WO2015053265A1 - In film, in sputtering target for forming in film, and method for manufacturing same - Google Patents

In film, in sputtering target for forming in film, and method for manufacturing same Download PDF

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WO2015053265A1
WO2015053265A1 PCT/JP2014/076811 JP2014076811W WO2015053265A1 WO 2015053265 A1 WO2015053265 A1 WO 2015053265A1 JP 2014076811 W JP2014076811 W JP 2014076811W WO 2015053265 A1 WO2015053265 A1 WO 2015053265A1
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film
sputtering target
sputtering
atomic
forming
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啓太 梅本
張　守斌
加藤　慎司
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三菱マテリアル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—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
    • 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
    • H01L31/0749—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 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • 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
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is used for forming a Cu—In—Ga—Se quaternary alloy film in the manufacture of a CIGS compound thin film solar cell having a Cu—In—Ga—Se quaternary alloy film as a light absorption layer. More particularly, the present invention relates to an In thin film formed by sputtering using the In sputtering target.
  • This application claims priority on October 7, 2013 based on Japanese Patent Application No. 2013-209977 for which it applied to Japan, and uses the content here.
  • a Mo electrode layer is formed on a soda lime glass substrate, and a light comprising a Cu—In—Ga—Se quaternary alloy film is formed on this Mo electrode layer.
  • An absorption layer is formed, and a buffer layer made of ZnS, CdS, or the like is formed on the light absorption layer made of the Cu—In—Ga—Se quaternary alloy film, and further, a transparent electrode layer is formed on the buffer layer. Is formed.
  • a CIGS compound thin film solar cell has such a basic structure.
  • a method for forming a light absorption layer comprising the above-described Cu—In—Ga—Se quaternary alloy film
  • a method of forming a film by vapor deposition is known, and Cu—In—Ga— obtained by this method is known.
  • the light absorption layer made of a Se quaternary alloy film has an advantage that high energy conversion efficiency can be obtained.
  • the film formation speed is low, and when a large-area compound thin film is formed, The uniformity of the in-plane distribution of film thickness is insufficient. Therefore, a method for forming a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film by a selenization method has been proposed.
  • an In film is formed on the Mo electrode layer by sputtering using an In sputtering target.
  • a Cu—Ga binary alloy film is formed on the In film by sputtering using a Cu—Ga binary alloy sputtering target, and the In film and Cu—Ga binary obtained here are formed.
  • a laminated film made of an alloy film, that is, a precursor film that is a precursor is formed.
  • a method of forming a Cu—In—Ga—Se quaternary alloy film by heat-treating this precursor film in a Se atmosphere has been proposed (see, for example, Patent Document 1).
  • an In film is formed by a sputtering method
  • In is aggregated in an island shape to form a discontinuous layer.
  • an In film is stacked on a Cu—Ga alloy film
  • a portion covered with In and a portion not covered with In are formed.
  • an In hillock is formed, a portion having no In becomes Cu-rich during the subsequent selenization treatment, and a low-resistance Cu—Se compound is locally generated.
  • the component composition of the light absorption layer varies, and the performance of the solar cell is reduced.
  • an object of the present invention is to provide an In sputtering target that can prevent In hillocks when an In film is formed by a sputtering method, and is suitable for forming a CIGS light absorption layer in a thin film solar cell.
  • a further object of the present invention is to provide an In film having in-plane uniformity, which is formed by sputtering using this In sputtering target and has improved film quality by preventing the formation of In hillocks.
  • various In sputtering targets are prepared by adding a small amount of an element selected from Bi, Sb, Sn, and Zn containing In as a main component, and direct current (DC) sputtering is performed using these In sputtering targets.
  • DC direct current
  • the present invention has been obtained from the above findings, and has the following configuration in order to solve the above-described problems.
  • One or more elements selected from Bi, Sb, Sn, and Zn are contained in a total amount of 0.5 to 10.0 atomic%, and the balance has a component composition composed of In and inevitable impurities.
  • In sputtering target (2) The In sputtering target according to (1), wherein the oxygen concentration in the sputtering target is 0.04% by mass or less.
  • One or more elements selected from Bi, Sb, Sn, and Zn are contained in a total amount of 0.5 to 10.0 atomic%, and the balance has a component composition consisting of In and inevitable impurities.
  • the addition of one or more elements selected from Bi, Sb, and Zn is 0.5 to 10 in total. Although it is said that it is contained at 0.0 atomic%, the reason for limiting the amount of this addition is that when this addition exceeds 10.0 atomic%, the conversion efficiency of the CIGS thin film solar cell decreases, On the other hand, if the amount of addition is less than 0.5 atomic%, the generation of In hillocks in the film, that is, the generation of island-like In cannot be suppressed.
  • an alloy phase containing one or more elements selected from Bi, Sb, Sn, and Zn in the sputtering target for example, a compound of one of these elements and In (BiIn 2 , Bi 3 In 5 , BiIn, InSb), or a compound of Zn and Sb, a solid solution between the elements, etc. (hereinafter referred to as an additive element-containing alloy phase) has a maximum particle size of 50 ⁇ m or less.
  • the particle size of the additive element-containing alloy phase is: Although it causes abnormal discharge and nodule generation, excessive abnormal discharge does not occur if the maximum particle size is 50 ⁇ m or less.
  • the oxygen content in the sputtering target is preferably as small as possible in order to suppress the occurrence of abnormal discharge during sputtering, which is the cause of the occurrence of surface roughness after sputtering. In the present invention, the oxygen content was made into 0.04 mass% or less. Furthermore, the oxygen content is desirably 0.03% by mass or less.
  • the In sputtering target of the present invention contains one or more elements selected from Bi, Sb, Sn, and Zn in a total amount of 0.5 to 10.0 atomic%, with the balance being In and inevitable. If the In sputtering target is used for sputtering, one or more elements selected from Bi, Sb, Sn, and Zn are added in a total amount of 0.5 to 10. It is possible to form an In film having a component composition of 0 atomic%, with the balance being In and inevitable impurities, and adding one or more elements selected from Bi, Sb, Sn, and Zn.
  • the film quality is improved, and a uniform In film can be obtained, which is effective for forming a light absorption layer in a CIGS compound thin film solar cell, and is an in-line type sputtering film. Applied to becomes possible, contributing to improved productivity of the thin film solar cell.
  • each weighed raw material powder is put into a carbon crucible and heated by high frequency induction heating in a vacuum to be melted.
  • dissolved for 5 minutes it casts on 125 mm diameter Cu backing plate which provided the weir beforehand.
  • the surface of the Cu backing plate is preferably wetted beforehand with an In alloy having a composition for casting.
  • the In raw material was previously placed on the Cu backing plate and the Cu backing plate was heated to dissolve In, and then It is also possible to produce an In sputtering target by solidification.
  • the target basic characteristics of the produced In sputtering targets of Examples and Comparative Examples were an average particle size of target structure: 200 ⁇ m or less, surface roughness Ra: 3 ⁇ m or less, and specific resistance: 10 ⁇ 1 ⁇ ⁇ cm or less.
  • the maximum particle size of the additive element-containing alloy phase was measured. The measuring method is as follows.
  • ⁇ Maximum particle size measurement method of additive element-containing alloy phase The surface (lathe surface) of the produced sputtering target is etched with aqua regia for about 1 minute, washed with pure water, and then subjected to mapping analysis using an electron beam microanalyzer (EPMA) at a magnification of 200 times and any arbitrary surface on the surface. Observations were made at five locations. If clear tissue was not visible, additional aqua regia etching was performed.
  • the maximum diameter of the largest region was defined as the maximum particle diameter of the additive element-containing alloy phase.
  • Table 1 The measurement results are shown in Table 1 below.
  • FIG. 1 shows an image of a COMPO image obtained with an electron microscope (SEM) for an In sputtering target containing 5 atomic% Bi.
  • SEM electron microscope
  • the element distribution image by EPMA is originally a color image, but is shown in a photograph converted into a black and white image. In the photograph, the whiter, the higher the concentration of Bi element.
  • the COMPO image related to In and Bi it is possible to observe a state in which the In—Bi compound in the grayish white portion is dispersed and distributed in the gray In base. .
  • the grayish white part is indicated by an arrow “In-Bi compound”.
  • ⁇ Measurement of oxygen concentration> About 1 g was sampled from the surface of the produced sputtering target, the surface was etched with aqua regia for about 1 minute, washed with pure water, and the oxygen concentration was measured by gas analysis. ⁇ Analysis of XRD diffraction measurement results> The surface of the produced sputtering target was measured in the range of 2 ⁇ 5 to 80 ° with an XRD apparatus (RINT-Ultima / PC) manufactured by Rigaku Corporation. In Table 1, the case where a peak derived from a Bi, Sb, Sn, and Zn added element appears was “present”, and the case where a peak was not present was “absent”.
  • the number of abnormal discharges was measured as follows, and the surface state after this measurement was observed.
  • the measurement results are shown in the “abnormal discharge (times / h)” column and “presence / absence of surface roughness after sputtering” column in Tables 3 and 4 below.
  • ⁇ Measurement of abnormal discharge times> Sputtering was performed for 12 hours under the above conditions, and the number of abnormal discharges was measured by an arc count function provided in the DC power supply. Thereafter, the sputtering chamber was opened, and particles in the chamber were confirmed.
  • the thickness of the In film obtained under the above film formation conditions was measured, and the presence or absence of hillocks (island state) was confirmed on the surface of the In film.
  • the observation results are shown in the “film thickness (nm)” column and the “in hillock presence / absence” column of Tables 3 and 4.
  • FE-SEM field emission scanning electron microscope
  • the In sputtering targets of Comparative Examples 1 and 2 were based on the prior art, and when they were used to form a film, In hillocks were generated because the target contained no additive elements.
  • the In sputtering target of Comparative Example 3 has a small amount of additive element Bi
  • the In sputtering target of Comparative Example 4 has a small amount of additive element Zn
  • the In sputtering target of Comparative Example 5 has an amount of additive element Sb.
  • the In sputtering target of Comparative Example 6 since the amount of the additive element Sn was small, no abnormal discharge was observed during sputtering, but In hillocks were generated. None of the In films formed using the In sputtering targets of Comparative Examples 1 to 6 showed improvement in film quality.
  • the In film formed with an In sputtering target having a composition contains one or more elements selected from Bi, Sb, Sn, and Zn in a total amount of 0.5 to 10.0 atomic%, with the balance being In. It was confirmed that the film composition was improved and a uniform In film was obtained. It has been found that the In film according to the present invention is suitable for forming a light absorption layer of a CIGS thin solar cell.

Abstract

Provided is an In sputtering target having a composition containing a total of 0.5 to 10.0 atom% of at least one type of element selected from the group consisting of Bi, Sb, Sn, and Zn, the remainder comprising In and unavoidable impurities.

Description

Ｉｎ膜、Ｉｎ膜を成膜するためのＩｎスパッタリングターゲット及びその製造方法In film, In sputtering target for forming In film, and manufacturing method thereof
　本発明は、光吸収層としてＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜を有するＣＩＧＳ系化合物薄膜太陽電池の製造に際して、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜を形成するときに使用するＩｎスパッタリングターゲット及びその製造方法に関し、さらに、そのＩｎスパッタリングターゲットを用いたスパッタリングで成膜されたＩｎ薄膜に関する。
　本願は、２０１３年１０月７日に、日本に出願された特願２０１３－２０９９７７号に基づき優先権を主張し、その内容をここに援用する。 The present invention is used for forming a Cu—In—Ga—Se quaternary alloy film in the manufacture of a CIGS compound thin film solar cell having a Cu—In—Ga—Se quaternary alloy film as a light absorption layer. More particularly, the present invention relates to an In thin film formed by sputtering using the In sputtering target.
This application claims priority on October 7, 2013 based on Japanese Patent Application No. 2013-209977 for which it applied to Japan, and uses the content here.
　近年、化合物半導体による薄膜太陽電池が実用に供せられている。この化合物半導体による薄膜太陽電池の製造においては、先ず、ソーダライムガラス基板上に、Ｍｏ電極層が形成され、このＭｏ電極層上に、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層が形成され、このＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層上に、ＺｎＳ、ＣｄＳなどからなるバッファ層が形成され、さらに、このバッファ層上に、透明電極層が形成される。ＣＩＧＳ系化合物薄膜太陽電池は、この様な基本構造を有している。 In recent years, thin film solar cells using compound semiconductors have been put into practical use. In the production of a thin film solar cell using this compound semiconductor, first, a Mo electrode layer is formed on a soda lime glass substrate, and a light comprising a Cu—In—Ga—Se quaternary alloy film is formed on this Mo electrode layer. An absorption layer is formed, and a buffer layer made of ZnS, CdS, or the like is formed on the light absorption layer made of the Cu—In—Ga—Se quaternary alloy film, and further, a transparent electrode layer is formed on the buffer layer. Is formed. A CIGS compound thin film solar cell has such a basic structure.
　上記のＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層の形成方法としては、蒸着法により成膜する方法が知られており、この方法により得られたＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層は、高いエネルギー変換効率が得られるという利点もあるが、この蒸着法によると、成膜速度が遅く、大面積の化合物薄膜を成膜する場合には、膜厚の面内分布の均一性が不足している。そのために、セレン化法によって、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜からなる光吸収層を形成する方法が提案されている。 As a method for forming a light absorption layer comprising the above-described Cu—In—Ga—Se quaternary alloy film, a method of forming a film by vapor deposition is known, and Cu—In—Ga— obtained by this method is known. The light absorption layer made of a Se quaternary alloy film has an advantage that high energy conversion efficiency can be obtained. However, according to this vapor deposition method, the film formation speed is low, and when a large-area compound thin film is formed, The uniformity of the in-plane distribution of film thickness is insufficient. Therefore, a method for forming a light absorption layer made of a Cu—In—Ga—Se quaternary alloy film by a selenization method has been proposed.
　上記のＣｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜をセレン化法で成膜する方法として、先ず、Ｉｎスパッタリングターゲットを使用したスパッタリングにより、Ｍｏ電極層上に、Ｉｎ膜を成膜し、このＩｎ膜の上に、Ｃｕ－Ｇａ二元系合金スパッタリングターゲットを使用してスパッタリングすることにより、Ｃｕ－Ｇａ二元系合金膜を成膜し、ここで得られたＩｎ膜及びＣｕ－Ｇａ二元系合金膜からなる積層膜、即ち、前駆体であるプリカーサー膜が形成される。このプリカーサー膜を、Ｓｅ雰囲気中で熱処理して、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合金膜を形成する方法が提案されている（例えば、特許文献１を参照）。 As a method for forming the Cu—In—Ga—Se quaternary alloy film by the selenization method, first, an In film is formed on the Mo electrode layer by sputtering using an In sputtering target. A Cu—Ga binary alloy film is formed on the In film by sputtering using a Cu—Ga binary alloy sputtering target, and the In film and Cu—Ga binary obtained here are formed. A laminated film made of an alloy film, that is, a precursor film that is a precursor is formed. A method of forming a Cu—In—Ga—Se quaternary alloy film by heat-treating this precursor film in a Se atmosphere has been proposed (see, for example, Patent Document 1).
　一方、Ｉｎスパッタリングターゲットを使用したスパッタリングにより、Ｉｎ膜を形成する際、低融点で表面張力が大きいというＩｎの物性に起因して、Ｉｎが粒状に成長してしまい、不連続に隙間を有した粗い、島状のＩｎ膜（以下、ヒロックという）が表面に生成されることが報告されている（例えば、非特許文献１、２を参照）。 On the other hand, when forming an In film by sputtering using an In sputtering target, In grew due to the physical properties of In having a low melting point and a large surface tension, and In was grown in a discontinuous manner. It has been reported that a rough, island-like In film (hereinafter referred to as hillock) is generated on the surface (for example, see Non-Patent Documents 1 and 2).
特許第３２４９４０８号公報Japanese Patent No. 3249408
　上述のように、Ｉｎ膜をスパッタリング法で形成すると、Ｉｎが島状に凝集して不連続層が形成されるようになり、例えば、Ｃｕ－Ｇａ合金膜上にＩｎ膜を積層する場合には、Ｉｎで覆われる部分と覆われない部分が形成されるようになる。この様なＩｎのヒロックが形成されると、その後のセレン化処理時に、Ｉｎのない箇所がＣｕリッチとなって、低抵抗のＣｕ－Ｓｅ化合物が局所的に生成されることになる。結果的に、光吸収層の成分組成にばらつきが生じ、太陽電池の性能低下をもたらす。 As described above, when an In film is formed by a sputtering method, In is aggregated in an island shape to form a discontinuous layer. For example, when an In film is stacked on a Cu—Ga alloy film, , A portion covered with In and a portion not covered with In are formed. When such an In hillock is formed, a portion having no In becomes Cu-rich during the subsequent selenization treatment, and a low-resistance Cu—Se compound is locally generated. As a result, the component composition of the light absorption layer varies, and the performance of the solar cell is reduced.
　そこで、本発明は、スパッタリング法によってＩｎ膜を成膜したときにＩｎのヒロックを防止でき、薄膜太陽電池におけるＣＩＧＳ系光吸収層の形成に好適なＩｎスパッタリングターゲットを提供することを目的とする。さらに、本発明は、このＩｎスパッタリングターゲットを用いたスパッタリングで成膜され、Ｉｎヒロックの形成を防止して膜質改善した、面内均一性を有するＩｎ膜を提供することを目的とする。 Therefore, an object of the present invention is to provide an In sputtering target that can prevent In hillocks when an In film is formed by a sputtering method, and is suitable for forming a CIGS light absorption layer in a thin film solar cell. A further object of the present invention is to provide an In film having in-plane uniformity, which is formed by sputtering using this In sputtering target and has improved film quality by preventing the formation of In hillocks.
　本発明者らは、Ｉｎ膜を成膜時に生じるＩｎヒロックの形成を防止するには、下地膜のＣｕＧａ膜、或いは、Ｃｕ又はＭｏ膜へのＩｎの濡れ性を改善することにより解決できることに着目し、検討の結果、Ｉｎに、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎを添加すると、この濡れ性を改善できることが判明した。 In order to prevent the formation of In hillocks that occur during the formation of an In film, the present inventors have focused on solving the problem by improving the wettability of In to the underlying CuGa film or Cu or Mo film. As a result of investigation, it has been found that the addition of Bi, Sb, Sn, Zn to In can improve this wettability.
　そこで、Ｉｎを主成分とし、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された元素を、少量添加したＩｎスパッタリングターゲットを種々作製し、これらのＩｎスパッタリングターゲットを用いて、直流（ＤＣ）スパッタリングで、Ｉｎ膜を成膜したところ、Ｉｎ膜の濡れ性が改善されて、ヒロックは、形成されず、面内均一性を有するＩｎ膜が得られることが確認された。 Accordingly, various In sputtering targets are prepared by adding a small amount of an element selected from Bi, Sb, Sn, and Zn containing In as a main component, and direct current (DC) sputtering is performed using these In sputtering targets. When the film was formed, it was confirmed that the wettability of the In film was improved, hillocks were not formed, and an In film having in-plane uniformity was obtained.
　したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成の態様を有する。
（１）Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素を、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＩｎスパッタリングターゲット。
（２）スパッタリングターゲット中の酸素濃度が０．０４質量％以下であることを特徴とする前記（１）に記載のＩｎスパッタリングターゲット。
（３）スパッタリングターゲット中のＢｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上を含む合金相の最大粒径が５０μｍ以下であることを特徴とする前記（１）に記載のＩｎスパッタリングターゲット。
（４）Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択される１種以上の元素を、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＣＩＧＳ太陽電製造用Ｉｎ膜。 Therefore, the present invention has been obtained from the above findings, and has the following configuration in order to solve the above-described problems.
(1) One or more elements selected from Bi, Sb, Sn, and Zn are contained in a total amount of 0.5 to 10.0 atomic%, and the balance has a component composition composed of In and inevitable impurities. In sputtering target.
(2) The In sputtering target according to (1), wherein the oxygen concentration in the sputtering target is 0.04% by mass or less.
(3) The In sputtering target according to (1) above, wherein the maximum particle size of the alloy phase containing one or more selected from Bi, Sb, Sn, and Zn in the sputtering target is 50 μm or less.
(4) One or more elements selected from Bi, Sb, Sn, and Zn are contained in a total amount of 0.5 to 10.0 atomic%, and the balance has a component composition consisting of In and inevitable impurities. An In film for CIGS solar power production.
　上記の本発明の態様のＩｎスパッタリングターゲット（以下、本願発明のＩｎスパッタリングターゲットと称する）においては、Ｂｉ、Ｓｂ、Ｚｎから選択された１種以上の元素の添加について、合計で０．５～１０．０原子％含有するとしているが、この添加量を範囲限定している理由は、この添加量が、１０．０原子％を超えて多くなると、ＣＩＧＳ系薄膜太陽電池の変換効率が低下し、一方、その添加量が、０．５原子％未満であると、膜中のＩｎヒロック発生、即ち、島状Ｉｎの発生の抑制ができないからである。 In the In sputtering target according to the aspect of the present invention described above (hereinafter referred to as the In sputtering target of the present invention), the addition of one or more elements selected from Bi, Sb, and Zn is 0.5 to 10 in total. Although it is said that it is contained at 0.0 atomic%, the reason for limiting the amount of this addition is that when this addition exceeds 10.0 atomic%, the conversion efficiency of the CIGS thin film solar cell decreases, On the other hand, if the amount of addition is less than 0.5 atomic%, the generation of In hillocks in the film, that is, the generation of island-like In cannot be suppressed.
　また、スパッタリングターゲット中のＢｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素を含む合金相（例えば、これら元素の１種とＩｎとの化合物（ＢｉＩｎ２、Ｂｉ３Ｉｎ５、ＢｉＩｎ、ＩｎＳｂ）、或いは、ＺｎとＳｂの化合物や各元素間の固溶体など。以下、添加元素含有合金相とする）の最大粒径が５０μｍ以下としている。ここで、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素が添加されたＩｎスパッタリングターゲットを用いて直流（ＤＣ）スパッタリングするとき、添加元素含有合金相の粒径の大きさは、異常放電、ノジュールの発生の要因となるが、最大粒径が５０μｍ以下であれば、過度な異常放電は発生しない。
　さらに、スパッタリングターゲット中の酸素含有量は、スパッタ後のターゲット表面の荒れ発生の原因である、スパッタリング時の異常放電の発生を抑制する上では、できるだけ少ないことが好ましく、本発明では、酸素含有量を０．０４質量％以下とした。さらに、望ましくは、酸素含有量は０．０３質量％以下が良い。 In addition, an alloy phase containing one or more elements selected from Bi, Sb, Sn, and Zn in the sputtering target (for example, a compound of one of these elements and In (BiIn 2 , Bi 3 In 5 , BiIn, InSb), or a compound of Zn and Sb, a solid solution between the elements, etc. (hereinafter referred to as an additive element-containing alloy phase) has a maximum particle size of 50 μm or less. Here, when direct current (DC) sputtering is performed using an In sputtering target to which one or more elements selected from Bi, Sb, Sn, and Zn are added, the particle size of the additive element-containing alloy phase is: Although it causes abnormal discharge and nodule generation, excessive abnormal discharge does not occur if the maximum particle size is 50 μm or less.
Furthermore, the oxygen content in the sputtering target is preferably as small as possible in order to suppress the occurrence of abnormal discharge during sputtering, which is the cause of the occurrence of surface roughness after sputtering. In the present invention, the oxygen content Was made into 0.04 mass% or less. Furthermore, the oxygen content is desirably 0.03% by mass or less.
　以上の様に、本発明のＩｎスパッタリングターゲットは、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素が、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴としており、このＩｎスパッタリングターゲットを用いてスパッタリングすれば、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素が、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎ膜を成膜することができ、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素が添加されることで、膜質が改善され、均一なＩｎ膜が得られるようになり、ＣＩＧＳ系化合物薄膜太陽電池における光吸収層の形成に有効であって、かつ、インライン方式のスパッタリングにも適用が可能となり、薄膜太陽電池の生産性向上に寄与する。 As described above, the In sputtering target of the present invention contains one or more elements selected from Bi, Sb, Sn, and Zn in a total amount of 0.5 to 10.0 atomic%, with the balance being In and inevitable. If the In sputtering target is used for sputtering, one or more elements selected from Bi, Sb, Sn, and Zn are added in a total amount of 0.5 to 10. It is possible to form an In film having a component composition of 0 atomic%, with the balance being In and inevitable impurities, and adding one or more elements selected from Bi, Sb, Sn, and Zn. The film quality is improved, and a uniform In film can be obtained, which is effective for forming a light absorption layer in a CIGS compound thin film solar cell, and is an in-line type sputtering film. Applied to becomes possible, contributing to improved productivity of the thin film solar cell.
Ｂｉを含有させたＩｎスパッタリングターゲットについて、電子顕微鏡で取得したＣＯＭＰＯ像の例を示す図である。It is a figure which shows the example of the COMPO image acquired with the electron microscope about In sputtering target containing Bi.
　つぎに、この発明のＩｎスパッタリングターゲット及びその製造方法、さらには、Ｉｎ薄膜について、以下に、実施例により具体的に説明する。 Next, the In sputtering target and the manufacturing method thereof according to the present invention, and the In thin film will be specifically described below with reference to examples.
〔実施例〕
　先ず、Ｉｎスパッタリングターゲットを製造するために、ターゲット製造原料として、Ｉｎ（純度４Ｎ以上）、Ｂｉ（純度４Ｎ以上）、Ｓｂ（純度４Ｎ以上）、Ｓｎ（純度４Ｎ以上）、Ｚｎ（純度４Ｎ以上）を用意した。ここで、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎに関しては、製造原料としてインゴットでも良いが、溶解のしやすさから、粉末のものを用意した。下記の表１に示されるように、Ｉｎと、添加元素としてのＢｉ、Ｓｂ、Ｓｎ、Ｚｎの各粉末とをそれぞれ秤量した。なお、表１には、添加元素の量（質量％）のみが示されているが、Ｉｎの量は、その残部であるため、表示されていない。 〔Example〕
First, in order to manufacture an In sputtering target, as target production raw materials, In (purity 4N or higher), Bi (purity 4N or higher), Sb (purity 4N or higher), Sn (purity 4N or higher), Zn (purity 4N or higher) Prepared. Here, regarding Bi, Sb, Sn, and Zn, an ingot may be used as a manufacturing raw material, but a powder is prepared for ease of dissolution. As shown in Table 1 below, In and each powder of Bi, Sb, Sn, and Zn as additive elements were weighed. In Table 1, only the amount (mass%) of the additive element is shown, but the amount of In is the remainder and is not displayed.
　次いで、秤量された各原料粉末を、カーボン製のるつぼに入れ、真空中にて、高周波誘導加熱により加熱を行い、溶解する。なお、真空中で加熱する代わりに、大気中或いは非酸化性雰囲気で加熱されてもよい。そして、各添加元素が溶けた時点の温度を５分間保持した後、予め、堰を設けた１２５ｍｍ径のＣｕバッキングプレート上に鋳込む。鋳造後のバッキングプレートとの密着性を向上させるため、Ｃｕバッキングプレート表面は、あらかじめ鋳込みを行う組成のＩｎ合金で濡らしておくことが好ましい。ここで、冷却の後、堰を外したうえで、機械加工にて、所定形状に整え、実施例１～２９のＩｎスパッタリングターゲットを作製した。なお、本実施例では、Ｉｎを溶解したのち、Ｃｕバッキングプレート上で鋳造したが、予めＣｕバッキングプレート上にＩｎ原料を配置し、Ｃｕバッキングプレートを加熱することにより、Ｉｎを溶解し、その後、凝固させてＩｎスパッタリングターゲットを作製することもできる。 Next, each weighed raw material powder is put into a carbon crucible and heated by high frequency induction heating in a vacuum to be melted. In addition, you may heat in air | atmosphere or a non-oxidizing atmosphere instead of heating in a vacuum. And after hold | maintaining the temperature when each additive element melt | dissolved for 5 minutes, it casts on 125 mm diameter Cu backing plate which provided the weir beforehand. In order to improve the adhesion to the backing plate after casting, the surface of the Cu backing plate is preferably wetted beforehand with an In alloy having a composition for casting. Here, after cooling, the weir was removed and the shape was adjusted to a predetermined shape by machining to produce In sputtering targets of Examples 1 to 29. In this example, after melting In, it was cast on the Cu backing plate, but the In raw material was previously placed on the Cu backing plate and the Cu backing plate was heated to dissolve In, and then It is also possible to produce an In sputtering target by solidification.
〔比較例〕
　また、本発明の実施例と比較するため、下記の表２に示すように、実施例の場合と同様の手法により、添加元素を含まないＩｎのみの比較例１及び２のＩｎスパッタリングターゲットと、Ｂｉ：０．０５原子％を添加した比較例３のＩｎスパッタリングターゲットと、Ｚｎ：０．０７原子％を添加した比較例４のＩｎスパッタリングターゲットと、Ｓｂ：０．０７原子％を添加した比較例５のＩｎスパッタリングターゲットと、Ｓｎを０．０５原子％添加した比較例６のＩｎスパッタリングターゲットをそれぞれ作製した。 [Comparative example]
In addition, in order to compare with the examples of the present invention, as shown in Table 2 below, the In sputtering target of Comparative Examples 1 and 2 containing only In and containing no additive element, by the same method as in the case of the examples, Bi: In sputtering target of Comparative Example 3 to which 0.05 atomic% was added, In sputtering target of Comparative Example 4 to which Zn: 0.07 atomic% was added, and Comparative example to which Sb: 0.07 atomic% was added 5 and an In sputtering target of Comparative Example 6 in which 0.05 atomic% of Sn was added.
　作製した実施例及び比較例のＩｎスパッタリングターゲットのターゲット基本特性は、ターゲット組織の平均粒径：２００μｍ以下、表面粗さＲａ：３μｍ以下、比抵抗：１０－１Ω・ｃｍ以下であった。次に、実施例１～２９及び比較例３～６のＩｎスパッタリングターゲットについて、添加元素含有合金相の最大粒径を測定した。その測定方法は、以下の様である。 The target basic characteristics of the produced In sputtering targets of Examples and Comparative Examples were an average particle size of target structure: 200 μm or less, surface roughness Ra: 3 μm or less, and specific resistance: 10 −1 Ω · cm or less. Next, for the In sputtering targets of Examples 1 to 29 and Comparative Examples 3 to 6, the maximum particle size of the additive element-containing alloy phase was measured. The measuring method is as follows.
＜添加元素含有合金相の最大粒径測定方法＞
　作製されたスパッタリングターゲットの表面（旋盤加工面）を王水で1分程度エッチングし、純水で洗浄後、電子線マイクロアナライザ（ＥＰＭＡ）によるマッピング分析を、倍率２００倍で、表面上の任意の５箇所で観測した。明確な組織が見えない場合には、王水のエッチングを追加で行った。ここで、ＥＰＭＡの１画像から観察される添加元素成分のうち、最も大きい領域に係る最大径を、添加元素含有合金相の最大粒径とした。その測定結果が、下記の表１に示されている。 <Maximum particle size measurement method of additive element-containing alloy phase>
The surface (lathe surface) of the produced sputtering target is etched with aqua regia for about 1 minute, washed with pure water, and then subjected to mapping analysis using an electron beam microanalyzer (EPMA) at a magnification of 200 times and any arbitrary surface on the surface. Observations were made at five locations. If clear tissue was not visible, additional aqua regia etching was performed. Here, among the additive element components observed from one image of EPMA, the maximum diameter of the largest region was defined as the maximum particle diameter of the additive element-containing alloy phase. The measurement results are shown in Table 1 below.
　なお、参考例として、Ｂｉを５原子％含有させたＩｎスパッタリングターゲットについて、電子顕微鏡（ＳＥＭ）で取得したＣＯＭＰＯ像の画像を、図１に示した。ＥＰＭＡによる元素分布像は、本来カラー像であるが、白黒像に変換した写真で示しているため、その写真中において、白いほど、Ｂｉ元素の濃度が高いことを表している。具体的には、図１の画像のように、Ｉｎ及びＢｉに関するＣＯＭＰＯ像では、灰色を示すＩｎの素地中に、灰白色部分のＩｎ－Ｂｉ化合物が分散分布している様子を観察することができる。なお、灰白色部分には、「Ｉｎ－Ｂｉ化合物」と矢示されている。 As a reference example, FIG. 1 shows an image of a COMPO image obtained with an electron microscope (SEM) for an In sputtering target containing 5 atomic% Bi. The element distribution image by EPMA is originally a color image, but is shown in a photograph converted into a black and white image. In the photograph, the whiter, the higher the concentration of Bi element. Specifically, as in the image of FIG. 1, in the COMPO image related to In and Bi, it is possible to observe a state in which the In—Bi compound in the grayish white portion is dispersed and distributed in the gray In base. . The grayish white part is indicated by an arrow “In-Bi compound”.
＜酸素濃度の測定＞
　作製されたスパッタリングターゲットの表面から１ｇ程度サンプリングを行い、表面を王水で1分程度エッチングし、純水で洗浄後、ガス分析により酸素濃度を測定した。
＜ＸＲＤ回折測定結果の解析＞
　作製されたスパッタリングターゲットの表面を理学電気社製ＸＲＤ装置（ＲＩＮＴ－Ultima/PC）により、２θ＝５～８０°の範囲で測定した。表１においては、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎ添加元素単体に由来するピークが現れた場合を「有」とし、現れない場合を「無」とした。 <Measurement of oxygen concentration>
About 1 g was sampled from the surface of the produced sputtering target, the surface was etched with aqua regia for about 1 minute, washed with pure water, and the oxygen concentration was measured by gas analysis.
<Analysis of XRD diffraction measurement results>
The surface of the produced sputtering target was measured in the range of 2θ = 5 to 80 ° with an XRD apparatus (RINT-Ultima / PC) manufactured by Rigaku Corporation. In Table 1, the case where a peak derived from a Bi, Sb, Sn, and Zn added element appears was “present”, and the case where a peak was not present was “absent”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　次に、上述した実施例１～２９及び比較例１～６のＩｎスパッタリングターゲットを用いて、以下の成膜条件により、Ｉｎ膜の成膜試験を行った。Ｉｎ膜の膜厚は、３００～５００ｎｍである。
＜成膜条件＞
・基板：ガラス基板
・基板サイズ：２０ｍｍ角
・電源：ＤＣ５００Ｗ
・全圧：０．１５Ｐａ
・スパッタリングガス：Ａｒ＝３０ｓｃｃｍ
・ターゲット－基板（ＴＳ）距離：７０ｍｍ Next, using the In sputtering targets of Examples 1 to 29 and Comparative Examples 1 to 6 described above, an In film formation test was performed under the following film formation conditions. The thickness of the In film is 300 to 500 nm.
<Film formation conditions>
・ Substrate: Glass substrate ・ Substrate size: 20mm square ・ Power supply: DC500W
・ Total pressure: 0.15Pa
・ Sputtering gas: Ar = 30 sccm
・ Target-substrate (TS) distance: 70mm
　上記の成膜条件に従った成膜試験により、以下の様にして、異常放電回数を測定し、この測定後における表面状態の観察を行った。この測定結果が、下記の表３及び表４の「異常放電（回／ｈ）」欄と「スパッタ後ターゲット表面荒れの有無」欄に示されている。
＜異常放電回数の測定＞
　上述の条件において１２時間のスパッタリングを行い、ＤＣ電源装置に備えられているアークカウント機能により異常放電の回数を計測した。その後、スパッタチャンバーを開放し、チャンバー内のパーティクルを確認した。
＜スパッタ後のターゲット表面状態の観察＞
　異常放電回数の測定後のターゲット表面を観察し、エロージョン部が凸凹に荒れている場合を、荒れ「有」とし、荒れのない場合を、荒れ「無」とした。 By the film formation test according to the above film formation conditions, the number of abnormal discharges was measured as follows, and the surface state after this measurement was observed. The measurement results are shown in the “abnormal discharge (times / h)” column and “presence / absence of surface roughness after sputtering” column in Tables 3 and 4 below.
<Measurement of abnormal discharge times>
Sputtering was performed for 12 hours under the above conditions, and the number of abnormal discharges was measured by an arc count function provided in the DC power supply. Thereafter, the sputtering chamber was opened, and particles in the chamber were confirmed.
<Observation of target surface condition after sputtering>
The surface of the target after measurement of the number of abnormal discharges was observed, and when the erosion portion was rough, the roughness was “Yes”, and when there was no roughness, the roughness was “None”.
　上記の成膜条件で得られたＩｎ膜の膜厚を測定し、さらに、そのＩｎ膜の表面について、ヒロック（島状態）の有無を確認した。この観察結果が、表３及び表４の「膜厚（ｎｍ）」欄と、「Ｉｎヒロック有無」欄とに示されている。
＜ヒロックの評価方法＞
　得られたＩｎ膜を取り出し、電界放射型走査電子顕微鏡（ＦＥ－ＳＥＭ）にて膜表面のＩｎヒロックの有無を確認した。Ｉｎ膜にＩｎヒロックが現れるものを「有」、現れないものを「無」とした。 The thickness of the In film obtained under the above film formation conditions was measured, and the presence or absence of hillocks (island state) was confirmed on the surface of the In film. The observation results are shown in the “film thickness (nm)” column and the “in hillock presence / absence” column of Tables 3 and 4.
<Evaluation method of Hillock>
The obtained In film was taken out, and the presence or absence of In hillocks on the film surface was confirmed with a field emission scanning electron microscope (FE-SEM). The case where In hillocks appeared in the In film was defined as “Yes”, and the case where it did not appear as “None”.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　以上の表３によれば、実施例１～２９のＩｎスパッタリングターゲットを用いたスパッタリングで成膜されたＩｎ膜のいずれも、Ｉｎヒロックが無いことが確認され、平坦で均一なＩｎ膜が得られた。また、実施例１、３、４、８、１０、１１、１５、１６、１８、２１～２４、２５、２６のＩｎスパッタリングターゲットを用いてスパッタリングを行った場合には、添加元素含有合金相の最大粒径が小さいため、異常放電の発生が皆無であることが分かった。なお、実施例２、５～３、９、１２～１４、１７、１９、２０、２７～２９のＩｎスパッタリングターゲットを用いてスパッタリングを行った場合には、添加元素含有合金相の最大粒径が大きいため、異常放電が発生したが、これは、成膜に影響するものではなく、均一なＩｎ膜が得られた。 According to Table 3 above, it was confirmed that none of the In films formed by sputtering using the In sputtering targets of Examples 1 to 29 were free of In hillocks, and a flat and uniform In film was obtained. It was. Further, when sputtering was performed using the In sputtering targets of Examples 1, 3, 4, 8, 10, 11, 15, 16, 18, 21 to 24, 25, and 26, the additive element-containing alloy phase Since the maximum particle size was small, it was found that no abnormal discharge occurred. When sputtering was performed using the In sputtering targets of Examples 2, 5 to 3, 9, 12 to 14, 17, 19, 20, and 27 to 29, the maximum particle size of the additive element-containing alloy phase was Since it was large, abnormal discharge occurred, but this did not affect the film formation, and a uniform In film was obtained.
　一方、比較例１、２のＩｎスパッタリングターゲットは、従来技術による場合であって、それらを用いて成膜すると、ターゲット中には、添加元素が含まれていないので、Ｉｎヒロックが発生した。また、比較例３のＩｎスパッタリングターゲットでは、添加元素Ｂｉの量が少なく、比較例４のＩｎスパッタリングターゲットでは、添加元素Ｚｎの量が少なく、比較例５のＩｎスパッタリングターゲットでは、添加元素Ｓｂの量が少なく、さらには比較例６のＩｎスパッタリングターゲットでは、添加元素Ｓｎの量が少ないため、スパッタリング時には、異常放電の発生が見られなかったものの、Ｉｎヒロックが発生した。比較例１～６のＩｎスパッタリングターゲットを用いて成膜されたＩｎ膜のいずれも、膜質改善が見られなかった。 On the other hand, the In sputtering targets of Comparative Examples 1 and 2 were based on the prior art, and when they were used to form a film, In hillocks were generated because the target contained no additive elements. In addition, the In sputtering target of Comparative Example 3 has a small amount of additive element Bi, the In sputtering target of Comparative Example 4 has a small amount of additive element Zn, and the In sputtering target of Comparative Example 5 has an amount of additive element Sb. In addition, in the In sputtering target of Comparative Example 6, since the amount of the additive element Sn was small, no abnormal discharge was observed during sputtering, but In hillocks were generated. None of the In films formed using the In sputtering targets of Comparative Examples 1 to 6 showed improvement in film quality.
　以上の様に、本発明による、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素が、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有するＩｎスパッタリングターゲットで成膜されたＩｎ膜は、Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択される１種以上の元素が、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有し、膜質が改善され、均一なＩｎ膜が得られることを確認した。本発明によるＩｎ膜は、ＣＩＧＳ系薄太陽電池の光吸収層の形成に好適なものであることが分かった。 As described above, in accordance with the present invention, a component containing at least one element selected from Bi, Sb, Sn, and Zn in a total amount of 0.5 to 10.0 atomic%, with the balance being In and inevitable impurities The In film formed with an In sputtering target having a composition contains one or more elements selected from Bi, Sb, Sn, and Zn in a total amount of 0.5 to 10.0 atomic%, with the balance being In. It was confirmed that the film composition was improved and a uniform In film was obtained. It has been found that the In film according to the present invention is suitable for forming a light absorption layer of a CIGS thin solar cell.
　セレン化法によって、Ｃｕ－Ｉｎ－Ｇａ－Ｓｅ四元系合成膜からなる光吸収層を形成するのに適したＩｎスパッタリングターゲットを提供することにより、その光吸収層を備える太陽電池の性能を向上させることができる。 Providing an In sputtering target suitable for forming a light-absorbing layer composed of a Cu—In—Ga—Se quaternary synthetic film by a selenization method, thereby improving the performance of a solar cell including the light-absorbing layer Can be made.
　１　　Ｉｎ
　２　　Ｉｎ－Ｂｉ化合物 1 In
2 In-Bi compounds

Claims (4)

  1. 　Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上の元素を合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＩｎスパッタリングターゲット。 In sputtering comprising at least one element selected from Bi, Sb, Sn, and Zn in a total content of 0.5 to 10.0 atomic%, with the balance being composed of In and inevitable impurities target.
  2. 　スパッタリングターゲット中の酸素濃度が０．０４質量％以下であることを特徴とする請求項１に記載のＩｎスパッタリングターゲット。 The In sputtering target according to claim 1, wherein the oxygen concentration in the sputtering target is 0.04 mass% or less.
  3. 　スパッタリングターゲット中のＢｉ、Ｓｂ、Ｓｎ、Ｚｎから選択された１種以上を含む合金相の最大粒径が５０μｍ以下であることを特徴とする請求項１に記載のＩｎスパッタリングターゲット。 2. The In sputtering target according to claim 1, wherein the maximum particle size of an alloy phase containing one or more selected from Bi, Sb, Sn, and Zn in the sputtering target is 50 μm or less.
  4. 　Ｂｉ、Ｓｂ、Ｓｎ、Ｚｎから選択される１種以上の元素を、合計で０．５～１０．０原子％含有し、残部がＩｎ及び不可避不純物からなる成分組成を有することを特徴とするＣＩＧＳ太陽電池製造用Ｉｎ膜。 CIGS characterized by containing one or more elements selected from Bi, Sb, Sn, and Zn in total in a range of 0.5 to 10.0 atomic% and the balance being composed of In and inevitable impurities In film for solar cell production.
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