TW201126003A - Cu-Ga sputtering target, method for manufacturing the target, light absorbing layer, and solar cell using the light absorbing layer - Google Patents

Cu-Ga sputtering target, method for manufacturing the target, light absorbing layer, and solar cell using the light absorbing layer Download PDF

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TW201126003A
TW201126003A TW099144878A TW99144878A TW201126003A TW 201126003 A TW201126003 A TW 201126003A TW 099144878 A TW099144878 A TW 099144878A TW 99144878 A TW99144878 A TW 99144878A TW 201126003 A TW201126003 A TW 201126003A
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target
film
alkali metal
cigs
absorbing layer
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TWI583811B (en
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Masakatsu Ikisawa
Hideo Takami
Tomoya Tamura
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Jx Nippon Mining & Metals Corp
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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
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Physical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)

Abstract

Disclosed is a Cu-Ga sputtering target, wherein the ratio of the number of the atoms of gallium (Ga) to the total number of the atoms of gallium (Ga) and copper (Cu), i.e., (Ga/(Ga+Cu)), is 0.2-0.6, and an alkali metal is contained. With the Cu-Ga target, additional manufacture of a layer that blocks diffusion of Na from an Na-containing layer and an Na-containing substrate is not required at the time of manufacturing the CIGS solar cell, and the concentration of the alkali metal in the CIGS layer can be made relatively uniform. A method for manufacturing the target, a light absorbing layer manufactured using the target, and the CIGS solar cell using the light absorbing layer are also provided.

Description

201126003 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種製作作為薄膜太陽電池層之光吸收 層之Cu-In-Ga-Se (以下，記載為cigs )四元系薄膜時所使 用之Cu-Ga系濺鍍靶、.該Cu_Ga系濺鍍靶之製造方法、由 該Cu-Ga系濺鍍靶所製作之光吸收層及使用有該光吸收層 之CIGS系太陽電池。 【先前技術】 近年來，正發展著將作為薄膜系太陽電池為高效率之 CIGS系太陽電池加以量產。作為其光吸收層即。⑽層之 製k方法已知有蒸鍍法及硒化法。藉由蒸鍍法而製造之 太陽電池具有轉換效率高之優點，但存在成膜速度低、成 本高、生產性低之缺點。 另一方面，硒化法雖然適合於產業性之大量生產，但 其進行如下之費事、複雜且危險之製程，而存在需要成本: 勞力、時間之缺點，上述製程係指於製作化與之積 層膜後，在氫化硒環境氣體中進行熱處理，將Cu、化、〇 硒化而形成CIGS膜。 n Ga 因此’最近業界正嘗試使用CIGS系機鍍乾，—[Technical Field] The present invention relates to a Cu-In-Ga-Se (hereinafter referred to as cigs) quaternary film which is used as a light absorbing layer of a thin film solar cell layer. A Cu-Ga-based sputtering target, a method for producing the Cu-Ga-based sputtering target, a light-absorbing layer produced by the Cu-Ga-based sputtering target, and a CIGS-based solar cell using the light-absorbing layer. [Prior Art] In recent years, CIGS-based solar cells, which are high-efficiency thin film solar cells, are being mass-produced. As its light absorbing layer, that is. The vapor deposition method and the selenization method are known as the method of the (10) layer. The solar cell produced by the vapor deposition method has the advantages of high conversion efficiency, but has a drawback of low film formation speed, high cost, and low productivity. On the other hand, although the selenization method is suitable for industrial mass production, it carries out the following complicated, complicated and dangerous processes, and there is a need for cost: labor and time defects, the above process refers to the production and After laminating the film, heat treatment is performed in a hydrogen selenide atmosphere to selenize Cu, ruthenium, and ruthenium to form a CIGS film. n Ga So 'the industry is currently trying to use the CIGS system to dry, —

製作CIGS系光吸收層，但現狀是未製作出用曰: 之合適之CIGS系濺鍍耙β 、T 雖然可使用CIGS系合今 ']：在έ士 <§*你炎、麻 速度快，生產性優里之為♦，進行成膜 屋性優異之直流（DC)濺鍍’但由於⑽系 201126003 合金燒結體之體電阻通常為數十Ω以上而比較高，因此存 在如下之問題··容易產生電弧等異常放電、膜中產生粒子 或膜質劣化。 一般而言，已知若於CIGS層中添加鈉（Na)等鹼金屬， 貝J藉由、纟σ晶粒徑之增大或載體濃度之增加等效果，而使得 太陽電池之轉換效率提高。 ^作為迄今為止已知之Na等之供給方法，有如下方法 等/·自含有Na之鈉鈣玻璃供給（專利文獻n ;以濕式法 於背面電極上設置含有鹼金屬之層（專利文獻2);以濕式 法於母材上設置含有鹼金屬之層（專利文獻3以乾式法 於背面電極上設置含有驗金屬之層（專利文獻4);以同時 蒸鍍法製作吸收層之同時、或者於成膜之前或之後添加鹼 金屬（專利文獻5 )。 j而，專利文獻1〜專利文獻3中所記載之方法均係藉 由CuGa硒化時的熱擴散來進行自含有鹼金屬之層向以gs 層之鹼金屬的供給，而難以恰當地控制鹼金屬於cigs層中 之濃度分佈。 其原因在於：當使用含有Na之鈉鈣玻璃作為基板時， 方面，因軟化點約為570。(：，故若設為6〇(Tc以上之高溫， 則容易產生龜裂，而不大能設定成高溫，另一方面，若不 於約500°C以上之高溫下進行硒化處理，則難以製作結晶性 良好之CIGS膜。即，存在硒化時之溫度可控範圍非常狹小， 於上述溫度範圍内難以控制Na之適當之擴散的問題。 又，專利文獻4及專利文獻5中所記載之方法存在如 201126003 下之情況，即因所形成之Na層具有吸濕性，故成膜後暴露 於大氣中時膜質發生變化並產生剝離，又，亦存在裝置之 設備成本非常高之問題。 又’有專利文獻記載當製作太陽電池用之吸收層時， 使用靶進行濺鍍，其中記載如下。 「驗金屬化合物之析出較有利的是藉由濺鍍或蒸鍍來 進打。此時，可使用鹼金屬化合物靶或鹼金屬靶與硒化銅 CuxSey之混合靶、或者鹼金屬靶與硒化銦之混合靶。 同樣地’亦可使用金屬-鹼金屬混合靶，例如Cu/Na、The CIGS-based light absorbing layer is produced, but the current situation is that it is not made of 曰: The suitable CIGS system is sputtered 耙β, T. Although the CIGS system can be used today]]: In the gentleman<§* you are hot and fast The production performance is excellent, and the direct current (DC) sputtering is excellent in film formation. However, since the body resistance of the (10) 201126003 alloy sintered body is usually several tens of Ω or more, the following problems exist. Abnormal discharge such as an arc is likely to occur, and particles or film quality are deteriorated in the film. In general, it is known that when an alkali metal such as sodium (Na) is added to the CIGS layer, the conversion efficiency of the solar cell is improved by the effect of increasing the particle diameter of the 纟σ crystal or increasing the concentration of the carrier. ^ As a supply method of Na, etc., which has been known so far, there are the following methods, etc. / supply of soda lime glass containing Na (Patent Document n; a layer containing an alkali metal is provided on the back electrode by a wet method (Patent Document 2) A layer containing an alkali metal is provided on the base material by a wet method (Patent Document 3 provides a layer containing a metal on the back electrode by a dry method (Patent Document 4); and an absorber layer is formed by simultaneous vapor deposition, or An alkali metal is added before or after the film formation (Patent Document 5). The methods described in Patent Documents 1 to 3 are all carried out from the layer containing the alkali metal by thermal diffusion during CuGa selenization. With the supply of the alkali metal of the gs layer, it is difficult to properly control the concentration distribution of the alkali metal in the cigs layer. The reason is that when a soda lime glass containing Na is used as the substrate, the softening point is about 570. However, if it is set to 6 〇 (high temperature of Tc or higher, cracks are likely to occur, and it is not possible to set it to a high temperature. On the other hand, it is difficult to perform selenization treatment at a high temperature of about 500 ° C or higher. Produce CIGS with good crystallinity That is, the temperature controllable range in the case of selenization is extremely narrow, and it is difficult to control the proper diffusion of Na in the above temperature range. Further, the methods described in Patent Document 4 and Patent Document 5 exist as in the case of 201126003. That is, since the Na layer formed is hygroscopic, the film quality changes and peels off when exposed to the atmosphere after film formation, and there is also a problem that the equipment cost of the device is very high. In the case of an absorber layer for a solar cell, sputtering is performed using a target, which is described below. "Precipitation of a metal compound is advantageously carried out by sputtering or vapor deposition. In this case, an alkali metal compound target or a base can be used. A mixed target of a metal target and a copper selenide CuxSey, or a mixed target of an alkali metal target and indium selenide. Similarly, a metal-alkali metal mixed target such as Cu/Na may be used.

Cu-Ga/Na或ln/Na。」（參照專利文獻4及專利文獻6之各 自之段落[0027])。 然而’此時之濺鍍係使用於形成太陽電池用吸收層之 前或製造過程中個別地摻雜鹼金屬時之靶的濺鍍。如此， 既然採用分別個別地摻雜之方法，則必需每次進行與其他 成分之調整，於成分不同之各靶之控制不充分之情形時， 存在成分產生變動之問題。 ^又，於下述專利文獻7中，揭示將鹼金屬化合物作為 蒸發源與其他成分元素同時進行蒸鍍，來形成膜之太陽電 “吸收層的开々成方式（參照該文獻之段落[〇〇 19]及圖})。 於$情形時，亦與上述專利文獻4及專利文獻6相同，存 ^ 不充》進彳了與其他蒸鍍物f之調整（成分及蒸鍵條 ^ 則產生成分之變動之問題。Cu-Ga/Na or ln/Na. (Refer to paragraphs [0027] of each of Patent Document 4 and Patent Document 6). However, sputtering at this time is used for sputtering of a target when an alkali metal is separately doped before or during the formation of an absorption layer for a solar cell. As described above, since the method of individually doping is employed, it is necessary to adjust the composition with other components each time, and when the control of each target having different components is insufficient, there is a problem that the composition fluctuates. Further, in the following Patent Document 7, it is disclosed that the alkali metal compound is vapor-deposited simultaneously with other constituent elements as an evaporation source to form a film solar photovoltaic "opening method of the absorption layer (refer to the paragraph of the document [〇 〇19] and Fig.}). In the case of $, the same as the above-mentioned Patent Document 4 and Patent Document 6, the adjustment of the other vapor deposition material f (the composition and the steaming key strip are generated) The problem of changes in ingredients.

.另方面，於非專利文獻1中，揭示於為奈米粉末原 ^之機械合金之粉末之製作後’進行HIP處理而成的CIGSOn the other hand, in Non-Patent Document 1, a CIGS which is subjected to HIP treatment after the production of a powder of a mechanical alloy of nano powder is disclosed.

5 S 201126003 四元系合金濺鍍靶之製造方法及該靶之特 藉由該製造方法所獲得之CIGS四元系合金生。然而，關於 雖然有密錢高此-定丨±記載1 之特性， 不明。 U之密度之數值完全 又，推測因使用奈米粉末，故氧濃 a 之氧濃度亦完全不明…亦完全未扩：广但燒結體 影響之體電阻。進而，由於使用昂貴之；米粉性造成 因此不適合作為要求板Λ 士 —丄扯 乍為原料， 哀低成本之太陽電池用材料。 又’於非專利文獻2中棍5 S 201126003 A method for producing a quaternary alloy sputtering target and a target of the CIGS quaternary alloy obtained by the production method. However, it is unclear as to the characteristics of the dense money, which is high. The value of the density of U is completely different. It is speculated that the oxygen concentration of oxygen concentration a is completely unknown due to the use of nano powder. It is also completely unexpanded: the bulk resistance affected by the sintered body. Furthermore, it is expensive to use; it is not suitable for use as a raw material for the use of rice flour, and it is a low-cost solar cell material. Further, in the non-patent document 2

Se2，且其密产為5.Λ 揭不有組成為α(Ά·2) 且其“為5_5g/cm3,相對密度為㈣之庐 而，其製造方法，僅凡、。體 t、m & 4有藉由熱壓㈣單獨合成之原料 知末進订燒結，而未明示具體之製造方法。又， 所獲得之燒結體之體電阻。 ° 專利文獻2 專利文獻3 專利文獻4 專利文獻5 專利文獻6 專利文獻7 專利文獻1 :日本特開2004-47917號公報 曰本專利第3876440號公報 曰本特開2006-210424號公報 曰本專利第4022577號公報 曰本專利第33 1 1873號公報 曰本特開2007-266626號公報 曰本特開平8-102546號公報 非專利文獻 非專利文獻 1 : Thin Solid Films, 3 32 (1998)，P.340-344 非專利文獻2 :電子材料2009年11月42-45頁 201126003 【發明内容】 #於上述情形，丰發明之目的在於提供一種於製作 CIGS系太陽電池時，無需另行製作含有Na之層或來自基 板之Na擴散阻斷層，並可使CIGS層中之驗金屬濃度比較 均勻之Cu-Ga系靶；以及提供該靶之製造方法、由該靶所 製作之光吸收層及使用_該光吸收層之CIGS系太陽電池。 為解決上述課題，本發明者等人發現：藉由將添加有 驗金屬之Cu-Ga用作濺鍍靶進行濺鍍而獲得之Cu-Ga膜， 在其膜厚方向上，鹼金屬濃度大致變得均勻，故於其後之 硒化後，CIGS膜中之鹼金屬之濃度分佈與以往之藉由擴散 之/辰度分佈相比，亦格外地提高，因此將該CIGS層作為光 吸收層之太陽電池之轉換效率會提高。又，本發明者等人 發現：藉由添加鹼金屬，可降低體電阻，進而可於濺鍍時 抑制異常放電。本發明係基於該見解而成者。 即本發明提供： l —種Cu-Ga系濺鍍靶，其特徵在於： 鎵（Ga)原子數相巧於鎵（以）及銅（Cu)之合計原 子數之比率（Ga/(Ga+Cu))為〇.2〜〇6，且含有驗金屬: 2·如上述1之濺鍍靶，其中，鹼金屬為選自鋰（u)、 鈉（Na)、鉀⑷中之至少一種元素。 3.如上述1或2之濺鍍靶，其中，鹼金屬之濃度為1…6 〜l〇18cm_3〇 、4.如上述1至3中任一項之濺鍍靶，其相對密度為97% 201126003 又，本發明提供： 5·種Cu-Ga系濺鍍靶之製造方法，其特徵在於： =藉由燒結來製造鎵（Ga)原子數相對於鎵 銅(㈤之合計原子數之比率（_a+Cu))為〇.2〜 •且含有驗金屬之cu_Ga㈣料時，❹選自U2〇、Se2, and its dense production is 5. 揭 Unexposed that the composition is α (Ά·2) and its "is 5_5g/cm3, the relative density is (4), and its manufacturing method, only the body, t, m &amp 4 There is a raw material which is separately synthesized by hot pressing (4), and the specific manufacturing method is not specified. Further, the body resistance of the obtained sintered body is obtained. Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 Patent Document 6 Patent Document 7 Patent Document 1: JP-A-2004-47917, JP-A No. 3, 876, 440, JP-A-2006-210424, PCT Patent No. 4022577, Japanese Patent No. 33 1 1873 JP-A-2007-266626, JP-A-H08-102546, Non-Patent Document Non-Patent Document 1: Thin Solid Films, 3 32 (1998), P. 340-344 Non-Patent Document 2: Electronic Materials 2009 November 42-45, 201126003 [Invention] In the above situation, the purpose of the invention is to provide a Na diffusion barrier layer for the production of CIGS-based solar cells without separately forming a layer containing Na or from a substrate. Cu-concentrating the metal concentration in the CIGS layer A Ga-based target; a method for producing the target, a light-absorbing layer made of the target, and a CIGS-based solar cell using the light-absorbing layer. In order to solve the above problems, the inventors have found that by adding A Cu-Ga film obtained by sputtering a metal-coated Cu-Ga as a sputtering target, the alkali metal concentration is substantially uniform in the film thickness direction, and thereafter, after selenization, in the CIGS film The concentration distribution of the alkali metal is also particularly improved as compared with the conventional diffusion/density distribution, so that the conversion efficiency of the solar cell using the CIGS layer as the light absorbing layer is improved. Further, the inventors and the like It has been found that by adding an alkali metal, the bulk resistance can be lowered, and abnormal discharge can be suppressed at the time of sputtering. The present invention is based on the findings. The present invention provides: a Cu-Ga-based sputtering target, The characteristic is that the ratio of the number of gallium (Ga) atoms to the total number of atoms of gallium (or) and copper (Cu) (Ga/(Ga+Cu)) is 〇.2~〇6, and the metal is included: 2 The sputtering target according to the above 1, wherein the alkali metal is selected from the group consisting of lithium (u), sodium (Na), and potassium (4). 3. The sputtering target of any one of the above 1 or 3, wherein the concentration of the alkali metal is 1...6~l〇18cm_3〇, 4. The sputtering target according to any one of the above 1 to 3, The density is 97%. 201126003 Further, the present invention provides: 5. A method for producing a Cu-Ga-based sputtering target, which is characterized in that: = a gallium (Ga) atomic number is produced by sintering relative to a gallium copper (a total atom of (5) When the ratio of the number (_a+Cu) is 〇.2~• and contains the metal cu_Ga (four) material, the ❹ is selected from U2〇,

Na20、K2〇、U2S、Na2S ' k2S、Li2Se、、〖A 中之 至少一種化合物作為用於添加鹼金屬之化合物e 又’本發明提供： 6·一種光吸收層，其係使用上述丨至4 Cu-Ga系濺鍍靶進行成膜而成。’ 7· 一種太陽電池，其使用有上述6之光吸收層。 本發明具有如下之非常優異之效果：因Cu_Ga系把中 含有驗金屬’故可提高對㈣進行舰所得之膜中之驗金 屬濃度之均句性’ CIGS膜巾之驗金屬之濃度分佈與以往之 藉由擴散之漠度分佈相比格外地提高’因此將該dGs層作 為光吸收層之太陽電池之轉換效率會提高。 又，本發明藉由於濺鍍靶中添加:鹼金屬，而具有可降 低體電阻，並可於濺鍍時抑制異常放電之優異之效果。 【實施方式】 本發明之Cu-Ga系濺鍍靶中，Ga原子數相對於&amp;及 Cu之合計原子數之比率（Ga/(Ga+Cu))為&quot;〜〇 6。其 原因在於：由該範圍之組成之Cu_Ga所製作的cigs膜之帶 隙在與太％光光譜之關係上較適合，並且會提高使用Gas 201126003 膜之CIGS系太陽電池之轉換效率。 ⑽係由銅（CU)、銦㈤、鎵（Ga)及袍⑻ 所構成之四元系合金，其組成係由組成式CUlni_xGaxSe2 (其中，X ' y分別表示原子比率） x 干^所表不，其組成範圍為 0 &lt; 0.5、0.04。 於Cu-Ga系錢㈣:中，於Ga之原子數比率為0之情形 時’ CIGS糸膜不含以而成為CIS膜。其帶隙為HV， 但在與太陽光之關係上最適合之太陽電池之帶隙為14 eV。因此，由於帶隙過小，故太陽電池之電壓會不夠高， 轉換效率無法變高。 Φ於Ga之原子數比率為〇 6之情形時，帶隙 成為1.42 eV，可使轉換效率變得比較高。然而，若〜之 原子數比率超過0.6,則形成如下之傾向：由於帶隙進一步 變^，因此為生成電子所必需之能量變得過高，無法增大 太陽電池之電流，轉換效率變小。因此，&amp;原子數比^ 適當範圍係（（^/ (Ga+in))為〇 2〜〇 6。 本發明之CU_Ga系濺㈣之特徵在於含有驗金屬。將 本發明不记載為Cu_Ga濺鍍靶，而記載為「…系」之Cu-仏 系濺鑛乾之原因在於：該義乾之主成分係由&amp;及〇 成’但亦含有鹼金屬。 田製作CIGS膜時，驗金屬帶來結晶粒徑增大或曲 度增加等效果，並且有提高CiGS系太陽電池之轉 : 效果。 、千芡 驗金屬亦被稱為週期表之Ia元素，但於本發明中，氣 201126003 。其原因在於：I、，ί 難Μ有效地添加氫 電特性及組織特性有致。 且 不包含於鹼金屬内 未發現其對表現出 至二由添加驗金屬，…價元素之驗金屬取代 μ 晶格位置’藉此釋放出孔；從而提高導電性。因 此，只要為驗金屬，則具有上述效果，因此任意元 政，，就化合物之容易利用程度或價格之觀點而言，較理 6的疋Li Na、κ 〇尤其，就表現出效果或化合物之利用容 易性等觀點而t ’較理想的是Na。 又，該等金屬為元素單體時反應性非常高，尤其與水 激’、、、反應而較危險’因此較理想的是以含有該等元素之化 合：之形態添加。因此，較理想的是使用容易獲取且比較 廉價,Li2〇、Na2〇、K2〇、Li2s、Na2S、K2S ' U2Se ' Na2Se、 、專作為化合物。尤其，於使用Se化合物之情形時，由 ； 於CIGS中為構成材料，因此無產生晶格缺陷或兌他 組成材料等之虞，故可謂更理想。£ '、 驗金屬之濃度與導電性及結晶性相關，較理想的是1 〇16 ]〇^ tv» * ^ ^.jl. m 。右驗金屬濃度未滿10丨6 cm·3，則當形成CiGS 膜時’無法獲得夠低且適當之導電性，故鹼金屬添加效果 不充分’另一方面，即使鹼金屬濃度超過1〇18 cm·3，效果 亦飽和且靶之相對密度會下降。 驗金屬濃度可藉由各種分析方法進行分析，例如， Cu-Ga系乾中之鹼金屬濃度可藉由rcp分析等方法求出，Na20, K2〇, U2S, Na2S 'k2S, Li2Se, and at least one compound of A as a compound for adding an alkali metal e. The present invention provides: 6. A light absorbing layer which uses the above-mentioned 丨 to 4 A Cu-Ga sputtering target is formed by film formation. </ RTI> A solar cell using the light absorbing layer of the above 6. The present invention has the following excellent effect: since the Cu_Ga system contains a metal test, it can improve the uniformity of the metal concentration of the metal in the film obtained by the ship. The diffusion distribution by diffusion is exceptionally improved. Therefore, the conversion efficiency of the solar cell in which the dGs layer is used as the light absorbing layer is improved. Further, the present invention has an effect of suppressing abnormal discharge and suppressing abnormal discharge during sputtering by adding an alkali metal to the sputtering target. [Embodiment] In the Cu-Ga-based sputtering target of the present invention, the ratio of the number of Ga atoms to the total number of atoms of &amp; and Cu (Ga/(Ga+Cu)) is &quot;~〇6. The reason for this is that the band gap of the cigs film made of Cu_Ga composed of this range is suitable in relation to the spectrum of the %% light, and the conversion efficiency of the CIGS-based solar cell using the Gas 201126003 film is improved. (10) A quaternary alloy composed of copper (CU), indium (five), gallium (Ga), and gown (8), the composition of which consists of the composition formula CUlni_xGaxSe2 (where X ' y represents the atomic ratio, respectively) x , its composition range is 0 &lt; 0.5, 0.04. In the case of Cu-Ga type money (4): when the atomic ratio of Ga is 0, the CIGS film does not contain CIS film. The band gap is HV, but the band gap of the solar cell that is most suitable for the relationship with sunlight is 14 eV. Therefore, since the band gap is too small, the voltage of the solar cell is not high enough, and the conversion efficiency cannot be increased. When the ratio of Φ to the atomic number of Ga is 〇 6, the band gap becomes 1.42 eV, which makes the conversion efficiency relatively high. However, if the atomic ratio is more than 0.6, the band gap is further changed. Therefore, the energy necessary for generating electrons is too high, and the current of the solar cell cannot be increased, and the conversion efficiency is small. Therefore, the &amp; atomic ratio ^ is an appropriate range ((^/(Ga+in))) is 〇2 to 〇6. The CU_Ga sputtering (four) of the present invention is characterized by containing a metal test. The present invention is not described as Cu_Ga. The reason why the Cu-lanthanum splash is described as "..." is that the main component of the stem is from &amp; and 〇成' but also contains alkali metal. When making CIGS film, the test The metal brings about an increase in crystal grain size or an increase in curvature, and has an effect of improving the conversion of the CiGS solar cell. The metal is also referred to as the Ia element of the periodic table, but in the present invention, the gas 201126003 The reason is: I,, ί is difficult to effectively add hydrogen-electric properties and structural properties. It is not included in the alkali metal, and it is not found in the alkali metal. The metal is replaced by the metal. The lattice position 'is thereby releasing the hole; thereby improving the conductivity. Therefore, as long as it is a metal test, the above effect is obtained, and therefore, any elemental policy, in terms of the ease of use of the compound or the price, is reasonable.疋Li Na, κ 〇 especially, it shows the effect From the viewpoints of easiness of use of the compound, etc., it is preferable that Na is preferable. When these metals are elemental monomers, the reactivity is extremely high, and in particular, it is more dangerous to react with water, and therefore it is preferable. The compound containing these elements is added in a form. Therefore, it is preferable to use it easily and inexpensively, and Li2〇, Na2〇, K2〇, Li2s, Na2S, K2S 'U2Se 'Na2Se, and specifically, as a compound. In the case of using the Se compound, it is a constituent material in CIGS, so it is more desirable because it does not cause lattice defects or composition of materials, etc., and the concentration, conductivity, and crystallinity of the metal are examined. Correspondingly, it is ideal that 1 〇16 ]〇^ tv» * ^ ^.jl. m. If the concentration of the right metal is less than 10丨6 cm·3, then when the CiGS film is formed, 'the low and proper conductivity cannot be obtained. Sex, the alkali metal addition effect is not sufficient. On the other hand, even if the alkali metal concentration exceeds 1〇18 cm·3, the effect is saturated and the relative density of the target is decreased. The metal concentration can be analyzed by various analytical methods, for example, , Cu-Ga dry base The metal concentration can be obtained by methods such as rcp analysis.

Cu-Ga系膜中之鹼金屬濃度及其膜厚方向之分佈可藉由 SIMS分析等求出。 201126003 本發明之CU-Ga系濺㈣之 佳為98%以上，更佳為991 “為97%以上’較 之實際之絕對密度除以'其目對密度係將燒結體乾 之比。 H成^之理論密度所獲得的值 若靶之相對密度較低，則靶 當濺鍍中顯露出内部空孔時，容 $内部空孔’故 之飛濺或異常放電，膜t之粒子產生:以空孔周邊為起點 陽電池之轉換效率下降之原因之…θ加，而成為㈣太 又，靶表面之凹凸化提早進行 (節結一》為起點之異常放電等。易因：生以表面突起 將乾之相對密度至少設定成97%以上。’較理想的疋 化4!!=等例如可如下般製作。將c&quot;a及驗金屬 放，内，於加壓至約。.5 Mpa = =行稱量後， 古於护赴奶α 大乳昼之加熱爐内設定成 ::嫁點約50〜200t之高溫，使混合原料溶解保持約丨 而押r:::取出1次合成原料。將該1次合成原料粉碎 水霧碎方法，有機械粉碎、氣體霧化法、 夂霧化法等，可使用任一種方法。 選調㈣合微粉原料之粒度分佈後，進行熱 例如1於熱壓條件’依Ga濃度的不同而適當條件有所不同， ; a濃度為30 at%之情形時，熱壓條件為 =、壓力3G〜4G贴左右。適當之保持時間為約卜3 =太適當之冷卻速度為5t/min以上、適#之對於混合原 枓杨末之加壓力為3〇〜4〇MPa。於此種之熱壓條件下，可 201126003 謀求提兩Cu-Ga系乾之密度。 又，於溫度上升速度或保持時間等溫度分佈與屋力施 加分佈之關係中’與將溫度定為設定之最高溫度之後再施 加壓力之後壓方式相比’先施加壓力之先壓方式因燒結前 原料粉末更細微地粉碎，故對提高燒結密度更有效。 所製作之Cu-Ga系燒結體之密度可藉由阿基米德法進 行分析，Ga濃度可㈣ICP分析法,行分析，驗金屬濃度 可使用GDMS法等進行分析。 將上述Cu-Ga系燒結體機械加工成例如直徑為6英 吋、厚度為6mm而製成靶。將該靶，錮作為焊料貼附於支 持板，而製成濺鍍靶-支持板組裝體： 藉由使用忒靶-支持板組裝體進行濺鍍，可獲得 系膜。 構成作為太陽電池之光吸收層之CIGS層之前一階段的 CuGa系膜可如上述般製作，因此該心分以外之太陽電池之 各構成部分可使用以往之方法而製作。 即，於玻璃基板上對鉬電極進行濺鍍後，將In濺鍍成 膜’然後將含有驗金屬之CuGa乾濺鍵成膜，其後以氮化场 對In與含有驗金屬之CuGa之積層膜部分進行硒化，形成 含有鹼金屬之CIGS膜，從而可製作光吸收層。 其後’進而於CIGS層上將CdS濕式成膜，形成緩衝層 之Zn〇或為透明導電臈之添加鋁之ZnO，藉此可製作使用 含有鹼金屬之CIGS層之太陽電池。 12 201126003 實施例 繼而，對本案發明之實施例及比較例進行說明。再者， 以下之實施例僅表示代表性之例，無需將本案發明限制於 s玄等實施例，而應在說明書所記載之技術思想之範圍内進 行解釋。 (實施例1 ) 將Cii原料及Ga原料以Ga原子數之比率成為ο」、 NasSe之濃度成為1〇i7 cm·3的方式進行稱量然後放入碳 製坩堝内，在施加有0.5 Mpa之氬氣之加熱爐内於丨〇〇〇 C下使其溶解之後，以5〜丨〇充/mjn之冷卻速度進行冷卻後 取出合成原料。 繼而’將該合成原料放入水霧化裝置之碳坩堝内，於 1000 C下使其熔解後，一面滴加炼解液一面向滴加液中噴 射10 Mpa之高壓水，獲得Cu-Ga系混合微粉。將該混合微 叙壓渡後，於12〇它下使其乾燥，獲得混合微粉原料。 以作為熱壓條件之5 °C /min之升溫速度將該混合微粉 原料自室溫升溫至65(TC為止後，於65(TC下保持2小時並 且施加35 Mpa之壓力。其後，以5。(： /min之降溫速度冷卻 後取出燒結體。所獲得之Cu-Ga系燒結體之相對密度為 99.9%。 將該燒結體加工成直徑為6英吋、厚度為6 mm之圓板 狀而製成濺鍍靶。繼而，^吏用直徑為4英吋且厚度為〇 .7 之Corning 173 7玻璃作為基板，於該玻璃基板上對In乾進 行減鑛，而使膜厚變成1以m。 13 5. 201126003 其後’於將賤鍍功率設定為直流（DC，Direct Current ) 1000 w，將環境負體畔宁 虱體°又疋為虱氣，將氣體流量設定為50 時壓力設定為〇.5 &amp;之條件下對上述所製作 之CUGa _練進行_，製成膜厚為l“m之膜。將所 製作之In及Cu-Ga系之積層膜放入爐内，—面供給硒化氫 氣體’一面將爐内1度設定為50〇4進行B時站化處理。 藉由四端子法測定所取出之膜之電阻率與膜厚，求出 膜之電阻率’結果A 3.1 QCm。將以上之結果示於表上。 如根攄以上可明確般，顯示出達成本案發明之目的之良好 之值。 [表1]The alkali metal concentration in the Cu-Ga film and the distribution in the film thickness direction can be determined by SIMS analysis or the like. 201126003 The CU-Ga sputtering (four) of the present invention is preferably 98% or more, more preferably 991 "97% or more", which is the actual absolute density divided by the ratio of the density to the sintered body. The value obtained by the theoretical density is lower if the relative density of the target is lower, then the target exhibits an internal void when it is sputtered, so that the internal void is splashed or abnormally discharged, and the particle of the film t is generated: The periphery of the hole is the cause of the decrease in the conversion efficiency of the starting point positive battery... θ is added, and (4) is too much, and the surface of the target surface is prematurely advanced (nodule 1) as the starting point of abnormal discharge, etc. Easy cause: the surface protrusion will be produced The relative density of the dryness is set to at least 97%. The preferred 疋化4!!= etc. can be produced as follows. The c&quot;a and the metal are placed, and the pressure is applied to about .5 Mpa = = After the weighing, the heating furnace in the ancient milk mash is set to:: the wedding point is about 50~200t high temperature, so that the mixed raw material is dissolved and kept at about r::: The synthetic raw material is taken out once. The method for pulverizing the primary synthetic raw material by water misting may be mechanical pulverization, gas atomization method, hydrazine atomization method, or the like. By using any method. After adjusting the particle size distribution of the (4) micro-powder raw material, the heat is, for example, 1 in the hot pressing condition 'different depending on the Ga concentration, and the appropriate conditions are different; when the concentration is 30 at%, the hot pressing condition For the =, pressure 3G ~ 4G stickers around. Appropriate holding time is about 3 = too appropriate cooling rate of 5t / min or more, suitable for the mixing of the original 枓 Yang end of the pressure is 3 〇 ~ 4 〇 MPa. Under such hot pressing conditions, it is possible to increase the density of the two Cu-Ga-based dry layers in 201126003. In addition, in the relationship between the temperature distribution such as the temperature rise rate or the holding time and the distribution of the house force, the temperature is set to be set. After the pressure is applied after the maximum temperature, the pressure method is more pulverized than the raw material powder before the sintering because of the first pressure application method. The density of the produced Cu-Ga sintered body can be borrowed. The analysis can be carried out by the Archimedes method, and the Ga concentration can be analyzed by the ICP analysis method, and the metal concentration can be analyzed by the GDMS method or the like. The Cu-Ga sintered body is machined to have a diameter of, for example, 6 inches and a thickness of Made of 6mm The target and ruthenium are attached as a solder to a support plate to form a sputtering target-supporting plate assembly: a sputtering film is used by sputtering using a ruthenium target-supporting plate assembly, and a film is obtained. The CuGa-based film of the previous stage of the CIGS layer of the light absorbing layer can be produced as described above, and thus the constituent parts of the solar cell other than the core can be produced by a conventional method. That is, the molybdenum electrode is sputtered on the glass substrate. After plating, In is sputtered into a film, and then a CuGa-containing dry-spray bond containing a metal is formed into a film, and then a portion of the laminated film of In and the metal-containing CuGa is selenized by a nitriding field to form an alkali metal-containing layer. A CIGS film to make a light absorbing layer. Thereafter, CdS is wet-formed on the CIGS layer to form a buffer layer of Zn or a transparent conductive germanium-added ZnO, whereby a solar cell using an alkali metal-containing CIGS layer can be produced. 12 201126003 EXAMPLES Next, examples and comparative examples of the present invention will be described. In addition, the following examples are merely representative examples, and the invention is not limited to the embodiment of the invention, but should be construed within the scope of the technical idea described in the specification. (Example 1) The Cii raw material and the Ga raw material were weighed so that the ratio of the number of Ga atoms was 」, and the concentration of NasSe was 1〇i7 cm·3, and then placed in a carbon crucible, and 0.5 Mpa was applied thereto. After the argon gas was dissolved in 加热C, it was cooled at a cooling rate of 5 to 丨〇/mjn, and the synthetic raw material was taken out. Then, the synthetic raw material was placed in a carbon crucible of a water atomizing device, and after melting at 1000 C, a molten iron solution was sprayed into the dripping liquid to spray 10 Mpa of high-pressure water to obtain a Cu-Ga system. Mix the fine powder. After the mixing was carried out, it was dried under 12 Torr to obtain a mixed fine powder material. The mixed fine powder material was heated from room temperature to 65 at a temperature increase rate of 5 ° C /min as a hot press condition, and was maintained at 65 (TC for 2 hours and applied at a pressure of 35 MPa). Thereafter, it was 5. (: /min was cooled at a cooling rate, and the sintered body was taken out. The relative density of the obtained Cu-Ga sintered body was 99.9%. The sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm. A sputtering target is formed. Then, Corning 173 7 glass having a diameter of 4 inches and a thickness of 〇.7 is used as a substrate, and the In dry is reduced on the glass substrate to make the film thickness 1 to m. 13 5. 201126003 After that, set the 贱 plating power to DC (Direct Current) 1000 W, and turn the ambient negative body into a helium gas. When the gas flow rate is set to 50, the pressure is set to Under the conditions of 〇.5 &amp; CUGa _ _ produced by the above, a film having a film thickness of l "m" was formed, and the produced In and Cu-Ga laminated film was placed in the furnace. The supply of hydrogen selenide gas is set to 50 〇 4 in the furnace to perform the B-time standing process. The four-terminal method is used to measure the taken out. The resistivity of the film and the film thickness were determined, and the resistivity of the film was determined as a result A 3.1 QCm. The above results are shown in the table. As can be clearly seen from the above, it is a good value for achieving the object of the present invention. Table 1]

14 201126003 (實施例2〜實施例5 ) 將Ga之原子數之比率、Ga/ (Ga+Cu)於實施例2中 設定為0.2,於實施例3中設定為〇4,於實施例4中設定 為〇.5’於實施例5中設定為〇.6β除此以外，以與實施例丄 相同之條件進行燒結體之製作 '薄膜之製作。將燒結體及 薄膜之特性之結果同樣示於表1。 如上述表i所示’於實施例2中，燒結體靶之相對密 度成為99.8%、CIGS膜電阻率成為31 ，於實施例3 中’燒結體乾之相對密度成為98 8%、CIGS膜電阻率成為 3.3 ，於實施例4中，燒結體乾之相對密度成為％篇、 CIGS膜電阻率成為3 4心爪，於實施例$巾，燒結體靶之 相對密度成為97.8%、CIGS膜電阻率成為3 2心：，均顯 示出達成本案發明之目的之良好之值。 (實施例6〜9 ) 除了將添加鹼金屬時之化合物變更為表丨中分別所圮 載者以外，以與實施例1相同之條件進行燒結體之製作°、 薄臈之製作。即，實施例6中使用Na2〇作為鹼金屬化合物， 實施例7中使用Na2S作為驗金屬化合物，實施例8中使用 作為驗金屬化合物’實施例9中使用❿作為驗金 屬化合物。將燒結體及薄膜之特性之結果同樣示於表卜 如上述表i所示’於實施例6中，燒結體靶之相對密 度成為99.2%、CIGS膜電阻率成為〇 电手成為3.9 Ω cm，於實施例7 中’燒結體乾之相對密度成為99_4%、cigs膜電 一，於實施例8中，燒結體乾之相對密度成為99.1%14 201126003 (Example 2 to Example 5) The ratio of the atomic number of Ga and Ga/(Ga+Cu) were set to 0.2 in Example 2, and was set to 〇4 in Example 3, and in Example 4 The production of a sintered film was carried out under the same conditions as in Example 除 except that the setting of 〇.5' was set to 〇.6β in Example 5. The results of the characteristics of the sintered body and the film are also shown in Table 1. As shown in the above Table i, in Example 2, the relative density of the sintered body target was 99.8%, and the CIGS film resistivity was 31. In Example 3, the relative density of the sintered body was 98 8%, and the CIGS film resistance was obtained. The ratio was 3.3. In Example 4, the relative density of the sintered body was %, and the CIGS film resistivity was 34 cm. In the example, the relative density of the sintered body target was 97.8%, and the CIGS film resistivity was obtained. Becoming a 3 2 heart: all show good value for achieving the purpose of the invention of the present invention. (Examples 6 to 9) The production of the sintered body was carried out under the same conditions as in Example 1 except that the compound in the case where the alkali metal was added was changed to the one shown in the Table. Namely, in Example 6, Na2〇 was used as the alkali metal compound, Na2S was used as the metal test compound in Example 7, and Example 8 was used as the metal test compound. The ruthenium used in Example 9 was used as the metal test compound. The results of the characteristics of the sintered body and the film are also shown in the table. As shown in the above Table i, in Example 6, the relative density of the sintered body target was 99.2%, and the CIGS film resistivity became 3.9 Ω cm. In Example 7, the relative density of the sintered body was 99_4%, and the cigs film was one. In Example 8, the relative density of the sintered body became 99.1%.

15 S 201126003 CIGS膜電阻率成 相對密度成為98.9〇/: “，於實施例9中，燒結體乾之 示出達成本案發明C:S膜電阻率成為3·7 ，均顯 之目的之良好之值。 (實施例10〜u ) @了將鹼金屬濃度變、 以與實施例1相同 ‘、’、 /刀別所記載者以外， 即，實施例1。中將二：行燒結體:之製作、薄膜之製作。 11中將驗全思凿 屬濃度設定為2χ1〇Ά實施例 特性之-果η:度設定為8Χ1°17 一將燒結體及薄膜之 竹丨王之、，.〇果冋樣示於表t。 度成電實施例10中’燒結體乾之相對密 中，燒結體…=阻率成為一，於實施例11 ⑴成為&quot;.5%、CIGS膜電阻率成為 (比較例卜2)成本案發明之目的之良好之值。 以與屬濃度變更為表1中分別所記載者以外， 與實施例1相同之條件進行燒結體之製作、薄膜之製作 即，比較例1中將驗金屬濃度較為2X1…m_3，、 中:驗金屬濃度設定為8xl〜。比較例i之驗： 又父低，相反比較你&quot;之鹼金屬濃度過高，均超出本荦發 明之條件。將燒結體及薄膜之特性之結果同樣示 =發 如上述表1所示’於中 度為L無特別問題 &lt; 』體乾之相對密 GS膜電阻率高達69.&quot;cm， 為不良。於比較例2中，CIGS膜電阻率為ΐ9“而良好， 但燒結體靶之相對密度下降為94 3%，成為問題。 201126003 [產業上之可利用性j 根據本發明，旦右1 / 货乃具有如τ之非常優異之效果 糸靶中含有鹼金屬，故可楹古 Cu'Ga 了鈐巧由該靶濺鍍所得之膜中夕认 金屬濃度之均勻性，CIGfSH^tb 、 ^ ⑽膜中之驗金屬之濃度分佈與以往 错由擴散之/辰度分佈相比格外地提高，因此將該cigs層 作為光吸收層之太陽電池之轉換效率提高。因此，本發明 作為CIGS系太陽電池之製造用材料有用。 【圖式簡單說明】 【主要元件符號說明】 Μ ***% 17 515 S 201126003 The CIGS film resistivity becomes a relative density of 98.9 〇/: "In the ninth embodiment, the sintered body is dried to achieve the invention. The C:S film resistivity is 3.7, which is good for the purpose. (Examples 10 to u) @ The alkali metal concentration was changed to be the same as in the first embodiment, except for the description of ', ', or Knife, that is, Example 1. The second: row sintered body: In the production of the film, the concentration of the test is set to 2χ1〇Ά. The characteristics of the example-fruit η: the degree is set to 8Χ1°17. The results are shown in Table t. In Example 10, the sintered body was relatively dense, the sintered body...=the resistivity became one, and in Example 11 (1), it became &quot;.5%, and the CIGS film resistivity became (comparative Example 2) A good value for the purpose of the invention of the invention. The production of the sintered body and the production of the film were carried out under the same conditions as in Example 1 except that the genus concentration was changed to that described in Table 1, that is, Comparative Example 1 The concentration of metal in the test will be 2X1...m_3, and the concentration of the test metal is set to 8xl~. The test of comparative example i: The father is low, on the contrary, the alkali metal concentration of you is too high, which exceeds the conditions of the invention. The results of the characteristics of the sintered body and the film are also shown as follows: = as shown in Table 1 above. The problem is that the relatively dense GS film resistivity of the body is as high as 69. &quot;cm, which is bad. In Comparative Example 2, the CIGS film resistivity is ΐ9" and is good, but the relative density of the sintered body target is decreased to 94 3 %, becomes a problem. 201126003 [Industrial Applicability j According to the present invention, the right 1 / cargo has a very excellent effect such as τ, the target contains alkali metal, so it can be obtained from the target by Cu'Ga The uniformity of the metal concentration in the film, the concentration distribution of the metal in the CIGfSH^tb and ^(10) films is exceptionally improved compared with the previous misdifference/density distribution, so the cigs layer is used as the light absorbing layer. The conversion efficiency of the solar cell is improved. Therefore, the present invention is useful as a material for manufacturing a CIGS-based solar cell. [Simple description of the diagram] [Explanation of main component symbols] Μ ***% 17 5

Claims (1)

201126003 七、申請專利範圍： 1'種Cu-Ga系濺鍍乾，其特徵在於： 嫁（Ga)原子數相對於鎵（（Ja)及銅（cu)之合計原 子數之比~率（Ga/(Ga+Cu))為〇 2〜〇 6，且含有鹼金屬。 2.如申凊專利範圍第丨項之濺鍍靶，其中，鹼金屬為選 自鋰（Li)、# (Na)'鉀（κ)中之至少一種元素。 3·如申請專利範圍第1項或第2項之濺鍍靶，其中，鹼 金屬之濃度為l〇16〜1〇18cm-3。 4. 如申請專利範圍帛i項至第3項中任一項之濺鍍靶， 其相對密度為97%以上。 5. 一種Cu-Ga系濺鍍靶之製造方法，其特徵在於. 於藉由燒結來製造鎵（Ga)原丰數相對於鎵（Ga) 鋼（Cu)之合計原子數之比率（Ga/( Ga+Cu))為〇 2〜〇 6 且3有驗金屬之Cu-Ga系濺鍍靶時，使用選自Li 〇、\ K 〇、τ 以 a】〇、 2 、Li2S、Na2S、K2S、Li2Se、Na2Se、K2Se 中之至 + 5物作為用於添加驗金屬之化合'物e 6· ~~種光吸收層，其係使用申請專利範圍第i 卜 項中杯 κ 崎至弟4 仕—項之Cu-Ga系濺鍍靶進行成膜而成。 7·~'種太陽電池，其使用有申請專利範圍第6 收層。 視之光吸201126003 VII. Patent application scope: 1' kind of Cu-Ga-based sputtering dry, characterized by: ratio of the number of married (Ga) atoms to the total number of atoms of gallium ((Ja) and copper (cu) (Ga) /(Ga+Cu)) is 〇2~〇6, and contains an alkali metal. 2. The sputtering target of the ninth aspect of the invention, wherein the alkali metal is selected from the group consisting of lithium (Li), # (Na) At least one element of 'potassium (κ). 3. A sputtering target according to item 1 or 2 of the patent application, wherein the concentration of the alkali metal is l〇16~1〇18cm-3. The sputtering target according to any one of the above items, wherein the relative density is 97% or more. 5. A method for producing a Cu-Ga sputtering target, which is characterized in that it is manufactured by sintering. The ratio of the original abundance of gallium (Ga) to the total number of atoms of gallium (Ga) steel (Cu) (Ga/(Ga+Cu)) is 〇2 to 〇6 and 3 is Cu-Ga-based sputtering of metal For the target, a substance selected from Li 〇, \ K 〇, τ with a 〇, 2, Li 2 S, Na 2 S, K 2 S, Li 2 Se, Na 2 Se, K 2 Se to + 5 is used as a compound for adding a metal. · ~~ kinds of light absorption layer, its application In the scope of the patent range, the cup κ 崎 崎 弟 4 — Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu Cu 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Light absorption 八、 無 18Eight, none 18
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