction of the drawing.
各光電変換セル１０は、下部電極層２と、光電変換層３と、上部電極層４と、グリッド電極５と、接続部４５とを備えている。光電変換装置２１では、上部電極層４およびグリッド電極５が配されている側の主面が受光面側となっている。また、光電変換装置２１には、第１溝部Ｐ１、第２溝部Ｐ２および第３溝部Ｐ３といった３種類の溝部が延在している。 Each photoelectric conversion cell 10 includes a lower electrode layer 2, a photoelectric conversion layer 3, an upper electrode layer 4, a grid electrode 5, and a connection portion 45. In the photoelectric conversion device 21, the main surface on which the upper electrode layer 4 and the grid electrode 5 are arranged is the light receiving surface side. Further, in the photoelectric conversion device 21, three kinds of groove portions such as a first groove portion P1, a second groove portion P2, and a third groove portion P3 extend.
基板１は、複数の光電変換セル１０を支持するものである。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採用され得る。本実施形態では、基板１は、１ｍｍ以上で且つ３ｍｍ以下程度の厚さを有する青板ガラス（ソーダライムガラス）である。 The substrate 1 supports a plurality of photoelectric conversion cells 10. As a material used for the substrate 1, for example, glass, ceramics, resin, metal and the like can be adopted. In the present embodiment, the substrate 1 is blue plate glass (soda lime glass) having a thickness of 1 mm or more and 3 mm or less.
下部電極層２は、基板１の＋Ｚ側の主面（一主面とも言う）の上に配されている導電層である。下部電極層２に含まれる主な材料としては、例えば、Ｍｏ、Ａｌ、Ｔｉ、ＴａまたはＡｕ等の導電性を有する各種金属等が採用され得る。また、下部電極層２の厚さは、０．２μｍ以上で且つ１μｍ以下程度であれば良い。下部電極層２は、例えば、スパッタリング法または蒸着法等の公知の薄膜形成方法によって形成され得る。 The lower electrode layer 2 is a conductive layer disposed on the main surface (also referred to as one main surface) on the + Z side of the substrate 1. As main materials included in the lower electrode layer 2, various conductive metals such as Mo, Al, Ti, Ta, or Au can be employed, for example. Moreover, the thickness of the lower electrode layer 2 should just be about 0.2 micrometer or more and 1 micrometer or less. The lower electrode layer 2 can be formed by a known thin film forming method such as a sputtering method or a vapor deposition method.
光電変換層３は、第１半導体層としての光吸収層３１と第２半導体層としてのバッファ層３２とを備える。光吸収層３１とバッファ層３２とは、積層されている。 The photoelectric conversion layer 3 includes a light absorption layer 31 as a first semiconductor layer and a buffer layer 32 as a second semiconductor layer. The light absorption layer 31 and the buffer layer 32 are laminated.
光吸収層３１は、下部電極層２の＋Ｚ側の主面（一主面とも言う）の上に配されており、第１の導電型を有する半導体を含んでいる。ここでは、第１の導電型は、ｐ型である。光吸収層３１の厚さは、例えば、１μｍ以上で且つ３μｍ以下程度であれば良い。光吸収層３１がカルコパイライト系（ＣＩＳ系とも言う）の化合物半導体であるＩ−III−VI族化合物半導体の層であれば、光吸収層３１の厚さが薄くても変換効率が高められ得る。これにより、光吸収層３１が少ない材料で安価に生成され得る。本実施形態では、光吸収層３１が、ｐ型の導電型を有するＩ−III−VI族化合物半導体の層である。 The light absorption layer 31 is disposed on the main surface (also referred to as one main surface) on the + Z side of the lower electrode layer 2 and includes a semiconductor having the first conductivity type. Here, the first conductivity type is p-type. The thickness of the light absorption layer 31 may be about 1 μm or more and about 3 μm or less, for example. If the light absorption layer 31 is a layer of a I-III-VI group compound semiconductor that is a chalcopyrite (also referred to as CIS) compound semiconductor, the conversion efficiency can be improved even if the light absorption layer 31 is thin. . Thereby, the light absorption layer 31 can be produced inexpensively with a small amount of material. In this embodiment, the light absorption layer 31 is a layer of an I-III-VI group compound semiconductor having p-type conductivity.
I−III−VI族化合物半導体とは、Ｉ−III−VI族化合物を主に含む半導体である。なお、Ｉ−III−VI族化合物を主に含む半導体とは、半導体がＩ−III−VI族化合物を７０ｍｏｌ％以上含むことを言う。以下の記載においても、「主に含む」は「７０ｍｏｌ％以上含む」ことを意味する。Ｉ−III−VI族化合物とは、Ｉ−Ｂ族元素（１１族元素とも言う）とIII−Ｂ族元素（１３族元素とも言う）とVI−Ｂ族元素（１６族元素とも言う）とを主に含む化合物である。Ｉ−III−VI族化合物としては、例えば、ＣｕＩｎＳｅ2（ＣＩＳとも言う）、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ2（ＣＩＧＳとも言う）、Ｃｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）2（ＣＩＧＳＳとも言う）等が採用され得る。なお、Ｃｕ（Ｉｎ，Ｇａ）Ｓｅ2は、ＣｕとＩｎとＧａとＳｅとを主に含む化合物である。また、Ｃｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）2は、ＣｕとＩｎとＧａとＳｅとＳとを主に含む化合物である。また、光吸収層３１は、薄膜のＣｕ（Ｉｎ，Ｇａ）（Ｓｅ，Ｓ）2層が表面層として配されているＣｕ（Ｉｎ，Ｇａ）Ｓｅ2等といった多元化合物半導体の薄膜であっても良い。The I-III-VI group compound semiconductor is a semiconductor mainly containing an I-III-VI group compound. Note that the semiconductor mainly containing the I-III-VI group compound means that the semiconductor contains 70 mol% or more of the I-III-VI group compound. Also in the following description, “mainly included” means “70 mol% or more included”. An I-III-VI group compound 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). Mainly included compounds. Examples of the I-III-VI group compound include CuInSe 2 (also referred to as CIS), Cu (In, Ga) Se 2 (also referred to as CIGS), and Cu (In, Ga) (Se, S) 2 (also referred to as CIGSS). ) Etc. may be employed. Note that Cu (In, Ga) Se 2 is a compound mainly containing Cu, In, Ga, and Se. Cu (In, Ga) (Se, S) 2 is a compound mainly containing Cu, In, Ga, Se, and S. Further, the light absorption layer 31 may be a thin film of a multi-component compound semiconductor such as Cu (In, Ga) Se 2 or the like in which a thin Cu (In, Ga) (Se, S) 2 layer is arranged as a surface layer. good.
また、第１半導体層としての光吸収層３１のうちのバッファ層３２側（図中の＋Ｚ側）の主面（一主面とも言う）には、複数の線状の窪み部３１ＨＷ（図３等参照）が延在している。そして、各窪み部３１ＨＷの内壁は、光吸収層３１の表面部によって形成されている。 In addition, a plurality of linear depressions 31HW (FIG. 3) are formed on the main surface (also referred to as one main surface) on the buffer layer 32 side (+ Z side in the drawing) of the light absorption layer 31 as the first semiconductor layer. Etc.) are extended. And the inner wall of each hollow part 31HW is formed of the surface part of the light absorption layer 31. As shown in FIG.
図３および図４は、光吸収層３１の一主面に線状の窪み部３１ＨＷが延在している具体例を示すＳＥＭ写真である。図５は、窪み部３１ＨＷの長手方向に垂直な面における該窪み部３１ＨＷおよびその周辺の構成の断面を例示する模式図である。 3 and 4 are SEM photographs showing a specific example in which a linear depression 31HW extends on one main surface of the light absorption layer 31. FIG. FIG. 5 is a schematic view illustrating a cross-section of the configuration of the recess 31HW and its periphery on a plane perpendicular to the longitudinal direction of the recess 31HW.
窪み部３１ＨＷは、光吸収層３１の一主面において、平坦な面（基準面）３１ＳＦを基準として窪んだ部分である。基準面３１ＳＦは、若干の粗さを有する略平坦な面であっても良い。窪み部３１ＨＷは、例えば、長手方向に垂直な断面が半円状の内部空間を有する。つまり、窪み部３１ＨＷの底部の形状が下部電極層２側に凸の円弧状の形状を有している。また、窪み部３１ＨＷの深さは、例えば、１μｍ以上で且つ５μｍ以下であれば良く、窪み部３１ＨＷの幅は、例えば、２μｍ以上で且つ１０μｍ以下であれば良い。また、窪み部３１ＨＷが一主面上で長手方向に延在している距離は、例えば、１００μｍ以上で且つ数１００μｍ以下であれば良い。 The recessed portion 31HW is a portion that is recessed with respect to a flat surface (reference surface) 31SF on one main surface of the light absorption layer 31. The reference surface 31SF may be a substantially flat surface having a slight roughness. The hollow portion 31HW has, for example, an internal space whose cross section perpendicular to the longitudinal direction is semicircular. That is, the shape of the bottom of the hollow portion 31HW has a circular arc shape that is convex toward the lower electrode layer 2 side. Further, the depth of the recess 31HW may be, for example, 1 μm or more and 5 μm or less, and the width of the recess 31HW may be, for example, 2 μm or more and 10 μm or less. Moreover, the distance which the hollow part 31HW is extended in the longitudinal direction on one main surface should just be 100 micrometers or more and several hundred micrometers or less, for example.
なお、ここで言う窪み部３１ＨＷの深さは、基準面３１ＳＦの位置を基準として−Ｚ方向に窪み部３１ＨＷが窪んでいる、基準面３１ＳＦから窪み部３１ＨＷの底までの距離を意味する。換言すれば、窪み部３１ＨＷの深さは、基準面３１ＳＦに垂直な方向（法線方向とも言い、ここでは−Ｚ方向）に窪み部３１ＨＷが窪んでいる、基準面３１ＳＦからの窪み部３１ＨＷの窪みの大きさを表わす距離（窪み距離とも言う）を意味する。基準面３１ＳＦの位置としては、窪み部３１ＨＷの周囲の所定範囲における基準面３１ＳＦのＺ座標の平均値等が採用され得る。所定範囲は、例えば窪み部３１ＨＷを中心とする１００μｍ四方の領域であれば良い。また、ここで言う窪み部３１ＨＷの幅は、窪み部３１ＨＷにおけるバッファ層３２側の開口のうち窪み部３１ＨＷの長手方向に垂直な方向の開口の大きさを表わす距離を意味する。 In addition, the depth of the hollow part 31HW here means the distance from the reference surface 31SF to the bottom of the hollow part 31HW where the hollow part 31HW is depressed in the −Z direction with reference to the position of the reference surface 31SF. In other words, the depth of the recess 31HW is such that the recess 31HW is recessed in a direction perpendicular to the reference surface 31SF (also referred to as a normal direction, in this case, the -Z direction). This means a distance (also referred to as a depression distance) representing the size of the depression. As the position of the reference surface 31SF, an average value of the Z coordinates of the reference surface 31SF in a predetermined range around the depression 31HW can be adopted. The predetermined range may be, for example, a 100 μm square area centered on the depression 31HW. The width of the depression 31HW referred to here means a distance representing the size of the opening in the direction perpendicular to the longitudinal direction of the depression 31HW among the openings on the buffer layer 32 side in the depression 31HW.
上記線状の窪み部３１ＨＷの延在により、例えば、光吸収層３１に対してバッファ層３２側から押圧力が付与される場合には、開口が狭まったり拡がったりする窪み部３１ＨＷの変形によって、光吸収層３１に付与される応力が緩和される。その結果、光吸収層３１におけるクラックの発生が低減される。また、図３で示されるように、光吸収層３１の一主面において複数の線状の窪み部３１ＨＷが相互に異なる方向に延在していれば、光吸収層３１に付与される種々の方向の応力が緩和され易い。 By the extension of the linear depression 31HW, for example, when a pressing force is applied to the light absorption layer 31 from the buffer layer 32 side, the deformation of the depression 31HW in which the opening narrows or expands, The stress applied to the light absorption layer 31 is relaxed. As a result, generation of cracks in the light absorption layer 31 is reduced. In addition, as shown in FIG. 3, if a plurality of linear depressions 31 </ b> HW extend in different directions on one main surface of the light absorption layer 31, various types of light applied to the light absorption layer 31 are provided. Directional stress is easily relaxed.
なお、光吸収層３１は、いわゆる塗布法または印刷法と称されるプロセスによって形成され得る。塗布法では、まず、光吸収層３１の主な構成元素が溶解されている状態および微粒子の状態でそれぞれ含有されている溶液（微粒子含有溶液とも言う）が下部電極層２の上に塗布された後に、乾燥処理が施されることで、半乾き状態の皮膜が形成される。そして、該皮膜に対する熱処理が行われる。 The light absorbing layer 31 can be formed by a process called a so-called coating method or printing method. In the coating method, first, a solution containing the main constituent elements of the light absorption layer 31 in a dissolved state and a state of fine particles (also referred to as a fine particle-containing solution) was applied on the lower electrode layer 2. Later, a semi-dry film is formed by performing a drying process. And the heat processing with respect to this membrane | film | coat is performed.
ここで、微粒子含有溶液としては、Ｉ−Ｂ族元素とIII−Ｂ族元素とVI−Ｂ族元素とが溶解した溶液（原料溶液とも言う）に、Ｉ−Ｂ族元素とIII−Ｂ族元素とVI−Ｂ族元素とを含むＩ−III−VI族化合物半導体の微粒子が分散している溶液が採用される。 Here, as the fine particle-containing solution, a IB group element and a III-B group element are dissolved in a solution (also referred to as a raw material solution) in which the IB group element, the III-B group element, and the VI-B group element are dissolved. And a solution in which fine particles of a group I-III-VI compound semiconductor containing a group VI-B element are dispersed is employed.
また、熱処理では、例えば、毎分２０℃以上昇温される比較的速い昇温速度で５６０℃以上まで皮膜が加熱され、所定の温度域（例えば５６０℃以上で且つ６００℃以下）に所定時間（例えば約１時間）保持された後、自然対流による冷却（自然冷却）が行われる。 In the heat treatment, for example, the film is heated to 560 ° C. or higher at a relatively high temperature rising rate of 20 ° C. or more per minute, and a predetermined time in a predetermined temperature range (for example, 560 ° C. or higher and 600 ° C. or lower). After being held (for example, about 1 hour), cooling by natural convection (natural cooling) is performed.
図６から図８は、熱処理によって線状の窪み部３１ＨＷが形成される際における皮膜の状態の変化を模式的に示す図である。熱処理によって線状の窪み部３１ＨＷが形成される工程には主に次の３つの段階(ｉ)〜(iii)が存在する。 6 to 8 are diagrams schematically showing changes in the state of the film when the linear depression 31HW is formed by heat treatment. There are mainly the following three stages (i) to (iii) in the process of forming the linear depression 31HW by the heat treatment.
(ｉ)熱処理の直前では、図６で示されるように、原料溶液３１ＬＱに多数のＩ−III−VI族化合物半導体の微粒子３１ＰＡが分散している皮膜が形成された状態となっている。 (i) Immediately before the heat treatment, as shown in FIG. 6, a film is formed in which a large number of fine particles 31PA of the I-III-VI group compound semiconductor are dispersed in the raw material solution 31LQ.
(ii)次に、皮膜が、毎分２０℃以上昇温される比較的速い昇温速度で５６０℃以上まで加熱される。これにより、Ｉ−III−VI族化合物半導体の多数の微粒子３１ＰＡが核となって、微粒子３１ＰＡの凝集と結晶の発生と結晶の成長とが急速に生じる。このとき、図７で示されるように、ある程度の粒径まで成長した多数の結晶３１ＳＣが生じるとともに、多数の微粒子の凝集等に起因する収縮力によって多数の結晶３１ＳＣの間に線状のクラック３１ＣＬが生じる。その結果、皮膜は、多数の結晶３１ＳＣの間に発生した線状のクラック３１ＣＬ内に原料溶液３１ＬＱが残存している状態となる。 (ii) Next, the film is heated to 560 ° C. or higher at a relatively high rate of temperature increase of 20 ° C. or more per minute. Thereby, the numerous fine particles 31PA of the I-III-VI group compound semiconductor serve as nuclei, and the aggregation of fine particles 31PA, the generation of crystals, and the growth of crystals occur rapidly. At this time, as shown in FIG. 7, a large number of crystals 31SC grown to a certain particle size are generated, and linear cracks 31CL are formed between the large number of crystals 31SC due to contraction force caused by aggregation of a large number of fine particles. Occurs. As a result, the film is in a state where the raw material solution 31LQ remains in the linear cracks 31CL generated between the numerous crystals 31SC.
(iii)その次に、皮膜が、所定の温度域（例えば５６０℃以上で且つ６００℃以下）に所定時間（例えば約１時間）保持されると、クラック３１ＣＬ内等に存在していた原料溶液３１ＬＱの有機成分が徐々に蒸散する。そして、Ｉ−III−VI族化合物半導体の結晶の析出および成長が生じ、図８で示されるように、Ｉ−III−VI族化合物半導体の比較的大きな結晶（大結晶とも言う）３１ＬＣが生じる。このとき、クラック３１ＣＬ内の原料溶液３１ＬＱが、クラック３１ＣＬの領域よりも相対的に体積が小さな大結晶３１ＬＣに変化することで、光吸収層３１の一主面に線状の窪み部３１ＨＷが形成される。なお、所定の温度域が６００℃以下であれば、基板１および下部電極層２から光吸収層３１が剥離し難くなる。 (iii) Next, when the film is held in a predetermined temperature range (for example, 560 ° C. or higher and 600 ° C. or lower) for a predetermined time (for example, about 1 hour), the raw material solution that existed in the crack 31CL or the like 31LQ of organic components gradually evaporate. Then, precipitation and growth of a crystal of the I-III-VI group compound semiconductor occurs, and as shown in FIG. 8, a relatively large crystal (also referred to as a large crystal) 31LC of the I-III-VI group compound semiconductor is generated. At this time, the raw material solution 31LQ in the crack 31CL changes to the large crystal 31LC having a relatively smaller volume than the region of the crack 31CL, so that a linear depression 31HW is formed on one main surface of the light absorption layer 31. Is done. If the predetermined temperature range is 600 ° C. or lower, the light absorption layer 31 is difficult to peel from the substrate 1 and the lower electrode layer 2.
このようにして形成された光吸収層３１では、線状の窪み部３１ＨＷの直下の部分におけるＩ−III−VI族化合物半導体の結晶粒径の平均値（第１平均粒径とも言う）は、残余の部分における結晶粒径の平均値（第２平均粒径とも言う）よりも大きい。ここで、光吸収層３１における線状の窪み部３１ＨＷの直下の部分は、線状の窪み部３１ＨＷの位置を基準として一主面に垂直な方向（法線方向とも言い、具体的には−Ｚ方向）に位置する部分である。 In the light absorption layer 31 thus formed, the average value (also referred to as the first average particle size) of the crystal grain size of the I-III-VI group compound semiconductor in the portion immediately below the linear depression 31HW is: It is larger than the average value of crystal grain size (also referred to as second average grain size) in the remaining part. Here, the portion immediately below the linear depression 31HW in the light absorption layer 31 is a direction perpendicular to one principal surface with respect to the position of the linear depression 31HW (also referred to as a normal direction, specifically − (Z direction).
具体的には、図８で示されるように、大結晶３１ＬＣの第１平均粒径が、結晶３１ＳＣの第２平均粒径よりも大きい。そして、光吸収層３１のうちの線状の窪み部３１ＨＷの直下の部分に大結晶３１ＬＣが配されており、窪み部３１ＨＷの内壁における凹凸は小さい。このため、光吸収層３１のうちの線状の窪み部３１ＨＷが存在する部分と、バッファ層３２との密着性が良好である。これにより、窪み部３１ＨＷによる応力の緩和時に、窪み部３１ＨＷが変形しても、バッファ層３２が光吸収層３１から剥離し難い。 Specifically, as shown in FIG. 8, the first average particle size of the large crystal 31LC is larger than the second average particle size of the crystal 31SC. And the large crystal 31LC is distribute | arranged to the part directly under the linear hollow part 31HW of the light absorption layer 31, and the unevenness | corrugation in the inner wall of the hollow part 31HW is small. For this reason, the adhesiveness of the buffer layer 32 with the part in which the linear hollow part 31HW exists in the light absorption layer 31 is favorable. Thereby, even when the dent 31HW is deformed when the stress due to the dent 31HW is relieved, the buffer layer 32 is hardly peeled off from the light absorption layer 31.
バッファ層３２は、光吸収層３１の一主面の上に配されている半導体層である。この半導体層は、光吸収層３１の導電型とは異なる導電型を有している。ここでは、異なる導電型は、ｎ型である。また、バッファ層３２と光吸収層３１とが、ヘテロ接合領域を形成している。光電変換セル１０では、光吸収層３１とバッファ層３２とが積層された光電変換層３において光電変換が生じる。なお、導電型が異なる半導体とは、伝導担体（キャリア）が異なる半導体のことである。また、光吸収層３１の導電型がｐ型であれば、バッファ層３２の導電型はｎ型でなく、ｉ型であっても良い。さらに、光吸収層３１の導電型がｎ型またはｉ型であれば、バッファ層３２の導電型はｐ型であっても良い。 The buffer layer 32 is a semiconductor layer disposed on one main surface of the light absorption layer 31. This semiconductor layer has a conductivity type different from that of the light absorption layer 31. Here, the different conductivity types are n-type. Further, the buffer layer 32 and the light absorption layer 31 form a heterojunction region. In the photoelectric conversion cell 10, photoelectric conversion occurs in the photoelectric conversion layer 3 in which the light absorption layer 31 and the buffer layer 32 are stacked. Note that semiconductors having different conductivity types are semiconductors having different conductive carriers. Further, if the conductivity type of the light absorption layer 31 is p-type, the conductivity type of the buffer layer 32 may be i-type instead of n-type. Furthermore, if the conductivity type of the light absorption layer 31 is n-type or i-type, the conductivity type of the buffer layer 32 may be p-type.
バッファ層３２は、化合物半導体を主に含む。バッファ層３２に含まれる化合物半導体としては、例えば、ＣｄＳ、Ｉｎ2Ｓ3、ＺｎＳ、ＺｎＯ、Ｉｎ2Ｓｅ3、Ｉｎ（ＯＨ，Ｓ）、（Ｚｎ，Ｉｎ）（Ｓｅ，ＯＨ）、および（Ｚｎ，Ｍｇ）Ｏ等が採用され得る。そして、バッファ層３２の抵抗率が１Ω・ｃｍ以上であれば、リーク電流が低減される。なお、バッファ層３２は、例えば、ケミカルバスデポジション（ＣＢＤ）法等で形成され得る。The buffer layer 32 mainly includes a compound semiconductor. Examples of the compound semiconductor included in the buffer layer 32 include CdS, In 2 S 3 , ZnS, ZnO, In 2 Se 3 , In (OH, S), (Zn, In) (Se, OH), and (Zn). , Mg) O or the like can be employed. If the resistivity of the buffer layer 32 is 1 Ω · cm or more, the leakage current is reduced. The buffer layer 32 can be formed by, for example, a chemical bath deposition (CBD) method.
また、バッファ層３２の厚さ方向は、光吸収層３１の一主面に垂直な方向と略一致する。バッファ層３２の厚さは、例えば、１０ｎｍ以上で且つ２００ｎｍ以下であれば良い。バッファ層３２の厚さが１００ｎｍ以上で且つ２００ｎｍ以下であれば、高温高湿の条件下における変換効率の低下が顕著に低減され得る。 The thickness direction of the buffer layer 32 substantially coincides with the direction perpendicular to one main surface of the light absorption layer 31. The thickness of the buffer layer 32 may be, for example, 10 nm or more and 200 nm or less. When the thickness of the buffer layer 32 is not less than 100 nm and not more than 200 nm, a decrease in conversion efficiency under high temperature and high humidity conditions can be remarkably reduced.
この場合、光吸収層３１における線状の窪み部３１ＨＷの窪み距離（第１距離とも言う）は、バッファ層３２が光吸収層３１の一主面（具体的には基準面３１ＳＦ）の法線方向（図中Ｚ方向）に設けられている距離（バッファ層３２の厚さに相当し、第２距離とも言う）よりも長い。別の観点から言えば、同一の長さを示す単位（例えばｎｍ）で比較した場合に、光吸収層３１の基準面３１ＳＦの位置を基準とした窪み部３１ＨＷの−Ｚ方向における深さを示す数値は、バッファ層３２のＺ方向における厚さを示す数値よりも大きい。このように、線状の窪み部３１ＨＷがある程度深ければ、線状の窪み部３１ＨＷの変形による応力緩和の効果が明確に得られる。 In this case, the depression distance (also referred to as the first distance) of the linear depression 31HW in the light absorption layer 31 is a normal line of the buffer layer 32 to one main surface (specifically, the reference surface 31SF) of the light absorption layer 31. It is longer than the distance (corresponding to the thickness of the buffer layer 32, also referred to as the second distance) provided in the direction (Z direction in the figure). From another viewpoint, the depth in the −Z direction of the recess 31HW with respect to the position of the reference surface 31SF of the light absorption layer 31 when compared in units (for example, nm) indicating the same length is shown. The numerical value is larger than the numerical value indicating the thickness of the buffer layer 32 in the Z direction. Thus, if the linear depression 31HW is deep to some extent, the effect of stress relaxation due to the deformation of the linear depression 31HW can be clearly obtained.
上部電極層４は、バッファ層３２の＋Ｚ側の主面（一主面とも言う）の上に配されている。この上部電極層４は、例えば、ｎ型の導電型を有する透明の導電膜（透明電極層とも言う）である。そして、上部電極層４は、光電変換層３において生じた電荷を取り出す電極（取出電極とも言う）である。また、上部電極層４に主に含まれる材料は、バッファ層３２よりも低い抵抗率を有する。上部電極層４には、いわゆる窓層と呼ばれるものが含まれても良いし、窓層と透明の導電膜とが含まれていても良い。 The upper electrode layer 4 is disposed on the main surface (also referred to as one main surface) on the + Z side of the buffer layer 32. The upper electrode layer 4 is, for example, a transparent conductive film (also referred to as a transparent electrode layer) having an n-type conductivity type. The upper electrode layer 4 is an electrode that extracts charges generated in the photoelectric conversion layer 3 (also referred to as an extraction electrode). The material mainly contained in the upper electrode layer 4 has a lower resistivity than the buffer layer 32. The upper electrode layer 4 may include what is called a window layer, or may include a window layer and a transparent conductive film.
上部電極層４は、禁制帯幅が広く且つ透明で低抵抗の材料を主に含んでいる。このような材料としては、例えば、ＺｎＯ、Ｉｎ2Ｏ3、およびＳｎＯ2等の金属酸化物半導体等が採用され得る。これらの金属酸化物半導体には、Ａｌ、Ｂ、Ｇａ、ＩｎおよびＦ等のうちの何れかの元素が含まれてもよい。このような元素が含まれた金属酸化物半導体の具体例としては、例えば、ＡＺＯ（Aluminum Zinc Oxide）、ＧＺＯ（Gallium Zinc Oxide）、ＩＺＯ（Indium Zinc Oxide）、ＩＴＯ（Indium Tin Oxide）、ＦＴＯ（fluorine tin oxide）等がある。The upper electrode layer 4 mainly includes a transparent and low resistance material having a wide forbidden band width. As such a material, for example, a metal oxide semiconductor such as ZnO, In 2 O 3 , and SnO 2 can be adopted. These metal oxide semiconductors may contain any element of Al, B, Ga, In, F, and the like. Specific examples of the metal oxide semiconductor containing such an element include, for example, AZO (Aluminum Zinc Oxide), GZO (Gallium Zinc Oxide), IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), FTO ( fluorine tin oxide).
上部電極層４は、スパッタリング法、蒸着法、または化学的気相成長（ＣＶＤ）法等によって形成され得る。上部電極層４の厚さは、０．０５μｍ以上で且つ３μｍ以下であれば良い。ここで、上部電極層４が、例えば、１Ω・ｃｍ未満の抵抗率と、５０Ω／□以下のシート抵抗とを有していれば、上部電極層４を介して光電変換層３から電荷が良好に取り出され得る。 The upper electrode layer 4 can be formed by sputtering, vapor deposition, chemical vapor deposition (CVD), or the like. The thickness of the upper electrode layer 4 may be 0.05 μm or more and 3 μm or less. Here, if the upper electrode layer 4 has, for example, a resistivity of less than 1 Ω · cm and a sheet resistance of 50 Ω / □ or less, the electric charge is good from the photoelectric conversion layer 3 through the upper electrode layer 4. Can be taken out.
バッファ層３２および上部電極層４が、光吸収層３１が吸収し得る光の波長帯域に対して、光を透過させ易い性質（光透過性とも言う）を有していれば、光吸収層３１における光の吸収効率の低下が低減され得る。 If the buffer layer 32 and the upper electrode layer 4 have a property (also referred to as light transmittance) that allows light to easily pass through the wavelength band of light that can be absorbed by the light absorption layer 31, the light absorption layer 31. The decrease in the light absorption efficiency in can be reduced.
また、上部電極層４の厚さが０．０５μｍ以上で且つ０．５μｍ以下であれば、上部電極層４における光透過性が高められるとともに、光電変換によって生じた電流が良好に伝送され得る。さらに、上部電極層４の絶対屈折率とバッファ層３２の絶対屈折率とが略同一であれば、上部電極層４とバッファ層３２との界面で光が反射することで生じる入射光のロスが低減され得る。 Further, when the thickness of the upper electrode layer 4 is 0.05 μm or more and 0.5 μm or less, the light transmittance in the upper electrode layer 4 can be improved and the current generated by the photoelectric conversion can be transmitted well. Further, if the absolute refractive index of the upper electrode layer 4 and the absolute refractive index of the buffer layer 32 are substantially the same, the incident light loss caused by the reflection of light at the interface between the upper electrode layer 4 and the buffer layer 32 is reduced. Can be reduced.
グリッド電極５は、上部電極層４の＋Ｚ側の主面（一主面とも言う）の上に設けられている導電性を有する線状の電極部である。このグリッド電極５は、複数の集電部５ａと連結部５ｂとを備えている。複数の集電部５ａは、Ｙ軸方向に離間して設けられ、それぞれがＸ軸方向に延在する。連結部５ｂは、各集電部５ａが接続されており、Ｙ軸方向に延在する。グリッド電極５の材料としては、例えば、Ａｇ等の金属が採用され得る。また、グリッド電極５に含まれる金属は、例えば、Ｃｕ、Ａｌ、Ｎｉ等であっても良い。 The grid electrode 5 is a conductive linear electrode portion provided on the main surface (also referred to as one main surface) on the + Z side of the upper electrode layer 4. The grid electrode 5 includes a plurality of current collecting portions 5a and connecting portions 5b. The plurality of current collectors 5a are provided separately in the Y-axis direction, and each extend in the X-axis direction. Each of the current collectors 5a is connected to the connecting part 5b and extends in the Y-axis direction. As a material of the grid electrode 5, for example, a metal such as Ag can be adopted. Further, the metal contained in the grid electrode 5 may be, for example, Cu, Al, Ni or the like.
集電部５ａは、光電変換層３において発生した後に上部電極層４によって取り出された電荷を集電する。集電部５ａが配されていることで、上部電極層４の薄層化が可能となる。上部電極層４は、光吸収層３１の上方に配されているので、上部電極層４が出来るだけ薄く形成されれば、上部電極層４における光透過性が高められ得る。しかし、上部電極層４では、該上部電極層４の厚さが薄くなれば薄くなるほど抵抗が大きくなり、電荷の取り出し効率が低下する。そこで、集電部５ａが配されることで、電荷の取り出し効率が確保され、上部電極層４の薄層化による光透過性の向上が可能となる。 The current collector 5 a collects the electric charges generated by the upper electrode layer 4 after being generated in the photoelectric conversion layer 3. By providing the current collector 5a, the upper electrode layer 4 can be thinned. Since the upper electrode layer 4 is disposed above the light absorption layer 31, if the upper electrode layer 4 is formed as thin as possible, the light transmittance in the upper electrode layer 4 can be enhanced. However, in the upper electrode layer 4, as the thickness of the upper electrode layer 4 decreases, the resistance increases and the charge extraction efficiency decreases. Therefore, by arranging the current collector 5a, the charge extraction efficiency is ensured, and the light transmittance can be improved by making the upper electrode layer 4 thinner.
グリッド電極５および上部電極層４によって集電された電荷は、第２溝部Ｐ２に配されている接続部４５を通じて、隣の光電変換セル１０に伝達される。接続部４５は、上部電極層４の延在部分４ａと、その上に配されている連結部５ｂからの垂下部分５ｃとを有している。これにより、光電変換装置２１においては、隣り合う光電変換セル１０の一方の下部電極層２と、他方の上部電極層４およびグリッド電極５とが、第２溝部Ｐ２に設けられている接続導体としての接続部４５によって電気的に直列接続されている。 The electric charges collected by the grid electrode 5 and the upper electrode layer 4 are transmitted to the adjacent photoelectric conversion cell 10 through the connection part 45 arranged in the second groove part P2. The connecting portion 45 has an extending portion 4a of the upper electrode layer 4 and a hanging portion 5c from the connecting portion 5b disposed thereon. Thereby, in the photoelectric conversion apparatus 21, one lower electrode layer 2, the other upper electrode layer 4, and the grid electrode 5 of the adjacent photoelectric conversion cell 10 are connected conductors provided in the second groove portion P2. Are electrically connected in series by the connecting portion 45.
グリッド電極５の幅は、５０μｍ以上で且つ４００μｍ以下であれば、良好な導電性が確保されつつ、光吸収層３１への光の入射量を左右する受光面積の低下が低減され得る。 If the width of the grid electrode 5 is not less than 50 μm and not more than 400 μm, a decrease in the light receiving area that affects the amount of light incident on the light absorption layer 31 can be reduced while ensuring good conductivity.
なお、グリッド電極５のうちの少なくとも連結部５ｂの表面は、例えば、光吸収層３１が吸収する波長帯域の光を反射する材料によって形成され得る。この場合、光電変換装置２１がモジュール化された際に、連結部５ｂが反射した光を、このモジュール内で再び反射させて光吸収層３１に再度入射させることが可能となる。これにより、光吸収層３１への光の入射量が増大し、光電変換装置２１における変換効率が向上する。このような表面が形成されるためには、例えば、透光性を有する樹脂に光反射率が高いＡｇ等の金属粒子が添加されたペーストが、上部電極層４の一主面上に塗布され、その後の乾燥によって該ペーストが固化されることでグリッド電極５が形成されれば良い。また、例えば、Ａｌ等の光反射率の高い金属がグリッド電極５の表面に蒸着されても良い。 Note that at least the surface of the connecting portion 5b of the grid electrode 5 can be formed of, for example, a material that reflects light in a wavelength band that the light absorption layer 31 absorbs. In this case, when the photoelectric conversion device 21 is modularized, the light reflected by the connecting portion 5b can be reflected again in the module and incident again on the light absorption layer 31. Thereby, the amount of light incident on the light absorption layer 31 is increased, and the conversion efficiency in the photoelectric conversion device 21 is improved. In order to form such a surface, for example, a paste in which metal particles such as Ag having a high light reflectance are added to a light-transmitting resin is applied onto one main surface of the upper electrode layer 4. The grid electrode 5 may be formed by solidifying the paste by subsequent drying. Further, for example, a metal having high light reflectance such as Al may be deposited on the surface of the grid electrode 5.
＜(2)光電変換装置の製造方法＞
図９から図１４で示される各断面図は、図２で示された光電変換装置２１の断面に対応する部分の製造途中の様子を示す。<(2) Manufacturing method of photoelectric conversion device>
Each of the cross-sectional views shown in FIGS. 9 to 14 shows a state in the middle of manufacturing a portion corresponding to the cross section of the photoelectric conversion device 21 shown in FIG.
まず、図９で示されるように、洗浄された基板１の略全面に、スパッタリング法等が用いられて、Ｍｏ等を主に含む下部電極層２が形成される。そして、下部電極層２の上面のうちのＹ方向に沿った直線状の形成対象位置からその直下の基板１の上面にかけて、第１溝部Ｐ１が形成される。第１溝部Ｐ１は、例えば、ＹＡＧレーザー等によるレーザー光が走査されつつ形成対象位置に照射されることで形成され得る。図１０は、第１溝部Ｐ１が形成された後の状態を示す図である。 First, as shown in FIG. 9, a lower electrode layer 2 mainly containing Mo or the like is formed on the substantially entire surface of the cleaned substrate 1 by using a sputtering method or the like. Then, the first groove portion P1 is formed from the linear formation target position along the Y direction on the upper surface of the lower electrode layer 2 to the upper surface of the substrate 1 immediately below the formation position. The first groove portion P1 can be formed by, for example, irradiating the formation target position while scanning with laser light from a YAG laser or the like. FIG. 10 is a diagram illustrating a state after the first groove portion P1 is formed.
第１溝部Ｐ１が形成された後、下部電極層２の上に、光吸収層３１とバッファ層３２とが順に形成される。図１１は、光吸収層３１およびバッファ層３２が形成された後の状態を示す図である。 After the first groove portion P1 is formed, the light absorption layer 31 and the buffer layer 32 are sequentially formed on the lower electrode layer 2. FIG. 11 is a diagram illustrating a state after the light absorption layer 31 and the buffer layer 32 are formed.
光吸収層３１が形成される際には、まず、光吸収層３１を形成するための微粒子含有溶液が準備される。この微粒子含有溶液は、溶液に微粒子が分散されている。この溶液は、光吸収層３１を形成するための原料となる金属元素（原料金属元素とも言う）と、カルコゲン元素を含有する有機化合物（カルコゲン元素含有有機化合物とも言う）と、ルイス塩基性有機化合物とが溶媒に溶解したものである。また、微粒子は原料金属元素を含む。上記溶液および微粒子に含まれる原料金属元素は、Ｉ−III−VI族化合物半導体に含まれる金属元素であり、原料金属元素には、例えば、Ｉ−Ｂ族元素およびIII−Ｂ族元素が含まれる。溶液に含まれる原料金属元素と微粒子に含まれる原料金属元素とは同じであっても異なっていてもよい。溶液に含まれる原料金属元素と微粒子に含まれる原料金属元素とが同じであれば、Ｉ−III−VI族化合物半導体の形成が良好となる。 When the light absorption layer 31 is formed, first, a fine particle-containing solution for forming the light absorption layer 31 is prepared. In the fine particle-containing solution, fine particles are dispersed in the solution. This solution includes a metal element (also referred to as a raw metal element) that is a raw material for forming the light absorption layer 31, an organic compound containing a chalcogen element (also referred to as a chalcogen element-containing organic compound), and a Lewis basic organic compound. Are dissolved in a solvent. The fine particles contain a raw metal element. The source metal element contained in the solution and the fine particles is a metal element contained in the I-III-VI group compound semiconductor, and the source metal element includes, for example, an I-B group element and a III-B group element. . The source metal element contained in the solution and the source metal element contained in the fine particles may be the same or different. If the source metal element contained in the solution and the source metal element contained in the fine particles are the same, the formation of the I-III-VI group compound semiconductor will be good.
カルコゲン元素含有有機化合物とは、カルコゲン元素を主に含む有機化合物である。カルコゲン元素は、VI−Ｂ族元素のうちのＳ、Ｓｅ、Ｔｅである。ここで、カルコゲン元素としてＳｅが採用される場合、カルコゲン元素含有有機化合物としては、例えば、セレノール、セレニド、ジセレニド、セレノキシドおよびセレノン等が採用され得る。セレノール、セレニドまたはジセレニド等が採用されれば、金属と錯体を形成して金属溶液が良好に生成され得る。特に、フェニル基を有するものが採用されれば、良好な塗布の容易性（塗布性とも言う）が高められる。このようなフェニル基を有するものとしては、例えば、フェニルセレノール、フェニルセレナイド、ジフェニルジセレナイド等およびこれらの誘導体が採用され得る。 The chalcogen element-containing organic compound is an organic compound mainly containing a chalcogen element. The chalcogen elements are S, Se, and Te among VI-B group elements. Here, when Se is employed as the chalcogen element, examples of the chalcogen element-containing organic compound include selenol, selenide, diselenide, selenoxide, and selenone. If selenol, selenide, diselenide or the like is employed, a metal solution can be formed favorably by forming a complex with the metal. In particular, if a material having a phenyl group is employed, the ease of good coating (also referred to as coating property) is enhanced. As what has such a phenyl group, phenyl selenol, phenyl selenide, diphenyl diselenide, etc., and derivatives thereof may be employed, for example.
ルイス塩基性有機化合物とは、ルイス塩基となり得る官能基を有する有機化合物である。ルイス塩基となり得る官能基としては、非共有電子対を有するＶ−Ｂ族元素（１５族元素とも言う）を具備した官能基、および非共有電子対を有するVI−Ｂ族元素を具備した官能基等が採用され得る。これらの官能基の具体例としては、例えば、アミノ基（１〜３級アミンの何れでも良い）、カルボニル基、シアノ基等がある。ルイス塩基性有機化合物の具体例としては、ピリジン、アニリン、トリフェニルフォスフィン、２，４−ペンタンジオン、３−メチル−２，４−ペンタンジオン、トリエチルアミン、トリエタノ−ルアミン、アセトニトリル、ベンジル、ベンゾイン等およびこれらの誘導体がある。特に、ルイス塩基性有機化合物として含窒素有機化合物が採用されれば、原料金属元素の溶解性が高められる。さらに沸点が１００℃以上のルイス塩基性有機化合物が採用されれば、微粒子含有溶液の塗布性が高められる。 A Lewis basic organic compound is an organic compound having a functional group that can be a Lewis base. The functional group that can be a Lewis base includes a functional group having a VB group element having an unshared electron pair (also referred to as a Group 15 element), and a functional group having a VI-B group element having an unshared electron pair. Etc. may be employed. Specific examples of these functional groups include amino groups (any of primary to tertiary amines), carbonyl groups, cyano groups, and the like. Specific examples of Lewis basic organic compounds include pyridine, aniline, triphenylphosphine, 2,4-pentanedione, 3-methyl-2,4-pentanedione, triethylamine, triethanolamine, acetonitrile, benzyl, benzoin and the like. And derivatives thereof. In particular, if a nitrogen-containing organic compound is employed as the Lewis basic organic compound, the solubility of the starting metal element can be enhanced. Furthermore, if a Lewis basic organic compound having a boiling point of 100 ° C. or higher is employed, the coating property of the fine particle-containing solution is improved.
上記の微粒子含有溶液は、例えば、次の工程(Ａ)，(Ｂ)が順に行われることで、作製される。 The fine particle-containing solution is produced, for example, by sequentially performing the following steps (A) and (B).
(Ａ)単体の地金、合金または金属塩の何れかの状態の原料金属元素が、カルコゲン元素含有有機化合物とルイス塩基性有機化合物とが混合された溶媒（混合溶媒Ｓとも言う）に溶解されて原料溶液が調製される。原料金属元素が単体の地金または合金の状態で混合溶媒Ｓに溶解されれば、不純物の混入が低減される。原料溶液では、金属元素とカルコゲン元素含有有機化合物とルイス塩基性有機化合物とが錯体を成しているため、金属元素とカルコゲン元素とが接近した状態で安定に存在している。なお、混合溶媒Ｓの採用により、カルコゲン元素含有有機化合物のみ、またはルイス塩基性有機化合物のみで原料金属元素が溶解されて原料溶液が作製される場合よりも、高濃度（例えば１０質量％以上）の原料金属元素が含有されている原料溶液が生成され得る。また、混合溶媒Ｓにおけるカルコゲン元素含有有機化合物の含有量がルイス塩基性有機化合物に対して１ｍｏｌ％以上で且つ２５０ｍｏｌ％以下であれば、混合溶媒Ｓは、室温で液状となるため、取り扱い易い。 (A) A raw metal element in a state of a simple metal, alloy or metal salt is dissolved in a solvent (also referred to as a mixed solvent S) in which a chalcogen element-containing organic compound and a Lewis basic organic compound are mixed. A raw material solution is prepared. If the raw metal element is dissolved in the mixed solvent S in the state of a simple metal or alloy, the contamination of impurities is reduced. In the raw material solution, since the metal element, the chalcogen element-containing organic compound, and the Lewis basic organic compound form a complex, the metal element and the chalcogen element are stably present in a close state. In addition, by the use of the mixed solvent S, the concentration is higher (for example, 10% by mass or more) than when the raw material metal element is dissolved only with the chalcogen element-containing organic compound or the Lewis basic organic compound to prepare the raw material solution. A raw material solution containing the raw metal element can be produced. Further, when the content of the chalcogen element-containing organic compound in the mixed solvent S is 1 mol% or more and 250 mol% or less with respect to the Lewis basic organic compound, the mixed solvent S becomes liquid at room temperature and is easy to handle.
(Ｂ)原料溶液が加熱されることで、原料金属元素とカルコゲン元素との化合物が多数の微粒子として形成され、原料溶液中に多数の微粒子が分散している微粒子含有溶液が作製される。なお、微粒子が、光吸収層３１に含まれるＩ−III−VI族化合物半導体と同じ成分を有していれば、光吸収層３１への不純物の混入が低減されて光吸収層３１の純度が高められる。なお、原料溶液が加熱されることで多数の微粒子が析出され、この多数の微粒子が一旦抽出された後に、原料溶液に対して多数の微粒子が混合されることで原料溶液中に多数の微粒子が分散している微粒子含有溶液が作製されても良い。 (B) By heating the raw material solution, a compound containing a raw metal element and a chalcogen element is formed as a large number of fine particles, and a fine particle-containing solution in which a large number of fine particles are dispersed in the raw material solution is produced. In addition, if the fine particles have the same components as the I-III-VI group compound semiconductor contained in the light absorption layer 31, the contamination of the light absorption layer 31 is reduced and the purity of the light absorption layer 31 is increased. Enhanced. When the raw material solution is heated, a large number of fine particles are precipitated. After the large number of fine particles are once extracted, a large number of fine particles are mixed with the raw material solution, so that a large number of fine particles are contained in the raw material solution. A dispersed fine particle-containing solution may be prepared.
本実施形態では、原料金属元素として、Ｉ−Ｂ族元素のＣｕとIII−Ｂ族元素のＩｎおよびＧａとが採用され、カルコゲン元素含有有機化合物としてフェニルセレノールが採用され、ルイス塩基性有機化合物としてアニリンが採用されて、原料溶液が調製される。この場合、原料溶液が１５０℃以上で且つ２００℃以下の温度域で所定時間（例えば１分間以上で且つ６０分間以内）加熱されると、原料溶液中において５０ｎｍ以上で且つ３００ｎｍ以下の粒径を有し且つＣＩＧＳを含む多数の微粒子が形成される。これにより、多数の微粒子が分散している微粒子含有溶液が生成される。 In this embodiment, Cu of the IB group element and In and Ga of the III-B group element are employed as the raw metal element, phenyl selenol is employed as the chalcogen element-containing organic compound, and a Lewis basic organic compound An aniline is employed as a raw material solution. In this case, when the raw material solution is heated in a temperature range of 150 ° C. or higher and 200 ° C. or lower for a predetermined time (for example, 1 minute or longer and within 60 minutes), the particle size of 50 nm or more and 300 nm or less in the raw material solution A large number of microparticles are formed that contain and contain CIGS. Thereby, a fine particle-containing solution in which a large number of fine particles are dispersed is generated.
次に、微粒子含有溶液が下部電極層２の表面に塗布された後に、乾燥されることで前駆体としての皮膜（前駆体層とも言う）が形成され得る。その後、この前駆体層に対して熱処理が施されることで光吸収層３１が形成される。 Next, the fine particle-containing solution is applied to the surface of the lower electrode layer 2 and then dried to form a film as a precursor (also referred to as a precursor layer). Then, the light absorption layer 31 is formed by heat-processing with respect to this precursor layer.
ここで、微粒子含有溶液の塗布には、例えば、スピンコータ、スクリーン印刷、ディッピング、スプレーまたはダイコータ等が適用され得る。多数の微粒子の分散によって微粒子含有溶液の粘度は高いため、下部電極層２の表面に対する一度の微粒子含有溶液の塗布によって、比較的厚く且つ所望の厚さを有する前駆体層が容易に形成され得る。 Here, for example, a spin coater, screen printing, dipping, spraying, or a die coater can be applied to the application of the fine particle-containing solution. Since the viscosity of the fine particle-containing solution is high due to the dispersion of a large number of fine particles, a precursor layer having a relatively thick and desired thickness can be easily formed by applying the fine particle-containing solution once to the surface of the lower electrode layer 2. .
前駆体層を形成するための乾燥は、例えば、不活性ガス雰囲気または還元ガス雰囲気において行われれば良い。その乾燥温度は、例えば、５０℃以上で且つ３００℃以下であれば良い。前駆体層に対して熱処理が施される際の雰囲気は、例えば、窒素雰囲気、水素雰囲気および水素と窒素またはアルゴンとの混合気体の雰囲気のうちの何れかの雰囲気であれば良い。 The drying for forming the precursor layer may be performed, for example, in an inert gas atmosphere or a reducing gas atmosphere. The drying temperature should just be 50 degreeC or more and 300 degrees C or less, for example. The atmosphere in which the heat treatment is performed on the precursor layer may be any atmosphere of, for example, a nitrogen atmosphere, a hydrogen atmosphere, and a mixed gas atmosphere of hydrogen and nitrogen or argon.
熱処理では、毎分２０℃以上昇温される昇温速度で５６０℃以上まで加熱され、５６０℃以上で且つ６００℃以下の温度域で約１時間保持された後に、自然対流による冷却（自然冷却）が行われれば良い。このような熱処理によって、図６から図８で示された状態の変化を経て、一主面に線状の窪み部３１ＨＷが延在しており、厚さが１μｍ以上で且つ３μｍ以下の光吸収層３１が形成される。なお、この熱処理時には、多数の微粒子の存在と、微粒子間における原料溶液の存在とによって、微粒子を核とした結晶成長の促進と、光吸収層３１の緻密化とが図られ得る。また、熱処理の途中で発生したクラックが埋められて、線状の窪み部３１ＨＷが形成される。このため、欠陥の少ない光吸収層３１が形成され、光電変換装置２１における変換効率の上昇が図られ得る。 In the heat treatment, it is heated to 560 ° C. or more at a temperature rising rate of 20 ° C. or more per minute, and is kept in a temperature range of 560 ° C. or more and 600 ° C. or less for about 1 hour, and then cooled by natural convection (natural cooling ) Should be done. By such heat treatment, the linear depression 31HW extends on one main surface through the change of the state shown in FIGS. 6 to 8, and the light absorption is 1 μm or more and 3 μm or less. Layer 31 is formed. In this heat treatment, promotion of crystal growth using fine particles as nuclei and densification of the light absorption layer 31 can be achieved by the presence of a large number of fine particles and the presence of the raw material solution between the fine particles. Moreover, the crack which generate | occur | produced in the middle of heat processing is filled, and the linear hollow part 31HW is formed. For this reason, the light absorption layer 31 with few defects is formed, and the conversion efficiency in the photoelectric conversion device 21 can be increased.
ところで、微粒子含有溶液中の微粒子の平均粒径が１μｍ以下であれば、微粒子含有溶液における微粒子の分散性の向上と過度な凝集の低減とが図られ得る。また、この微粒子の平均粒径が５００ｎｍ以下であれば、光吸収層３１におけるボイドの発生が低減され得る。また、この微粒子の平均粒径が１０ｎｍ以上であれば、熱処理中に前駆体層において線状のクラックを生じさせた後に線状の窪み部３１ＨＷを発生させ得る。さらに、この微粒子の平均粒径が５０ｎｍ以上で且つ３００ｎｍ以下であれば、微粒子含有溶液の塗布性が向上し得る。 By the way, if the average particle diameter of the fine particles in the fine particle-containing solution is 1 μm or less, the dispersibility of the fine particles in the fine particle-containing solution can be improved and excessive aggregation can be reduced. Further, when the average particle diameter of the fine particles is 500 nm or less, generation of voids in the light absorption layer 31 can be reduced. Further, if the average particle size of the fine particles is 10 nm or more, the linear depression 31HW can be generated after generating a linear crack in the precursor layer during the heat treatment. Furthermore, when the average particle diameter of the fine particles is 50 nm or more and 300 nm or less, the coating property of the fine particle-containing solution can be improved.
バッファ層３２は、溶液成長法（ＣＢＤ法）によって形成され得る。例えば、酢酸カドミウムとチオ尿素とがアンモニア水に溶解させられることで作製された溶液に光吸収層３１まで形成された基板１が浸漬されることで、ＣｄＳを主に含むバッファ層３２が形成され得る。 The buffer layer 32 can be formed by a solution growth method (CBD method). For example, the buffer layer 32 mainly containing CdS is formed by immersing the substrate 1 formed up to the light absorption layer 31 in a solution prepared by dissolving cadmium acetate and thiourea in aqueous ammonia. obtain.
光吸収層３１およびバッファ層３２が形成された後、バッファ層３２の上面のうちのＹ方向に沿った直線状の形成対象位置からその直下の下部電極層２の上面にかけて、第２溝部Ｐ２が形成される。第２溝部Ｐ２は、例えば、４０μｍ以上で且つ５０μｍ以下程度のスクライブ幅のスクライブ針を用いたスクライビングが、位置をずらせながら連続して数回行われることで形成される。また、先端形状が第２溝部Ｐ２の幅に近い程度にまで広げられたスクライブ針でスクライブされることによって第２溝部Ｐ２が形成されても良い。あるいは、２本以上のスクライブ針が相互に当接または近接した状態で固定され、１回から数回のスクライブが行われることによって第２溝部Ｐ２が形成されても良い。図１２は、第２溝部Ｐ２が形成された後の状態を示す図である。第２溝部Ｐ２は、第１溝部Ｐ１よりも若干Ｘ方向（図中では＋Ｘ方向）にずれた位置に形成される。 After the light absorption layer 31 and the buffer layer 32 are formed, the second groove portion P2 extends from the linear formation target position along the Y direction on the upper surface of the buffer layer 32 to the upper surface of the lower electrode layer 2 immediately below the formation position. It is formed. The second groove portion P2 is formed, for example, by performing scribing using a scribe needle having a scribe width of about 40 μm or more and about 50 μm or less continuously several times while shifting the position. Further, the second groove portion P2 may be formed by scribing with a scribe needle whose tip shape is expanded to a degree close to the width of the second groove portion P2. Alternatively, the second groove portion P2 may be formed by fixing two or more scribe needles in a state where they are in contact with each other or in close proximity to each other and performing one to several scribes. FIG. 12 is a diagram illustrating a state after the second groove portion P2 is formed. The second groove portion P2 is formed at a position slightly shifted in the X direction (in the drawing, + X direction) from the first groove portion P1.
第２溝部Ｐ２が形成された後、バッファ層３２の上に、例えば、ＩＴＯ等を主成分とする透明の上部電極層４が形成される。上部電極層４は、スパッタリング法、蒸着法またはＣＶＤ法等で形成され得る。図１３は、上部電極層４が形成された後の状態を示す図である。 After the second groove portion P2 is formed, the transparent upper electrode layer 4 mainly composed of ITO or the like is formed on the buffer layer 32, for example. The upper electrode layer 4 can be formed by sputtering, vapor deposition, CVD, or the like. FIG. 13 is a view showing a state after the upper electrode layer 4 is formed.
上部電極層４が形成された後に、グリッド電極５が形成される。例えば、Ａｇ等の金属粉が樹脂バインダー等に分散している導電性を有するペースト（導電ペーストとも言う）が所望のパターンを描くように印刷され、これが乾燥によって固化されることで、グリッド電極５が形成される。なお、固化された状態は、導電ペーストに用いられるバインダーが熱可塑性樹脂である場合の熔融後の固化状態およびバインダーが熱硬化性樹脂または光硬化性樹脂等の硬化性樹脂である場合の硬化後の状態の双方を含む。図１４は、グリッド電極５が形成された後の状態を示す図である。 After the upper electrode layer 4 is formed, the grid electrode 5 is formed. For example, a conductive paste (also referred to as a conductive paste) in which a metal powder such as Ag is dispersed in a resin binder or the like is printed so as to draw a desired pattern, and this is solidified by drying, whereby the grid electrode 5 Is formed. The solidified state is the solidified state after melting when the binder used in the conductive paste is a thermoplastic resin, and after curing when the binder is a curable resin such as a thermosetting resin or a photocurable resin. Including both states. FIG. 14 is a diagram illustrating a state after the grid electrode 5 is formed.
グリッド電極５が形成された後、上部電極層４の上面のうちの直線状の形成対象位置からその直下の下部電極層２の上面にかけて、第３溝部Ｐ３が形成される。これにより、図１および図２で示された光電変換装置２１が得られる。第３溝部Ｐ３の幅は、例えば、４０μｍ以上で且つ１０００μｍ以下程度であれば良い。また、第３溝部Ｐ３は、第２溝部Ｐ２と同様に、メカニカルスクライビングによって形成され得る。 After the grid electrode 5 is formed, a third groove portion P3 is formed from the linear formation target position on the upper surface of the upper electrode layer 4 to the upper surface of the lower electrode layer 2 immediately below the formation position. Thereby, the photoelectric conversion device 21 shown in FIGS. 1 and 2 is obtained. The width of the third groove portion P3 may be, for example, about 40 μm or more and about 1000 μm or less. Moreover, the 3rd groove part P3 can be formed by mechanical scribing similarly to the 2nd groove part P2.
＜(3)具体例＞
次に、製造条件と線状の窪み部３１ＨＷの発生との関係、ならびに線状の窪み部３１ＨＷの発生による光電変換装置２１の変換効率の向上について、具体例を示して説明する。<(3) Specific example>
Next, the relationship between the manufacturing conditions and the generation of the linear depression 31HW and the improvement of the conversion efficiency of the photoelectric conversion device 21 due to the generation of the linear depression 31HW will be described with specific examples.
ここでは、Ｉ−Ｂ族元素、III−Ｂ族元素およびVI−Ｂ族元素の含有比率がそれぞれ等しい原料溶液と微粒子とが用いられた。そして、原料溶液と微粒子との混合比率が異なる微粒子含有溶液が用いられてＣＩＧＳを主に含む半導体層が形成されることで、光電変換装置２１と同様な構造を有する５つの光電変換装置（具体的には実施例１〜５）が作製された。また、微粒子が含まれていない原料溶液が用いられてＣＩＧＳを主に含む半導体層が形成されることで、光電変換装置２１と同様な構造を有する光電変換装置（具体的には比較例）が作製された。 Here, a raw material solution and fine particles having the same content ratios of the IB group element, the III-B group element, and the VI-B group element were used. Then, five photoelectric conversion devices (specifically) having the same structure as the photoelectric conversion device 21 are formed by using a fine particle-containing solution in which the mixing ratio of the raw material solution and the fine particles is different to form a semiconductor layer mainly containing CIGS. Specifically, Examples 1 to 5) were produced. Moreover, the photoelectric conversion apparatus (specifically comparative example) which has the same structure as the photoelectric conversion apparatus 21 is formed by using the raw material solution which does not contain fine particles, and forming the semiconductor layer which mainly contains CIGS. It was made.
詳細には、まず、ルイス塩基性有機化合物であるアニリンに対して、１００ｍｏｌ％のカルコゲン元素含有有機化合物であるフェニルセレノールが溶解されることで、混合溶媒Ｓが調製された。次に、地金のＣｕ、地金のＩｎ、地金のＧａおよび地金のＳｅが、上記混合溶媒Ｓに直接溶解させられて、第１の原料溶液が調製された。この第１の原料溶液では、Ｃｕの含有量が２．３質量％、Ｉｎの含有量が３．２質量％、Ｇａの含有量が１．３質量％およびＳｅの含有量が７．２質量％とされた。そして、この第１の原料溶液が攪拌されながら、１５５℃で２０時間加熱されることで、ＣＩＧＳの微粒子が分散している微粒子含有溶液が得られた。さらに、遠心分離器によって、微粒子含有溶液から多数の微粒子が得られた。この多数の微粒子の平均粒径は、走査型電子顕微鏡（ＳＥＭ）で得られる画像の解析によって測定され、約５０ｎｍであった。 Specifically, first, a mixed solvent S was prepared by dissolving 100 mol% of a phenyl selenol, which is a chalcogen element-containing organic compound, in aniline, which is a Lewis basic organic compound. Next, the ingot Cu, the indium In, the ingot Ga and the ingot Se were directly dissolved in the mixed solvent S to prepare a first raw material solution. In the first raw material solution, the Cu content is 2.3 mass%, the In content is 3.2 mass%, the Ga content is 1.3 mass%, and the Se content is 7.2 mass%. %. The first raw material solution was stirred and heated at 155 ° C. for 20 hours to obtain a fine particle-containing solution in which CIGS fine particles were dispersed. Furthermore, a large number of microparticles were obtained from the microparticle-containing solution by a centrifuge. The average particle diameter of the large number of fine particles was measured by analysis of an image obtained with a scanning electron microscope (SEM), and was about 50 nm.
次に、第１の原料溶液と同一の成分を有する第２の原料溶液が調製された。具体的には、まず、ルイス塩基性有機化合物であるアニリンに対して、１００ｍｏｌ％のカルコゲン元素含有有機化合物であるフェニルセレノールが溶解されることで、混合溶媒Ｓが調製された。次に、地金のＣｕ、地金のＩｎ、地金のＧａおよび地金のＳｅが、上記混合溶媒Ｓに直接溶解させられて、第２の原料溶液が調製された。この第２の原料溶液では、Ｃｕの含有量が２．３質量％、Ｉｎの含有量が３．２質量％、Ｇａの含有量が１．３質量％およびＳｅの含有量が７．２質量％とされた。 Next, a second raw material solution having the same components as the first raw material solution was prepared. Specifically, first, mixed solvent S was prepared by dissolving 100 mol% of phenylselenol, which is a chalcogen element-containing organic compound, in aniline, which is a Lewis basic organic compound. Next, the ingot Cu, the indium In, the ingot Ga and the ingot Se were directly dissolved in the mixed solvent S to prepare a second raw material solution. In this second raw material solution, the Cu content is 2.3 mass%, the In content is 3.2 mass%, the Ga content is 1.3 mass%, and the Se content is 7.2 mass%. %.
そして、遠心分離によって得られた多数の微粒子と第２の原料溶液とが混合されて、微粒子含有溶液が作製された。ここでは、実施例１〜５としての光電変換装置を形成するために、多数の微粒子に含まれるＣｕの物質量の合計と、第２の原料溶液に含まれるＣｕの物質量の合計との比（混合比とも言う）が、表１の関係を有する５種類の微粒子含有溶液が作製された。換言すれば、実施例１〜５に係る各微粒子含有溶液では、多数の微粒子に含まれているＣｕの物質量の合計値を、第２の原料溶液に含まれているＣｕの物質量の合計値で除した値（以下、微粒子含有倍率とも言う）が、表１の値を示す。具体的には、微粒子含有倍率が、実施例１に係る微粒子含有溶液では２０、実施例２に係る微粒子含有溶液では１０、実施例３に係る微粒子含有溶液では６、実施例４に係る微粒子含有溶液では４、実施例５に係る微粒子含有溶液では２とされた。また、比較例としての光電変換装置を形成するために、第２の原料溶液がそのまま採用された。そして、各実施例１〜５に係る第２の原料溶液と微粒子含有溶液との間におけるＩｎ、Ｇａ、Ｓｅの各含有量の関係は、Ｃｕの含有量の関係と略同一とされた。 And many fine particles obtained by centrifugation and the 2nd raw material solution were mixed, and the fine particle content solution was produced. Here, in order to form the photoelectric conversion devices as Examples 1 to 5, the ratio of the total amount of Cu contained in a large number of fine particles to the total amount of Cu contained in the second raw material solution Five types of fine particle-containing solutions having a relationship shown in Table 1 (also referred to as mixing ratio) were prepared. In other words, in each of the fine particle-containing solutions according to Examples 1 to 5, the total value of the amount of Cu contained in a large number of fine particles is set to the total amount of the substance of Cu contained in the second raw material solution. The value divided by the value (hereinafter also referred to as the fine particle content magnification) shows the values in Table 1. Specifically, the microparticle content ratio is 20 for the microparticle-containing solution according to Example 1, 10 for the microparticle-containing solution according to Example 2, 6 for the microparticle-containing solution according to Example 3, and microparticle-containing according to Example 4. It was 4 for the solution and 2 for the fine particle-containing solution according to Example 5. Further, the second raw material solution was employed as it was to form a photoelectric conversion device as a comparative example. And the relationship of each content of In, Ga, and Se between the second raw material solution and the fine particle-containing solution according to each of Examples 1 to 5 was made substantially the same as the relationship of the Cu content.
次に、ガラスを主に含む基板１の表面にＭｏ等を主に含む下部電極層２が形成されたものが用意された。そして、この下部電極層２の上に、微粒子含有溶液（比較例については第２の原料溶液）がブレード法によって塗布された後に乾燥されることで、前駆体層としての皮膜が形成された。ここでは、この前駆体層は、ブレード法による塗布とその後の乾燥とが行われる処理が順に２回実施されることで形成された。その後、水素ガスとセレン蒸気ガスとの混合気体の雰囲気下で熱処理が実施された。この熱処理では、室温付近から５６０℃まで５分間で昇温され、５６０℃で１時間保持された後に、自然冷却が行われることで、厚さが約２μｍのＣＩＧＳを主に含む半導体層が形成された。この半導体層が光吸収層に相当する。 Next, a substrate in which a lower electrode layer 2 mainly containing Mo or the like was formed on the surface of a substrate 1 mainly containing glass was prepared. Then, a fine particle-containing solution (second raw material solution in the comparative example) was applied on the lower electrode layer 2 by a blade method and then dried to form a film as a precursor layer. Here, this precursor layer was formed by carrying out the treatment in which application by the blade method and subsequent drying were performed twice in order. Thereafter, heat treatment was performed in an atmosphere of a mixed gas of hydrogen gas and selenium vapor gas. In this heat treatment, the temperature is raised from near room temperature to 560 ° C. over 5 minutes, and after holding at 560 ° C. for 1 hour, natural cooling is performed to form a semiconductor layer mainly containing CIGS having a thickness of about 2 μm. It was done. This semiconductor layer corresponds to a light absorption layer.
その次に、アンモニア水に酢酸亜鉛とチオ尿素が溶解させられた溶液に、ＣＩＧＳを主に含む半導体層までが形成された基板１が浸漬されることで、半導体層の上に厚さが約５０ｎｍのＺｎＳを主に含むバッファ層が形成された。さらに、このバッファ層の上に、スパッタリング法によってＡｌがドープされたＺｎＯを主に含む透明の導電膜が形成された。そして、最後に蒸着によってＡｌを含むグリッド電極が形成されて、実施例１〜５および比較例としての光電変換装置がそれぞれ作製された。 Next, the substrate 1 on which the semiconductor layer mainly containing CIGS is formed is immersed in a solution in which zinc acetate and thiourea are dissolved in aqueous ammonia, so that the thickness of the substrate 1 is approximately about the semiconductor layer. A buffer layer mainly containing 50 nm of ZnS was formed. Further, a transparent conductive film mainly containing ZnO doped with Al was formed on the buffer layer by sputtering. Finally, grid electrodes containing Al were formed by vapor deposition, and Examples 1 to 5 and a photoelectric conversion device as a comparative example were produced.
このようにして作製された実施例１〜５および比較例としての各光電変換装置が対象とされて、ＣＩＧＳを主に含む半導体層のうちのバッファ層側の一主面に、線状のクラックおよび線状の窪み部が存在しているか否かがそれぞれ調査された。この調査は、実施例１〜５および比較例としての各光電変換装置の作製過程においてＣＩＧＳを主に含む半導体層が形成された時点で、この半導体層の表面が走査型電子顕微鏡（ＳＥＭ）で観察されることによって行われた。また、実施例１〜５および比較例としての光電変換装置における変換効率は、いわゆる定常光ソーラシミュレーターが用いられて、光電変換装置の受光面に対する光の照射強度が１００ｍＷ／ｃｍ2であり且つＡＭ（エアマス）が１．５である条件下で測定された。In this way, each of the photoelectric conversion devices as Examples 1 to 5 and the comparative example is targeted, and a linear crack is formed on one main surface of the buffer layer side of the semiconductor layer mainly including CIGS. Whether or not a linear depression exists is investigated. In this investigation, when a semiconductor layer mainly containing CIGS was formed in the manufacturing process of each of the photoelectric conversion devices as Examples 1 to 5 and the comparative example, the surface of the semiconductor layer was scanned with a scanning electron microscope (SEM). Made by being observed. The conversion efficiencies in the photoelectric conversion devices of Examples 1 to 5 and the comparative example are such that a so-called stationary light solar simulator is used, the light irradiation intensity on the light receiving surface of the photoelectric conversion device is 100 mW / cm 2 , and AM It was measured under the condition that (air mass) is 1.5.
実施例１〜５および比較例としての光電変換装置が対象とされた、線状のクラックおよび線状の窪み部の有無についての調査結果、ならびに変換効率の測定結果は、表１にそれぞれ示されている。 Table 1 shows the results of the investigation on the presence or absence of linear cracks and linear depressions, and the measurement results of conversion efficiency, which were targeted for Examples 1 to 5 and the photoelectric conversion device as a comparative example. ing.
表１で示されるように、実施例１〜５については、線状の窪み部３１ＨＷの延在が確認された。そして、微粒子含有溶液において多数の微粒子が占める割合（例えば、微粒子含有倍率）が高くなれば高くなるほど、窪み部３１ＨＷの幅が広くなり、窪み部３１ＨＷの深さが深くなる傾向が認められた。また、実施例１〜４については、線状のクラックの発生が全く確認されなかった。実施例５については、線状のクラックが若干確認された。その一方で、比較例については、線状の窪み部３１ＨＷの延在が全く確認されず、線状のクラックの存在が確認された。また、実施例１〜５では、９．２％以上で且つ１２．８％以下（具体的には１０．２％、１２．５％、１２．８％、１１．９％、９．２％）の変換効率が得られた。これに対して、比較例では、６．８％の変換効率しか得られなかった。 As shown in Table 1, in Examples 1 to 5, the extension of the linear depression 31HW was confirmed. And the tendency that the width of the hollow part 31HW becomes wide and the depth of the hollow part 31HW becomes deep, so that the ratio (for example, fine particle content magnification) which many fine particles occupy in a fine particle containing solution becomes high. Moreover, about Examples 1-4, generation | occurrence | production of the linear crack was not confirmed at all. About Example 5, some linear cracks were confirmed. On the other hand, about the comparative example, extension of the linear hollow part 31HW was not confirmed at all, but existence of the linear crack was confirmed. Moreover, in Examples 1-5, it is 9.2% or more and 12.8% or less (specifically 10.2%, 12.5%, 12.8%, 11.9%, 9.2%). ) Conversion efficiency was obtained. On the other hand, in the comparative example, only a conversion efficiency of 6.8% was obtained.
以上の調査結果および測定結果から、微粒子含有溶液が採用されることで、ＣＩＧＳを主に含む半導体層では、一主面において線状の窪み部３１ＨＷの発生に伴って線状のクラックが減少し、変換効率が顕著に向上することが確認された。そして、線状の窪み部３１ＨＷが延在すれば、光電変換装置に対して外力が付与されても線状の窪み部３１ＨＷにおける応力の緩和によって光吸収層にクラックが生じ難く、変換効率が維持されるものと推定された。また、微粒子含有溶液における微粒子含有倍率が４以上で且つ１０以下であれば、光電変換装置の実用化レベルで要求される１１％以上の変換効率が得られることが分かった。そして、微粒子含有溶液における微粒子含有倍率が４以上で且つ１０以下であれば、線状の窪み部３１ＨＷが適度な幅および深さを有することが判った。そして、このような適度な幅および深さの線状の窪み部３１ＨＷの延在により、光電変換装置に対して外力が付与されても線状の窪み部３１ＨＷにおける応力の緩和によって光吸収層でさらにクラックが生じ難いものと推定された。 From the above investigation results and measurement results, by using the fine particle-containing solution, in the semiconductor layer mainly including CIGS, linear cracks are reduced along with the generation of the linear depression 31HW on one main surface. It was confirmed that the conversion efficiency was remarkably improved. And if linear hollow part 31HW is extended, even if an external force is provided with respect to a photoelectric conversion apparatus, a crack will not easily arise in a light absorption layer by relaxation of the stress in linear hollow part 31HW, and conversion efficiency is maintained. It was estimated that Further, it was found that if the fine particle content ratio in the fine particle-containing solution is 4 or more and 10 or less, the conversion efficiency of 11% or more required at the practical use level of the photoelectric conversion device can be obtained. And when the fine particle content ratio in the fine particle-containing solution is 4 or more and 10 or less, it was found that the linear depression 31HW has an appropriate width and depth. And by extension of the linear hollow part 31HW of such moderate width and depth, even if an external force is applied to the photoelectric conversion device, the light absorption layer is formed by relaxation of the stress in the linear hollow part 31HW. Further, it was presumed that cracks hardly occur.
＜(4)変形例＞
なお、本発明は上述の実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において種々の変更、改良等が可能である。<(4) Modification>
It should be noted that the present invention is not limited to the above-described embodiment, and various changes and improvements can be made without departing from the gist of the present invention.
例えば、上記一実施形態では、光吸収層３１が、Ｉ−Ｂ族元素とIII−Ｂ族元素とVI−Ｂ族元素とを含むＩ−III−VI族化合物半導体の層であったが、これに限られない。例えば、光吸収層３１が、II−Ｂ族元素とVI−Ｂ族元素とを主に含むII−VI族化合物半導体の層であっても良いし、２以上の元素を含むその他の化合物半導体の層であっても良い。なお、II−VI族化合物半導体は、II−Ｂ族元素（１２族元素とも言う）とVI−Ｂ族元素とを主に含む化合物半導体である。このII−VI族化合物半導体としては、例えば、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＣｄＳ，ＣｄＳｅおよびＣｄＴｅ等が採用され得る。光吸収層３１がII−VI族化合物半導体の層である場合には、微粒子含有溶液に含有される原料金属元素にII−Ｂ族元素が含まれる態様が考えられる。 For example, in the above-described embodiment, the light absorption layer 31 is a layer of an I-III-VI group compound semiconductor containing a group I-B element, a group III-B element, and a group VI-B element. Not limited to. For example, the light absorption layer 31 may be a layer of a II-VI group compound semiconductor mainly containing a II-B group element and a VI-B group element, or other compound semiconductors containing two or more elements. It may be a layer. Note that the II-VI group compound semiconductor is a compound semiconductor mainly including a group II-B element (also referred to as a group 12 element) and a group VI-B element. As this II-VI group compound semiconductor, for example, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe and the like can be adopted. In the case where the light absorption layer 31 is a II-VI group compound semiconductor layer, an embodiment in which a II-B group element is included in the raw metal element contained in the fine particle-containing solution is conceivable.
また、上記一実施形態では、複数の線状の窪み部３１ＨＷが、相互に異なる方向に延在していたが、これに限られない。例えば、少なくとも１本の線状の窪み部３１ＨＷが存在しているだけでも良く、複数の線状の窪み部３１ＨＷが、略同一の方向に延在していても良い。 Moreover, in the said one Embodiment, although the some linear hollow part 31HW extended in the mutually different direction, it is not restricted to this. For example, at least one linear depression 31HW may be present, and a plurality of linear depressions 31HW may extend in substantially the same direction.
複数の線状の窪み部３１ＨＷが略同一の方向に延在する態様は、例えば、次の工程によって実現され得る。まず、下部電極層２の上に微粒子含有溶液が１回塗布された後に、加熱処理が施されてＣＩＧＳの結晶を主に含む皮膜が形成される。次に、該皮膜が形成された基板１に対して曲げ応力が加えられることで該皮膜において略同一方向に延在する複数本のクラックが発生させられる。次に、複数本のクラックが延在している皮膜の上に原料溶液が塗布されて、熱処理が施される。これにより、複数の線状の窪み部３１ＨＷが略同一の方向に延在している光吸収層３１が形成され得る。但し、複数の線状の窪み部３１ＨＷが相互に異なる方向に延在していれば、光吸収層３１の種々の方向に付与される応力が緩和され易い。 A mode in which the plurality of linear depressions 31HW extend in substantially the same direction can be realized, for example, by the following process. First, after the fine particle-containing solution is applied once on the lower electrode layer 2, heat treatment is performed to form a film mainly containing CIGS crystals. Next, a bending stress is applied to the substrate 1 on which the coating is formed, whereby a plurality of cracks extending in substantially the same direction are generated in the coating. Next, a raw material solution is applied on the film in which a plurality of cracks extend, and heat treatment is performed. Thereby, the light absorption layer 31 in which the plurality of linear depressions 31HW extend in substantially the same direction can be formed. However, if the plurality of linear depressions 31 </ b> HW extend in different directions, stress applied in various directions of the light absorption layer 31 is easily relaxed.
また、上記一実施形態では、下部電極層２の上に微粒子含有溶液が塗布されることで、光吸収層３１が形成されたが、これに限られない。例えば、下部電極層２の上に微粒子含有溶液が塗布された後に乾燥されることで皮膜が形成され、その皮膜の上に原料溶液が塗布された後に熱処理が施されることで、一主面に少なくとも１本の線状の窪み部３１ＨＷが延在している光吸収層３１が形成されても良い。 Moreover, in the said one Embodiment, although the light absorption layer 31 was formed by apply | coating the microparticles | fine-particles containing solution on the lower electrode layer 2, it is not restricted to this. For example, a film is formed by applying a fine particle-containing solution on the lower electrode layer 2 and then drying, and a heat treatment is applied after a raw material solution is applied on the film. The light absorption layer 31 in which at least one linear hollow portion 31HW extends may be formed.
また、上記一実施形態では、カルコゲン元素としてＳｅが採用されたが、これに限られない。例えば、カルコゲン元素としてＳが採用される場合、カルコゲン元素含有有機化合物としては、例えば、チオール、スルフィド、ジスルフィド、チオフェン、スルホキシド、スルホン、チオケトン、スルホン酸、スルホン酸エステルおよびスルホン酸アミド等が採用され得る。そして、カルコゲン元素含有有機化合物が、チオール、スルフィドおよびジスルフィド等であれば、金属と錯体を形成するため、金属溶液が良好に生成され得る。特に、カルコゲン元素含有有機化合物として、フェニル基を有するものが採用されれば、微粒子含有溶液の塗布性が高められる。フェニル基を有するカルコゲン元素含有有機化合物としては、例えば、チオフェノール、ジフェニルスルフィド等およびこれらの誘導体が採用され得る。また、カルコゲン元素としてＴｅが採用される場合、カルコゲン元素含有有機化合物としては、例えば、テルロール、テルリドおよびジテルリド等が採用され得る。 Moreover, in the said one Embodiment, Se was employ | adopted as a chalcogen element, However, It is not restricted to this. For example, when S is employed as the chalcogen element, examples of the chalcogen element-containing organic compound include thiol, sulfide, disulfide, thiophene, sulfoxide, sulfone, thioketone, sulfonic acid, sulfonic acid ester, and sulfonic acid amide. obtain. If the chalcogen element-containing organic compound is thiol, sulfide, disulfide or the like, a metal solution can be formed satisfactorily because a complex is formed with the metal. In particular, if a chalcogen element-containing organic compound having a phenyl group is employed, the coating property of the fine particle-containing solution is improved. As the chalcogen element-containing organic compound having a phenyl group, for example, thiophenol, diphenyl sulfide and the like and derivatives thereof can be employed. When Te is employed as the chalcogen element, examples of the chalcogen element-containing organic compound include tellurol, telluride, and ditelluride.
なお、上記一実施形態および各種変形例をそれぞれ構成する全部または一部を、適宜、矛盾しない範囲で組み合わせ可能であることは、言うまでもない。 Needless to say, all or a part of each of the above-described embodiment and various modifications can be combined as appropriate within a consistent range.
１ 基板
２ 下部電極層
３ 光電変換層
４ 上部電極層
５ グリッド電極
１０ 光電変換セル
２１ 光電変換装置
３１ 光吸収層
３１ＣＬ クラック
３１ＨＷ 窪み部
３１ＬＣ 大結晶
３１ＬＱ 原料溶液
３１ＰＡ 微粒子
３１ＳＣ 結晶
３１ＳＦ 基準面
３２ バッファ層
４５ 接続部DESCRIPTION OF SYMBOLS 1 Substrate 2 Lower electrode layer 3 Photoelectric conversion layer 4 Upper electrode layer 5 Grid electrode 10 Photoelectric conversion cell 21 Photoelectric conversion device 31 Light absorption layer 31CL Crack 31HW hollow part 31LC Large crystal 31LQ Raw material solution 31PA Fine particle 31SC Crystal 31SF Reference plane 32 Buffer layer 45 connections
上記課題を解決するために、第１の態様に係る光電変換装置は、一主面において平坦な面の中に複数の線状の窪み部が相互に異なる方向に延在し且つ第１の導電型を有している第１半導体層と、前記一主面の上に配されている第２の導電型を有する第２半導体層と、を備える。 In order to solve the above problems, a photoelectric conversion device according to the first aspect, and the recessed portion of the plurality of linear in Oite flat surface on one main surface extends in different directions to each other first And a second semiconductor layer having a second conductivity type disposed on the one main surface.
また、第２の態様に係る光電変換装置の製造方法は、原料溶液および化合物半導体の微粒子を含有する微粒子含有溶液を準備する工程と、前記微粒子含有溶液を電極層の上に塗布して皮膜を形成する工程と、前記皮膜に対して熱処理を施すことで、前記化合物半導体を含むとともに一主面に線状の窪み部が延在している半導体層を形成する工程と、を備え、前記原料溶液に、ルイス塩基性有機化合物、カルコゲン元素を含有する有機化合物および金属元素をそれぞれ溶解した状態で含ませ、前記化合物半導体の微粒子に前記金属元素を含ませ、該化合物半導体の微粒子を前記原料溶液中に分散させる。 In addition, a method for manufacturing a photoelectric conversion device according to the second aspect includes a step of preparing a raw material solution and a fine particle-containing solution containing fine particles of a compound semiconductor, and applying the fine particle-containing solution onto an electrode layer to form a film. And a step of forming a semiconductor layer including the compound semiconductor and having a linear depression extending on one main surface by applying a heat treatment to the coating, and the raw material solution, Lewis base organic compound, an organic compound containing a chalcogen element and contained a metal element in a state of being dissolved, respectively, the compound moistened with pre Symbol metal element in the semiconductor fine particles, the raw material particles of the compound semiconductor Ru is dispersed in the solution.
上記課題を解決するために、第１の態様に係る光電変換装置は、一主面において平坦な面の中に複数の線状の窪み部が相互に異なる方向に延在し且つ第１の導電型を有している第１半導体層と、前記一主面の上に配されている第２の導電型を有する第２半導体層と、を備える。この光電変換装置では、前記第２半導体層は、前記一主面に垂直な方向に厚さを有し、前記線状の窪み部が前記一主面に垂直な方向に窪んでいる前記一主面からの深さの値は、前記第２半導体層の前記厚さの値よりも大きく、前記第１半導体層は、Ｉ−III−VI族化合物半導体を含む。そして、前記第１半導体層において、前記線状の窪み部を基準として前記一主面に垂直な方向に位置する結晶の平均粒径である第１平均粒径が、残余の結晶の平均粒径である第２平均粒径よりも大きい。 In order to solve the above-described problem, the photoelectric conversion device according to the first aspect includes a plurality of linear depressions extending in different directions in a flat surface on one main surface, and the first conductive A first semiconductor layer having a mold, and a second semiconductor layer having a second conductivity type disposed on the one main surface. In this photoelectric conversion device, the second semiconductor layer has a thickness in a direction perpendicular to the one principal surface, and the linear depression is recessed in a direction perpendicular to the one principal surface. The depth value from the surface is larger than the thickness value of the second semiconductor layer, and the first semiconductor layer includes an I-III-VI group compound semiconductor. In the first semiconductor layer, the first average grain size which is an average grain size of crystals located in a direction perpendicular to the one main surface with respect to the linear depression is an average grain size of the remaining crystals. Is larger than the second average particle diameter .
Claims (9)
前記一主面の上に配されている第２の導電型を有する第２半導体層と、を備える光電変換装置。A first semiconductor layer having a linear depression extending on one main surface and having a first conductivity type;
And a second semiconductor layer having a second conductivity type disposed on the one main surface.
前記線状の窪み部が前記一主面に垂直な方向に窪んでいる前記一主面からの深さの値は、前記第２半導体層の前記厚さの値よりも大きい請求項１に記載の光電変換装置。The second semiconductor layer has a thickness in a direction perpendicular to the one main surface,
2. The depth value from the one principal surface in which the linear depression is recessed in a direction perpendicular to the one principal surface is greater than the thickness value of the second semiconductor layer. Photoelectric conversion device.
前記複数の線状の窪み部は、前記一主面において相互に異なる方向に延在している請求項１から請求項３の何れか１つの請求項に記載の光電変換装置。The first semiconductor layer is provided with a plurality of the linear depressions,
4. The photoelectric conversion device according to claim 1, wherein the plurality of linear depressions extend in different directions on the one main surface. 5.
前記微粒子含有溶液を電極層の上に塗布して皮膜を形成する工程と、
前記皮膜に対して熱処理を施すことで、一主面に線状の窪み部が延在している半導体層を形成する工程と、を備え、
前記原料溶液に、ルイス塩基性有機化合物、カルコゲン元素を含有する有機化合物および金属元素を含ませ、
前記化合物半導体の微粒子に、前記金属元素を含ませる光電変換装置の製造方法。Preparing a fine particle-containing solution containing a raw material solution and fine particles of a compound semiconductor;
Applying the fine particle-containing solution on the electrode layer to form a film;
Forming a semiconductor layer in which a linear depression extends on one main surface by applying a heat treatment to the film, and
The raw material solution contains a Lewis basic organic compound, an organic compound containing a chalcogen element, and a metal element,
A method of manufacturing a photoelectric conversion device, wherein the metal element is contained in the compound semiconductor fine particles.
前記化合物半導体として、Ｉ−III−VI族化合物半導体を含ませる請求項６に記載の光電変換装置の製造方法。As the metal element, an IB group element and an III-B group element are included,
The method for producing a photoelectric conversion device according to claim 6, wherein an I-III-VI group compound semiconductor is included as the compound semiconductor.
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