201118190 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種形成Cu-In-Ga-Se(以下記為CIGS) 四元系合金薄膜（即薄膜太陽電池層之光吸收層）時所使用 之Cu-Ga燒結體濺鍍靶及該靶之製造方法。 【先前技術】 近年來，作為薄膜系太陽電池具有高效率之CiGS系太 陽電池的量產正在進展中，其光吸收層製造方法，已知有 蒸鍍法與硒化法（selenizati〇n^以蒸鍍法所製造之太陽電池 雖然有高轉換效率之優點，但有低成膜速度、高成本、低 生產性之缺點，硒化法較適於產業上大量生產。 硒化法的製程概要如下。首先，於鈉鈣玻璃基板上形 成鉬電極g，再於其上濺鍍成膜出Cu_Ga層與h層後，利 用氫化硒氣體中之高溫處理來形成⑽層。在利用此硒化 去之CIGS層形成程序中之Cu_Ga層之_成膜時係使用有 m-Lra靶之製造方法 另塔解凌興粉末A -—驭叩了，以 熔解法所製造之cu_Ga歡雖然雜質污染較 析大、縮孔（shrinkage eavitvbf A # t 成偏 age Cavity)所致產率降低等問題，以粉太 、所製造之靶有燒結密度低、容易破裂等問題。 要素皆會對CIGS系太陽電池的轉換 響，而⑽膜特性亦會帶來报大 二帶來- 前階段的Cu-Ga膜的特 成CIGS膜之 很大的影響。將粉末加以燒::= 也的轉換效率帶來 境、·。所侍之靶與熔解品相比，且 201118190 有成分偏析少 '製造容易 '及易於視需要進行成分調整之 特徵，與熔解品相比有較大的優點。 然而，燒結所得之靶有Cu-Ga靶脆性高且易破裂之問 題。若於靶加工中破裂則耙製造產率會降低，若於濺鍍中 破裂則會產生cIGS太陽電池製造產率降低之_。兩者最 終皆與CIGS系太陽電池製造成本的上升有關。 至目前為止有關Cu-Ga靶之文獻之一，可舉出下述專 利文獻卜此專利讀i係以熔解法來製作〜以乾。而此 專利文獻i之特徵’係⑨Cu_Ga &注人In。此專利文獻i 中，雖有無異常放電等記載與相對密度為95%以上之記載， 但關於所得之靶的破裂並無特別的記載。 -般而言，熔解品相較於燒結品，當然密度較高，线 常未滿之密度者少。然而，專利文獻ι之段落[〇〇1〇 把載著「相對密度#95%以上之高密度」，破有實現此箱 程度的密度之記載。 因此相對密纟95%左右絕對無法稱為高密度。實際上 吾人認為此專利文獻丨中’於炼解品中產生了會使密度降 低之孔洞、不佳之空孔（空隙）。 又，雖然 示分析結果等 認知水準程度 已有未觀察到組成偏析之記載，但完全未揭 。從上述程度之相對密度的記載，僅敘述已 之偏析的提升。 ^般而言，熔解法通常組成偏析大，因為未經過用以 析：斤之特別的步驟’故認為其會殘存有-般程度之偏 4 201118190 此種熔解品特有之偏析有於濺鍍中發生膜組成變化之 不良情況。且濺鍍條件亦不明。 因此’於熔解品產生會使密度降低之孔洞、不良之空 孔（空隙）、或偏析之靶，相較於粉末燒結體更有易於發生破 裂之可能。 又，關於Cu-Ga靶之其他文獻（專利文獻2)中記載了燒 結體靶，其有關於切削靶時易發生破裂、缺損之脆性之習 知技術的說明，為了解決此情況，製造二種粉末並將其加 以混合進行燒結。而二種粉末之一為提高Ga含量之粉末， 另一者為減少Ga含量之粉末，為做成以晶界相包圍之二相 共存組織者。 此步驟因為是於事前製造二種粉末，故當然步驟複 雜，且各種粉末之硬度等物性值、組織不同，故僅進行混 合燒結難以作成均勻的燒結體，無法期待密度的提升。密 度變低的靶當然會造成破裂。 此專利文獻2中，切削時之破裂情況雖評價為良好， 但關於濺鍍時之破裂問題仍不明。由於靶的組織構造並非 表面而是内部的問題，二相共存組織於濺鍍時破裂之問題 吾人認為與表面的切削性是不同的問題。即使可解決賤錢 時破裂之問題，但因為靶的組織成為二相共存組織，故可 能產生不均勻之濺鍍膜。可以說皆隱含了製作二種粉末所 致之成本增加與上述問題。 專利文獻3中，除了例示有CuGa2以作為光記錄媒體 之記錄層的材料之一以外，還有以濺鍍法積層AuZn記錄層 S. 201118190 之記載。然而，並無濺鑛CuGa2之記載，只不過暗示了 cu^ 之濺鍍。 專利文獻4中❺了例不有CuGa2以作為光記錄媒體 之記錄層的材料之一以外，還有以濺鍍法積層AuSn記錄層 之記載。並無濺鍍CuGa2之記載，只不過暗示了 Cu%之 減鍍。 專利文獻5中於請求項29記載了—種銅合金[其含 有l〇〇PPm以上且未滿10重量％之以’具有丨至2〇… 千均結晶粒度，且乾整體之結晶粒度均句性具有未滿抓 之標準偏差。其目的係使之Ga濃度低，且使經鍛造、壓延 所作成之靶具有特定的織構。 專利文獻6中主張了 ―錄太 種在0·1〜2〇.〇at%之固溶限範 圍内添加有含Ga之添加元素的銅合金。然而，實施例所干201118190 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of forming a Cu-In-Ga-Se (hereinafter referred to as CIGS) quaternary alloy thin film (i.e., a light absorbing layer of a thin film solar cell layer). A Cu-Ga sintered body sputtering target used and a method of producing the target. [Prior Art] In recent years, mass production of a CiGS-based solar cell having high efficiency as a thin film system solar cell is progressing, and a method for producing a light absorbing layer is known as a vapor deposition method and a selenization method (selenizati〇n^ Although the solar cell manufactured by the vapor deposition method has the advantages of high conversion efficiency, it has the disadvantages of low film formation speed, high cost, and low productivity, and the selenization method is more suitable for mass production in the industry. The process of the selenization method is summarized as follows First, a molybdenum electrode g is formed on a soda lime glass substrate, and then a Cu_Ga layer and a h layer are sputtered thereon, and then a (10) layer is formed by high temperature treatment in a hydrogen selenide gas. The Cu_Ga layer in the CIGS layer formation process is formed by using the m-Lra target manufacturing method. The other is to solve the Lingxing powder A--驭叩, and the cu_Ga Huan produced by the melting method is larger than the impurity contamination. Holes (shrinkage eavitvbf A # t is a partial age Cavity) caused by problems such as yield reduction, the target produced by the powder is too low, the sintered density is low, and it is easy to break. The factors are all about the conversion of CIGS solar cells. And (10) membrane Sex will also bring a big impact on the special CIGS film of the Cu-Ga film in the pre-stage. The powder is burned::= The conversion efficiency also brings the environment. Compared with the melted product, 201118190 has the characteristics of less component segregation, easy to manufacture, and easy to adjust the composition as needed. Compared with the melted product, it has a great advantage. However, the target obtained by sintering has a high brittleness of the Cu-Ga target. And the problem of easy rupture. If the rupture in the target processing, the manufacturing yield will be reduced, and if the rupture during sputtering will result in a decrease in the manufacturing yield of the cIGS solar cell, both of them will eventually be related to the manufacturing cost of the CIGS solar cell. Regarding the rise of the Cu-Ga target, one of the documents relating to the Cu-Ga target is exemplified by the following patent document, which is produced by the melting method to dry. The feature of the patent document i is 9Cu_Ga & Injecting In. In the patent document i, there is no description of the abnormal discharge or the like and the relative density is 95% or more. However, the crack of the obtained target is not particularly described. - Generally, the molten product is compared with Sintered products, of course, the density is high, the line is often not However, the paragraph of the patent document ι [〇〇1〇 carries the "high density of relative density #95% or more", and the density of the degree of realization of the box is broken. Therefore, the relative density is about 95%. It is absolutely impossible to call it high density. In fact, I believe that in this patent document, 'there are holes and poor pores (voids) that reduce the density in the refining product. Moreover, although the level of cognition such as the analysis results has not been Observed the composition segregation, but it has not been revealed. From the above description of the relative density, only the improvement of the segregation has been described. ^Generally, the melting method usually has a large segregation because it has not been analyzed. The special step 'I think it will remain to the same extent. 4 201118190 The segregation characteristic of this type of melted product has the problem of film composition change during sputtering. The sputtering conditions are also unknown. Therefore, a hole which causes a decrease in density, a defective void (void), or a target of segregation in the melted product is more likely to be broken than the powder sintered body. Further, in the other literature (Patent Document 2) of the Cu-Ga target, a sintered body target is described, and there is a description of a conventional technique in which cracking and defect brittleness are likely to occur when the target is cut, and in order to solve this problem, two types of manufacturing are manufactured. The powder is mixed and sintered. One of the two powders is a powder which increases the Ga content, and the other is a powder which reduces the Ga content, and is a two-phase coexisting organizer surrounded by a grain boundary. In this step, since the two kinds of powders are produced in advance, the steps are complicated, and the physical properties and the structure of the hardness of the various powders are different. Therefore, it is difficult to form a uniform sintered body only by mixing and sintering, and the density cannot be expected to be improved. A target with a reduced density will of course cause cracking. In Patent Document 2, although the crack at the time of cutting is evaluated as good, the problem of cracking at the time of sputtering is still unknown. Since the target structure is not a surface but an internal problem, the problem of cracking of the two-phase coexisting structure during sputtering is considered to be a problem different from the machinability of the surface. Even if the problem of rupture at the time of saving is solved, since the target tissue becomes a two-phase coexisting structure, a non-uniform sputtering film may be generated. It can be said that the cost increase caused by the two kinds of powders is implied and the above problems are caused. In Patent Document 3, in addition to the fact that CuGa2 is exemplified as one of the materials of the recording layer of the optical recording medium, the AuZn recording layer S. 201118190 is deposited by sputtering. However, there is no record of splashing CuGa2, but it implies the sputtering of cu^. Patent Document 4 discloses that CuGa2 is not included as one of the materials of the recording layer of the optical recording medium, and the AuSn recording layer is deposited by sputtering. There is no record of sputtering CuGa2, but it implies a Cu% reduction. Patent Document 5 describes in claim 29 a copper alloy [which contains l〇〇PPm or more and less than 10% by weight of 'having 丨 to 2 〇... thousand-period crystal grain size, and the dry overall crystal grain size is uniform. Sex has a standard deviation of underfill. The purpose is to make the Ga concentration low and to make the target made by forging and calendering have a specific texture. Patent Document 6 proposes a copper alloy in which a Ga-containing additive element is added to a solid solution limit of 0·1 to 2〇.〇at%. However, the examples are dry
Cu-Mn合金’且關於乾之製法並未具體記載，認為 疋熔解法所製得者。用途為顯示裝置用。 專利文獻7中’為一種將粉末之原料 級縮所製得之銅合金乾，實施 進订冷靜水The Cu-Mn alloy' is not specifically described in the dry process, and is considered to be obtained by the ruthenium melting method. The purpose is for display devices. In Patent Document 7, 'the copper alloy obtained by down-sizing the raw material of the powder is dried, and the cooling water is implemented.
Cu-Ga合金粉末所構成之混合物為1 :=以銦… 請發明相比，並未進行燒二的製法。與本申 仃心、組成亦不同，無相關之要素。 專利文獻8中雖有含有卜㈣⑽之a合金 用淹鍍乾之記载，但實施例所記載的是 炫魅隨 '、Cu添加有〜或Mn之材料而得以作為铸鍵者，並| 任何有關添加有Ga之鋼合金靶之具體記載。 ‘、 專利文獻9中’雖然實施例記載了用以用於aGs型薄 6 201118190 的CuGa合金靶 並無任何記載。 膜太陽電池製造之10、20、30重量％之Ga 的使用例’但關於CuGa合金靶本身之製法 又，同樣地關於靶的諸特性亦無記載。 專利文獻W巾’記載了以锻造急冷法製造含有〜 67at%Ga的CuGa合錄之方法。雖與本巾請發明—樣是薄 膜太陽電池用it ’但具有鍛造特有的缺點，由本中請發明 所解決之課題依然存在。 專利文獻11中界定了含有2〇〜96重量％之以的c仙 合金乾，且在實施例中記载了 Ga25重量％、Cu75重量％特 別有效。然而，關⑨Cu-Ga合金乾本身之製法並未有任何 記載，關於靶的諸特性亦同樣未有記載。上述任一之專利 文獻中，未能發現對於本申請發明之課題及其之解決手段 月匕作為參考之技術的揭示。 又 1 Η 不将 開 專 利 文 獻 2 曰 本特 開 專 利 文 獻 3 曰 本特 開 專 利 文獻 4 曰 本特 開 專 利 文 獻 5 曰 本特表 專 利 文 獻 6 國 際公 開 專 利 文 獻 7 國 際公 開 專 利 文 獻 8 國 際公 開 專 利 文 獻 9 曰 本特 開 2000-73163 號公報 2008-138232 號公報 昭63-37834號公報 昭62-379533號公報 2005-533 1 87 號公報 W02006-025347 號公報 WO2007-137824 號公報 W02007-004344 號公報 平10-135498號公報 專利文獻10 :中華人民共和國特開1 7 1 9626號公報 專利文獻11 :曰本特開平丨U60724號公報 S. 7 201118190 【發明内容】 有鑑於上述狀況，本發明之課題在於提供一種Cu_Ga 燒體乾及其之製造方法，肖Cu_Ga燒結體乾抗可提高抗 彎強度、抑㈣製造時及_成料之破裂，且提升產 率、降低cms層形成程序及CIGS太陽電池製造之成本。 為了解決上述課題’本發明人等努力研究之結果發 現，為了防止組成偏析，使用炫解法有其限度，而必須要 使用以粉末法使組成均一之原料是有效的；而為了減低脆 性’提高_度、將平均粒徑定於衫範圍内等是有效的， 而本發明於焉完成。 亦即，本發明提供 1) -種Cu-Ga合金燒結體濺鍍靶，其特徵在於：係由 Ga濃度為20〜60at%、剩餘部份為Cu及無法避免的雜質之 Cu-Ga合金粉末之燒結體所構成，該燒結體的相對密度為 97%以上，平均結晶粒徑為$〜、仓a > « 30# m，進而抗彎強度為 1 50Mpa 以上、 2) 如上述1)之Cii-Ga合金燒結體濺鍍靶，其中，合使 乾之抗彎強度為，Pa)、Ga浪度為N(at%)時，滿足二 XN+ 600之關係、 3) 如上述1)或2)之Cu.Ga合金燒結體濺鐘乾，其中， Cu-Ga合金係由單一組成所構成' 4) 如上述1)〜3)中任一瑁 Γ 人a & 項之C Ga 5金燒結體濺鍍 乾，其中，Cu-Ga合金之X私始认6丄Λ Λ射線繞射之主峰以外的峰強度 相對於主峰強度為5%以下、 8 201118190 5)如上述1)〜4)中任一項之Cu-Ga合金燒結體濺鍍 粗’其中’ Cu-Ga合金組成實質上為r相或者主要相為r相。 又’本發明提供 6)—種合金燒結體濺鍍靶之製造方法，係將 Ga原料加以熔解、冷卻後，再以熱壓法將經粉碎之 混口原料秦製作成上述〇〜5)中任-項之Cu-Ga合金燒結 體滅錢無之方法，其特徵在於： 。、塱時之保持溫度定為較混合原料粉熔點低5 0〜 、C將保持時間定為i〜3小時冷卻速度定為代 以上、對混合原料粉之加壓壓力定為30〜4GMPa來進行孰 壓、 … 7)如上述6)之Cu-Ga合金燒結體濺鍍靶之製造方法， 其係以機械粉碎法、裔_ @ 纤古矾體霧化法或水霧化法來進行Cu及The mixture of Cu-Ga alloy powders is 1 := indium... Compared to the invention, the method of firing is not performed. There is no difference between the heart and the composition of this application. In Patent Document 8, although the alloy containing a (4) (10) is described as being dried by flooding, in the examples, it is described that the material of the glamour is added with the material of the Mn or the Mn, and the material is cast as a bond. Specific description of the steel alloy target to which Ga is added. In the case of the patent document 9, the CuGa alloy target used for the aGs type thin 6 201118190 is not described. The use example of 10, 20, and 30% by weight of Ga in the production of a membrane solar cell is described. However, the method of producing the CuGa alloy target itself is similarly described in terms of the characteristics of the target. The patent document W towel describes a method of producing a CuGa containing ～67 at% Ga by a forging quenching method. Although it is invented with this towel, it is a thin film solar cell, but it has the disadvantages of forging, and the problem solved by the present invention still exists. Patent Document 11 defines a dry alloy of 2 to 96% by weight, and in the examples, it is described that Ga25 wt% and Cu75 wt% are particularly effective. However, there is no description of the method for producing the 9Cu-Ga alloy itself, and the properties of the target are also not described. In the above-mentioned patent documents, the disclosure of the subject matter of the present invention and the means for solving the same is not found. 1 Η 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特 特Japanese Laid-Open Patent Publication No. 2000-73163, No. 2008-138232, No. Sho 63-37834, No. 62-379533, No. 2005-533, No. 1, No. PCT Publication No. WO-A No. WO2007-137824, No. WO2007-004344 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The invention provides a Cu_Ga sintered body and a manufacturing method thereof, and the dry Cu_Ga sintered body dry resistance can improve the bending strength, suppress the cracking during the manufacturing and the formation, and improve the yield, reduce the formation of the cms layer, and the CIGS solar cell. The cost of manufacturing. In order to solve the above-mentioned problems, the inventors of the present invention have found that in order to prevent composition segregation, there is a limit to using a dazzling method, and it is necessary to use a powder method to make a uniform composition of raw materials effective; and to reduce fragility 'improvement_ It is effective to set the average particle diameter within the range of the shirt, and the present invention is completed. That is, the present invention provides a 1) Cu-Ga alloy sintered body sputtering target characterized by Cu-Ga alloy powder having a Ga concentration of 20 to 60 at% and a balance of Cu and unavoidable impurities. The sintered body is composed of a sintered body having a relative density of 97% or more, an average crystal grain size of $ 〜, a bar a > 30 30 m, and further a bending strength of 150 MPa or more, 2) as in the above 1) A Cii-Ga alloy sintered body sputtering target, wherein the bending strength of the combined dryness is Pa, the Ga wave is N (at%), the relationship of two XN+600 is satisfied, and 3) is as in the above 1) or 2 The Cu.Ga alloy sintered body is splash-dried, wherein the Cu-Ga alloy is composed of a single composition '4) as in any of the above 1) to 3), a C a 5 gold sintering of the a & The body is sputter-dried, wherein the peak intensity of the main peak of the X-ray diffraction of the Cu-Ga alloy is 5% or less with respect to the main peak intensity, 8 201118190 5) as in the above 1) to 4) Any of the Cu-Ga alloy sintered bodies is sputtered thick 'where the 'Cu-Ga alloy composition is substantially r phase or the main phase is r phase. Further, the present invention provides a method for producing a sintered body sputtering target of a alloy, in which a Ga raw material is melted and cooled, and then the pulverized mixed raw material Qin is produced into the above-mentioned 〇~5 by a hot pressing method. The method for killing money of the Cu-Ga alloy sintered body of any of the items is characterized in that: The temperature is kept at a lower temperature than the melting point of the mixed raw material powder, and the holding time is set to i~3 hours, the cooling rate is set to be higher than the above, and the pressing pressure of the mixed raw material powder is set to 30 to 4 GMPa.孰压, 7) The method for producing a Cu-Ga alloy sintered body sputtering target according to 6) above, which is carried out by mechanical pulverization, _ @ 矾 矾 矾 雾化 或 or water atomization method for Cu and
Ga原料的熔解冷卻後之粉碎。 據本發明’於〜如燒結體靶中，由於可提高抗- 強度、抑制靶製造時及濺鍍成膜時之靶破裂，而提升產率， 故具有可減少CIGS層形成裎序及CIGS太陽電池製造之成 本之優異效果。 【實施方式】 接著’記載用以實施發 要件的定義、範圍規定之理 法等。 明之形態，亦即本發明之構成 由、意義、調整方法、測定方 發明之Cu-Ga合金燒結體濺鍍祀 一 μ狀p〜淚厪範圍為 ，剩餘部份為〜及無法避免的雜質。因為此乃 201118190 較佳之Ga濃度範 於此範圍以外之組 實際製作CIGS系太陽電池時之適切且 圍。但本發明之技術思想本身亦可適用 成。 本發明之Cu-Ga合金燒結體濺鍍靶，燒結體的相對密 度為97%以上，較佳為98%以上，更佳$ 99%以上。相對 密度係燒結體無之實際的絕對密度除以其組成之㈣理論 祖度所付之值的比。 靶的相對密度低，意指靶中存在大量内部空孔，故會 成為Cu-Ga合金燒結體靶脆化的主要原因。如後述之實施 例及比較例所示，Cu-以合金燒結體靶若^含量增加，則 會急速地脆化。因此’提高靶的密度，會有抑制Cu_Ga合 金燒結體靶的脆化、提高抗彎強度之功能。 再者，本發明之Cu-Ga合金燒結體濺鍍靶係將平均結 晶粒徑定為5〜30" m。平均粒徑可視需要將靶表面輕微蝕 刻’使日日界明破後再以平面（planimetric)法求出。 若平均粒徑小則容易高密度化，可藉由上述之高密度 特徵抑制破裂的發生。又，相反地，平均粒徑若大，則各 結晶粒會隨機配向，因此容易推進破裂的進行。 由上述之機制來看，藉由減小平均粒徑可抑制破裂。 隨著平均粒徑增加而抗彎強度會變小，因為平均粒徑為超 過30 左右，且因為與施加至靶之加工時及濺鍍時的應 力之關係，故易於產生破裂、龜裂。又，雖然平均粒徑較 小為佳，但若使平均粒徑未滿5 // m，則因為製造上需要增 加步驟故並不利於實用。 10 201118190 平均粒徑可由熱壓時之保持溫度來調整，越高溫粒徑 越大。 一般而S，加工時及濺鍍時之破裂、龜裂，具有在靶 的抗彎強度越小時越容易發生之傾向，但並非僅與抗彎強 度的值1對1對應，而是有一定程度之範圍的幅度，即使 是相同抗彎強度，若密度、粒徑相異，破裂容易度仍會有 些許差異。本發明中，將加工時及濺鍍時之破裂 '龜裂不 會發生之程度的抗彎強度界定為l5〇Mpa以上。The melt of the Ga raw material is cooled and pulverized. According to the present invention, in the case of a sintered body target, since the anti-strength can be improved, the target crack during the target production and the sputtering film formation can be suppressed, and the yield is improved, the CIGS layer formation order and the CIGS sun can be reduced. The excellent effect of the cost of battery manufacturing. [Embodiment] Next, a description is given of a method for implementing the definition of a hair piece, a range specification, and the like. The form of the invention, that is, the composition of the present invention, the meaning, the adjustment method, and the measurement method of the Cu-Ga alloy sintered body sputtering 祀 a μ-like p~ teardrop range, the remainder is ~ and unavoidable impurities. This is because the better the concentration of Ga in 201118190 is outside the range, and it is suitable for the actual production of CIGS solar cells. However, the technical idea of the present invention itself can also be applied. In the Cu-Ga alloy sintered body sputtering target of the present invention, the sintered body has a relative density of 97% or more, preferably 98% or more, more preferably $99% or more. The relative density is the ratio of the actual absolute density of the sintered body divided by the value of the theoretical ancestor of its composition. The low relative density of the target means that there are a large number of internal pores in the target, which may be the main cause of embrittlement of the sintered body of the Cu-Ga alloy. As shown in the examples and comparative examples described later, Cu-based alloy sintered body target is rapidly embrittled if the content of the alloy sintered body target increases. Therefore, increasing the density of the target has a function of suppressing embrittlement of the Cu_Ga alloy sintered body target and improving the bending strength. Further, the Cu-Ga alloy sintered body sputtering target system of the present invention has an average crystal grain size of 5 to 30 " m. The average particle size may be slightly etched by the target surface as needed. The daytime boundary is broken and then determined by a planimetric method. When the average particle diameter is small, the density is easily increased, and the occurrence of cracking can be suppressed by the above-described high density characteristic. On the other hand, if the average particle diameter is large, the crystal grains are randomly aligned, and thus it is easy to advance the crack. From the above mechanism, cracking can be suppressed by reducing the average particle diameter. As the average particle diameter increases, the bending strength becomes small, since the average particle diameter is more than about 30, and cracking and cracking are liable to occur due to the relationship with the stress applied during the processing to the target and the sputtering. Further, although the average particle diameter is preferably small, if the average particle diameter is less than 5 // m, it is not advantageous for practical use because of an increase in manufacturing steps. 10 201118190 The average particle size can be adjusted by maintaining the temperature during hot pressing. The higher the temperature, the larger the particle size. In general, S, cracking and cracking during processing and sputtering have a tendency to occur when the bending strength of the target is small, but it does not correspond to the value of the bending strength of 1 to 1, but has a certain degree. The range of the range, even if the same bending strength, if the density and particle size are different, the ease of rupture will be slightly different. In the present invention, the bending strength at the time of processing and sputtering is defined as the degree of bending resistance which does not occur, and is defined as l5 〇 Mpa or more.
Cu-Ga系合金具有Ga濃度若增加則抗彎強度會降低之 傾向。本發明中，當將靶的抗彎強度定為F(MPa)、Ga濃度 為N(at%)時，將抗·彎強度高之靶界定為滿足+ 之關係之程度。 至今習知文獻等中並未記載Cu_Ga系靶之抗彎強度， 而本發明之抗f強度於各濃度皆高，故於Cu_Ga系靶2破 裂抑制方面具有效果。抗彎強度可由3點彎曲法求得。 本發明之Cu-Ga合金燒結體濺鍍靶之較佳條件之一， 係提供-種Cu-Ga合金由單一組成所構成之CM 結體濺鍍靶。 金現 :發明中單一組成一詞，細「僅以經通常之物理手 奴專無法檢測出其他組成存在之組成所構成之組 義來使用。又，微觀而t ’當即使微量含有其他组： 被認為會對各種特性造成不良影響時，實質上仍合’、 單-組成相同之效果。 實質上仍會展現與 本發明之Cu-Ga合金燒結體濺鍍靶之較佳條件之一 201118190 係提供-種Cu-Ga合金燒結體義乾，其Cu Ga合金 射線繞射之主峰料的峰強度相對於主峰強度為5%以下。 可以X射線峰強度比來界定 單— 組成之峰相比，其他組成之峰強度只要為π:可= 上展現與單一組成相同之效果。 、 :氣體霧化或水霧化法所製作之混合原料粉 =均勻，將該混合原料加以熱壓所得之心成亦可接 勻。又，於熱壓冷卻中冷卻 — 度右小’則有時冷卻中會析 出/、相。此種異相若量多則可以χ射線繞射♦檢測出。 合金當Ga組成為約3G〜43at%時會具有加瑪 =相。此相具有脆性’具有易於破裂之特徵 :電：中所使用之一成大多特別是在 ： =了避免此一合金的脆性，提升密度、提升 考強度特別有效。 才几 二著=對本發明之免的製造方法，記載其範圍界定 由和思義'對於該乾諸特性所造成之影響等。 鍋，在：：之組成比例秤量Cu及Ga原料後，置於碳製坩 t在Μ至約0·清a大氣壓之加熱爐内，定為高於溶點 分：:rC’使混合原料炫解。保持約1小時以上，於充 出初級合成原料。 “加熱’進行冷卻之後，取 法有2初級合成原料加以粉碎以獲得微粉原料。粉碎方 :=、氣體霧化法、水霧化法等，任一方法皆可， 低成本且可大量處理者為水霧化法。 12 201118190 s為水霧化的情況時’方法如下：使初級合成原料再 度在坩鍋内熔解’使成為液狀之原料液滴了，對該滴下液 噴射約lOMpa左右之高壓水，以獲得微粉。所得之微粉係 於其後經壓濾、乾燥等再作為混合微粉原料來使用。 使混合微粉原料經過特定開口的筛，調整粒度分布後 進仃熱壓。熱壓條件依Ga濃度而適當條件會不同，例如當 仏濃度為30at%的情況時，為溫度600〜70(rc、壓力3〇: 4〇MPa左右。 亦即，就此熱壓之較佳條件而言，有效者如下：使教 $時之保持溫度低於混合原料粉熔點5〇〜2〇(rc、保持時間 疋為1 3小時冷卻速度定為代以上、對混合原料 為之加壓壓力定為3G〜4GMPa。適當選擇此熱壓條件，則 可謀求Cu.Ga合絲之密度提升、進而抗彎強度的提升。 在里度上汁速度保持時間等溫度剖面（ρΓ0fiie)與壓力 施加剖面的關係方面’相較於使溫度成為設定最高溫度後 再施加壓力之後壓方式’先施加壓力之先壓方式因為於燒 結前原料粉會粉粹成較細微故對於提高燒結密度是有效 的。 又，熱壓之冷卻速度若為緩慢的，則於其之間會產生 異相’故冷料度定$ 5〇C/min以上之快速溫度是有效的。 ,以上述方法所製作之Cu-Ga燒結體之密度可以阿基米 k法、平均粒徑可於表面蝕刻後以平面法、組成可以X射 線繞射法分別求出。 可將上述Cu-Ga燒結體加工成例如直徑6吋、厚度 13 201118190 6mm，再於底板（backing plate)貼附銦作為硬焊填充金屬 (brazing Hller metal)’做為濺鍍靶，再進行成膜調查對膜 之粒子產生狀況、結球 '異常放電等狀況。 實施例 接著，說明本發明之實施例及比較例。又，因為以下 之實施例頂多表示代表的例子’故本發明並不需要被限制 於該等實施例，應以說明書所記載之技術思想範圍來解釋。 (實施例1) 之Ga濃度為3〇at%， 狎量Cu原料與Ga原料以使組成 置於碳製坩鍋，在施加有〇 5Moa夕气沾I办此a 。 巧u.JMPa之虱的加熱爐内以1〇00 C炫解後’再以冷卻速度5〜丨〇γ /…· „ 3 10 C/min冷卻後取出合成原 料。 接著’將此合成原料置於水霧化裝置之碳㈣，以1〇〇〇 °〇溶解後’滴下熔解液同時對於滴下液噴射刪pa的高墨 ,，而獲# Cii-Ga混合微粉。將混合微粉壓濾後以12代乾 燥之’獲得混合微粉原料。 。以5°C/min之升溫速度將此混合微粉從室溫升溫至65〇 c之後，保持在65(rc2小時同時施加35Mpa之壓力。其後， 以5口广之降溫速度進行冷卻之後取出燒結體。 所付之Cu-Ga燒結體的相對密度為99 9%，平均粒徑為 主相與異相之X射線繞射峰強度比為G 2%。將此 凡結體加工成直徑6 °子、厘疮/； _ 旱度6mm之圓板狀，做成濺鍍耙， 遠行濺鍍。 就濺錢條件而言 環境氣體為氬且氣體流量為 14 201118190 50sccm，濺鍍時壓力為〇_5Pa，尤其使濺鍍功率（與乾破裂相 關之重要條件）大至直流（DC) 1000W。濺鍍時間2〇小時後， 總滅鑛量20kWhr後’觀察乾表面，並未確認到破裂。 將以上之結果示於表1。 表 實施例 Ga濃度 (at%) 相對密度 (%) 平均粒徑 (μιη) X射線強度比 (%)In the Cu-Ga-based alloy, if the Ga concentration is increased, the bending strength tends to decrease. In the present invention, when the bending strength of the target is F (MPa) and the Ga concentration is N (at%), the target having high anti-bending strength is defined as the degree of satisfying the relationship of +. The bending strength of the Cu-Ga-based target has not been described in the conventional literature and the like, and the anti-f-strength of the present invention is high at each concentration, so that the Cu-Ga-based target 2 has an effect of suppressing the cracking. The bending strength can be obtained by a 3-point bending method. One of the preferable conditions for the Cu-Ga alloy sintered body sputtering target of the present invention is to provide a CM junction sputtering target composed of a single composition of a Cu-Ga alloy. Jin Xian: The term "single composition" in the invention, "only" can be used only by the composition of the composition of the other components that can not be detected by the usual physical hand slaves. Also, microscopically, t's even if the trace contains other groups: When it is considered that it will adversely affect various characteristics, it is substantially the same as the effect of 'single-composite composition. It is still substantially one of the better conditions for the Cu-Ga alloy sintered body sputtering target of the present invention. Providing a sintered body of a Cu-Ga alloy sintered body, the peak intensity of the main peak of the Cu Ga alloy ray diffraction is 5% or less with respect to the main peak intensity. The X-ray peak intensity ratio can be defined as a single-composition peak, The peak intensity of other compositions is as long as π: can show the same effect as the single composition. : : The mixed raw material powder produced by gas atomization or water atomization method is uniform, and the mixed raw material is hot pressed. It can also be evenly connected. In addition, cooling in the hot-press cooling - the right is small - sometimes the precipitation / phase will be precipitated during cooling. If the amount of such heterophase is large, it can be detected by χ ray diffraction. About 3G~43at% will be Gamma = phase. This phase has brittleness. It has the characteristics of being easy to break: the one used in electricity is mostly in: = avoiding the brittleness of this alloy, increasing the density and improving the strength of the test is particularly effective. In the manufacturing method of the present invention, the scope is defined by the influence of the thinking and the characteristics of the dryness. The pot is placed in a carbon crucible after the composition ratio of Cu: and Ga raw materials is weighed. t In the heating furnace of Μ to about 0·clear a atmosphere, set the mixture to be higher than the melting point::rC' to disperse the mixed raw material. Hold for about 1 hour or more to charge the primary synthetic raw material. Thereafter, the raw material of the primary synthetic material is pulverized to obtain a fine powder raw material. The pulverization method: =, gas atomization method, water atomization method, etc., any method is available, and the low-cost and large-volume treatment is a water atomization method. 12 201118190 s is the case of water atomization. The method is as follows: the primary synthetic raw material is melted again in the crucible to make the liquid material droplets, and the dripping liquid is sprayed with about 1 OMpa of high-pressure water to obtain fine powder. . The obtained fine powder is then subjected to pressure filtration, drying, or the like as a raw material for mixing fine powder. The mixed fine powder raw material is passed through a sieve of a specific opening, and the particle size distribution is adjusted, followed by hot pressing. The hot pressing conditions may differ depending on the Ga concentration. For example, when the cerium concentration is 30 at%, the temperature is 600 to 70 (rc, pressure 3 〇: 4 〇 MPa or so. That is, the preferable conditions for the hot pressing) In other words, the effective ones are as follows: the temperature at which the teaching is held is lower than the melting point of the mixed raw material powder 5 〇 2 〇 (rc, the holding time 疋 is 13 hours, the cooling rate is set to be higher than the above, and the pressure of the mixed raw material is pressed. It is set to 3G to 4GMPa. When this hot pressing condition is properly selected, the density of the Cu.Ga wire can be increased and the bending strength can be improved. The temperature profile (ρΓ0fiie) and the pressure application profile are maintained in the rinsing speed. In terms of the relationship, the pressure is applied first before the pressure is set to the maximum temperature, and the pressure is applied first. Since the raw material powder is fined before sintering, it is effective for increasing the sintered density. If the cooling rate of hot pressing is slow, it will produce a hetero phase between them. Therefore, it is effective to set a rapid temperature of more than 5 〇 C/min. The Cu-Ga sintering prepared by the above method is effective. Density of body can be Aki The k method and the average particle diameter can be obtained by a plane method and a composition by X-ray diffraction after surface etching. The Cu-Ga sintered body can be processed into, for example, a diameter of 6 吋, a thickness of 13 201118190 6 mm, and then a bottom plate ( The backing plate is attached with indium as a brazing Hller metal as a sputtering target, and a film formation investigation is performed to investigate the state of the particles of the film and the abnormal discharge of the ball. Examples Next, the present invention will be described. EXAMPLES AND COMPARATIVE EXAMPLES. Since the following examples are at most representative of the examples, the present invention is not necessarily limited to the embodiments, and should be construed in the scope of the technical idea described in the specification. The Ga concentration is 3〇at%, and the Cu raw material and the Ga raw material are weighed so that the composition is placed in a carbon crucible, and the crucible is applied to the crucible with a Mo5Moa immersion. After concentrating at 1〇00 C, 'after cooling, 5~丨〇γ /...· „ 3 10 C/min, the synthetic raw material is taken out. Then, the synthetic raw material is placed in the carbon of the water atomizing device (4) to After 1〇〇〇°〇 dissolved, 'drop the melt at the same time The dripping liquid is sprayed to remove the high ink of pa, and the #Cii-Ga mixed fine powder is obtained. The mixed fine powder is subjected to pressure filtration and dried in 12 passages to obtain a mixed fine powder raw material. The mixed fine powder is heated at a heating rate of 5 ° C / min. After raising the temperature from room temperature to 65 ° C, the pressure was maintained at 65 rc for 2 hours. Thereafter, the sintered body was taken out after cooling at a wide temperature of 5 ports. The relative density of the Cu-Ga sintered body was paid. 99 9%, the average particle diameter of the main phase and the X-ray diffraction peak intensity ratio of the heterogeneous phase is G 2%. This can be processed into a circular plate with a diameter of 6 °, a sore /; _ drought of 6 mm , made of sputtered enamel, and splashed away. In terms of splashing conditions, the ambient gas is argon and the gas flow rate is 14 201118190 50sccm. The sputtering pressure is 〇_5Pa, especially the sputtering power (important conditions related to dry cracking) is as large as DC (DC) 1000W. After the sputtering time of 2 hours, the total amount of the ore was 20 kWhr after the observation of the dry surface, no crack was confirmed. The above results are shown in Table 1. Table Example Ga concentration (at%) Relative density (%) Average particle diameter (μιη) X-ray intensity ratio (%)
(實施例2〜實施例6) 以與實施例1相同之方法分別製作將Ga組成與平均粒 徑加以變化之靶，將進行濺鍍評價之結果統整示於表1。由 此結果可知’ Ga組成、平均粒徑、抗彎強度在一定範圍内 之靶，獲得加工時及濺鍍時無破裂之良好結果。 (比較例1〜比較例2) 以與實施例i大致相同之條件製作乾，但分別使執壓 時之溫度低至60(TC、55(rc，藉此製作密度低之乾。 將靶之特性、破裂等之有無的結果整理記於表工。加工 15 201118190 時之破裂此欄中所記載之「少」，意指雖然靶並未破裂分 離’ 2有些許呈龜裂狀態。由此結果來看，若㈣密度低 ;寺定值則加工時會確涊到龜裂。但並未確認到濺鍍後 之乾表面的龜裂。 (比較例3〜比較例5 ) 以與實施例丨大致相同之條件製作靶，但分別使冷卻 速度小至rc/min' rc/min、θ α/—，藉此製作平均粒 徑大、X射線強度比大且確認到異相之靶。 將靶的特性、破裂等之有無的結果整理記於表1。由此 、·-。果叮去賤鑛時並未確認到龜裂，但加工時有些許龜裂。 (比較例6〜比較例8) 以溶解法製作Cu_Ga靶。秤量Cll與Ga原料以使Ga ’’且成成為特定之濃度並置於碳製坩鍋’於施加有〇 5Mpa氬 之加熱爐内’比較例6以1〇〇(rc、比較例7及8以高於分 別之材料的熔點約2〇(rc使之熔解後，以約rc/min之冷卻 速度冷卻再取出，將評價該取出之靶的特性、破裂等之有 無的結果整理記於表1。 由此結果可知’以熔解法所製作之靶平均粒徑非常大 且抗彎強度非常小’確認到加工時及濺鍍時之破裂。 圖1兄載表示本發明之實施例及比較例之Ga濃度與 Cu-Ga系靶之抗彎強度之關係圖。由此圖可知本發明實施例 之乾的抗彎強度大，故無加工時及濺鍍時之破裂，且可產 率良好地製造Cu-Ga系靶及膜。 (產業上之可利用性） 201118190 根據本發明，可提供一種無組成偏析、脆性低且Ga濃 度為25〜45at%之高Ga濃度的Cu-Ga靶及其之製造方法， 因為乾製造及CIGS系太陽電池製造之產率可提升，製造成 本可降低’故有用於作為利用硒化法之CIGS系太陽電池的 製造用材料。 【圖式簡單說明】 圖1係表示實施例及比較例之Ga濃度與Cu_Ga系把的 抗彎強度之關係之圖。 【主要元件符號說明】 無 17(Example 2 to Example 6) Targets in which the Ga composition and the average particle diameter were changed were prepared in the same manner as in Example 1, and the results of the sputtering evaluation were collectively shown in Table 1. From this result, it was found that the target having a Ga composition, an average particle diameter, and a bending strength within a certain range was obtained as a result of no cracking during processing and sputtering. (Comparative Example 1 to Comparative Example 2) Drying was carried out under substantially the same conditions as in Example i, but the temperature at the time of pressing was as low as 60 (TC, 55 (rc), whereby the density was low. The result of the presence or absence of characteristics, cracking, etc. is recorded in the table. Processing 15 201118190 The rupture described in this column is "less", meaning that although the target is not broken and separated, 2 is somewhat cracked. It can be seen that if the density is low, the crack is confirmed during processing, but the crack on the dry surface after the sputtering is not confirmed. (Comparative Example 3 to Comparative Example 5) The target was produced under the same conditions, but the cooling rate was reduced to rc/min' rc/min and θ α/-, respectively, whereby a target having a large average particle diameter and a large X-ray intensity ratio and having a different phase was observed. The result of the presence or absence of cracking, etc., is shown in Table 1. Therefore, the crack was not confirmed when the ore was removed from the ore, but some cracks occurred during the processing. (Comparative Example 6 to Comparative Example 8) Method for making a Cu_Ga target. Weighing Cll and Ga raw materials to make Ga '' and into a specific concentration and placing it in a carbon crucible' In a heating furnace with 〇5Mpa argon, 'Comparative Example 6 is 1 〇〇 (rc, Comparative Examples 7 and 8 are higher than the melting point of the respective materials by about 2 〇 (rc is melted, and then cooled by about rc/min). The results of the evaluation of the characteristics of the extracted target, the occurrence of cracks, and the like are shown in Table 1. The results show that the average particle diameter of the target produced by the melting method is very large and the bending strength is very small. The crack at the time of processing and the sputtering was confirmed. Fig. 1 shows the relationship between the Ga concentration of the examples and comparative examples of the present invention and the flexural strength of the Cu-Ga target, and the figure shows the embodiment of the present invention. Since the dry bending strength is large, cracking is not performed at the time of processing and sputtering, and a Cu-Ga-based target and film can be produced with good yield. (Industrial Applicability) 201118190 According to the present invention, a A Cu-Ga target having a high Ga concentration which is segregated, has low brittleness and a Ga concentration of 25 to 45 at%, and a method for producing the same, because the yield of dry manufacturing and CIGS-based solar cell manufacturing can be improved, and the manufacturing cost can be reduced. For the manufacture of CIGS solar cells using the selenization method Feed.] [Brief Description of the drawings Figure 1 is showing the concentration of Ga-based Cu_Ga of the Examples and Comparative Examples illustrates the relationship of the bending strength of the embodiment. The main element 17 None REFERENCE SIGNS