TW201529862A - In film and in sputtering target for depositing same - Google Patents

In film and in sputtering target for depositing same Download PDF

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TW201529862A
TW201529862A TW103134885A TW103134885A TW201529862A TW 201529862 A TW201529862 A TW 201529862A TW 103134885 A TW103134885 A TW 103134885A TW 103134885 A TW103134885 A TW 103134885A TW 201529862 A TW201529862 A TW 201529862A
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indium
film
sputtering target
sputtering
zinc
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Keita Umemoto
shou-bin Zhang
Shinji Kato
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Mitsubishi Materials Corp
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    • C—CHEMISTRY; METALLURGY
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Abstract

An In sputtering target which has component composition made of: one or more elements selected from a group consisting of Bi, Sb, Sn, and Zn; and the In balance and inevitable impurities, is provided. The total content of the one or more elements is 0.5 to 10.0 atomic %.

Description

銦膜、供形成銦膜之銦濺鍍靶及其製造方法 Indium film, indium sputtering target for forming indium film, and manufacturing method thereof

本發明，係有關在製造具有光吸收層之銅-銦-鎵-硒四元系合金膜之CIGS系化合物薄膜太陽電池時，在形成銅-銦-鎵-硒四元系合金膜時所使用之銦濺鍍靶及其製造方法，再者，有關以採用該銦濺鍍靶之濺鍍被形成之銦薄膜。 The present invention relates to a copper-indium-gallium-selenium quaternary alloy film formed when a CIGS-based compound thin film solar cell having a copper-indium-gallium-selenium quaternary alloy film having a light absorbing layer is produced. The indium sputtering target and the method of manufacturing the same, and further, an indium thin film formed by sputtering using the indium sputtering target.

本發明根據2013年10月7日於日本提出申請之特願2013-209977號專利申請案來主張優先權，於此處援用其內容。 The present invention claims priority based on Japanese Patent Application No. 2013-209977, filed on Jan.

近年，由化合物半導體所形成的薄膜太陽電池被供給至實際應用。在由這化合物半導體所形成的薄膜太陽電池之製造上，首先，在鈉鈣玻璃基板上形成鉬電極層，在此鉬電極層上形成由銅-銦-鎵-硒四元系合金膜所構成的光吸收層，在此由銅-銦-鎵-硒四元系合金膜所構成的光吸收層上，形成由硫化鋅、硫化鎘等所構成的緩衝層，進而，在此緩衝層上形成透明電極層。CIGS系化合物薄 膜太陽電池係具有這樣的基本構造。 In recent years, thin film solar cells formed of compound semiconductors have been supplied to practical applications. In the manufacture of a thin film solar cell formed by the compound semiconductor, first, a molybdenum electrode layer is formed on a soda lime glass substrate, and a copper-indium-gallium-selenium quaternary alloy film is formed on the molybdenum electrode layer. In the light absorbing layer, a buffer layer made of zinc sulfide, cadmium sulfide or the like is formed on the light absorbing layer made of a copper-indium-gallium-selenium quaternary alloy film, and further formed on the buffer layer. Transparent electrode layer. CIGS series compound thin The membrane solar cell system has such a basic structure.

作為上述由銅-銦-鎵-硒四元系合金膜所構成之光吸收層之形成方法，習知為利用蒸鍍法來形成薄膜之方法，利用此方法得到之由銅-銦-鎵-硒四元系合金膜所構成之光吸收層，雖具有可以得到高的能源轉換效率之優點，但依照此蒸鍍法，成膜速度慢，且在把大面積的化合物形成薄膜之場合下，膜厚的面內分佈的均一性不足。為此，提出利用硒化法(selenide)來形成由銅-銦-鎵-硒四元系合金膜所構成的光吸收層之方法。 As a method of forming the light absorbing layer composed of the copper-indium-gallium-selenium quaternary alloy film, a method of forming a thin film by a vapor deposition method is known, and copper-indium-gallium is obtained by this method. The light absorbing layer composed of the selenium quaternary alloy film has an advantage of obtaining high energy conversion efficiency, but according to the vapor deposition method, the film formation rate is slow, and when a large-area compound is formed into a film, The uniformity of the in-plane distribution of the film thickness is insufficient. For this reason, a method of forming a light absorbing layer composed of a copper-indium-gallium-selenium quaternary alloy film by selenide has been proposed.

作為上述以硒化法形成銅-銦-鎵-硒四元系合金膜之方法，首先提出，利用使用銦濺鍍靶之濺鍍，在鉬(Mo)電極層上形成銦膜，在此銦膜上，藉由使用銅-鎵二元系合金濺鍍靶予以濺鍍，形成銅-鎵二元系合金膜，在此得到的由銦膜及銅-鎵二元系合金膜所構成的層積膜，亦即形成前驅體之先驅膜(precursor film)。將此先驅膜於硒空氣中予以熱處理，形成銅-銦-鎵-硒四元系合金膜之方法(例如，參照專利文獻1)。 As a method of forming a copper-indium-gallium-selenium quaternary alloy film by selenization, it is first proposed to form an indium film on a molybdenum (Mo) electrode layer by sputtering using an indium sputtering target. On the film, a copper-gallium binary alloy sputtering film is used to form a copper-gallium binary alloy film, and a layer composed of an indium film and a copper-gallium binary alloy film is obtained. The film, that is, the precursor film forming the precursor. The precursor film is heat-treated in selenium air to form a copper-indium-gallium-selenium quaternary alloy film (for example, refer to Patent Document 1).

另一方面，報告指出在利用使用銦濺鍍靶之濺鍍形成銦膜時，因低融點且表面張力大等銦的物理性質，會引起銦成長成粒狀，使表面生成有不連續間隙的粗的島狀銦膜(以下，簡稱小丘；hillock)之情事(例如，參照非專利文獻1、2)。 On the other hand, the report indicates that when an indium film is formed by sputtering using an indium sputtering target, the physical properties of indium due to a low melting point and a large surface tension cause the indium to grow into a granular shape, resulting in a discontinuous gap on the surface. The rough island-shaped indium film (hereinafter referred to as hillock) is referred to (for example, refer to Non-Patent Documents 1 and 2).

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

[專利文獻1]日本特許第3249408號公報 [Patent Document 1] Japanese Patent No. 3249408

〔非專利文獻〕 [Non-patent literature]

[非專利文獻1]Hyenwook Park, etc. “Effect of precursor structure on Cu(InGa)Se2 formation by reactive annealing” Thin Solid Film 519 (2011) 7245-7249, Fig.2(a), (c) [journal homepage: www.elesevier.com/locate/tsf] [Non-Patent Document 1] Hyenwook Park, etc. "Effect of precursor structure on Cu (InGa) Se 2 formation by reactive annealing" Thin Solid Film 519 (2011) 7245-7249, Fig. 2(a), (c) [ Journal homepage: www.elesevier.com/locate/tsf]

[非專利文獻2]S. Merdes, etc. “Influence of precursor stacking on the absorber growth in Cu(InGa)Se2 based solar cells prepared by a rapid thermal process” Thin Solid Film 519 (2011) 7189-7192, Fig.1 (a) [journal homepage: www.elesevier.com/locate/tsf] [Non-Patent Document 2] S. Merdes, etc. "Influence of precursor stacking on the absorber growth in Cu (InGa) Se 2 based solar cells prepared by a rapid thermal process" Thin Solid Film 519 (2011) 7189-7192, Fig .1 (a) [journal homepage: www.elesevier.com/locate/tsf]

如上述方式，以濺鍍法來形成銦膜時，銦會凝集成島狀並形成不連續層，例如，在銅-鎵合金膜上層積銦膜之場合下，會形成銦覆蓋的部分與銦沒有覆蓋到的部分。一旦這樣的銦的小丘形成，在之後的硒化處理時，會使沒有銦之處成為富有銅，讓低電阻的銅-硒化合物在局部被生成。結果，使光吸收層的成分組成出現散亂，造成太陽電池的性能降低。 As described above, when an indium film is formed by sputtering, indium aggregates into an island shape and forms a discontinuous layer. For example, in the case where an indium film is laminated on a copper-gallium alloy film, an indium-covered portion and an indium are not formed. The part that is covered. Once such a hillock of indium is formed, in the subsequent selenization treatment, copper is not rich and copper is formed, and a low-resistance copper-selenium compound is locally formed. As a result, the composition of the light absorbing layer is scattered, resulting in a decrease in the performance of the solar cell.

於是，本發明之目的在於提供一種銦濺鍍靶，在利用濺鍍法形成銦膜時能夠防止銦的小丘，適宜薄膜太陽電池之CIGS系光吸收層的形成之銦濺鍍靶。再者，本發明之目的在於提供一種銦膜，以採用該銦濺鍍靶之濺鍍來成膜、防止銦小丘的形成而改善膜質之、具有面內均一性之銦膜。 Accordingly, an object of the present invention is to provide an indium sputtering target which is capable of preventing hillocks of indium when an indium film is formed by a sputtering method, and is suitable for forming a CIGS-based light absorbing layer of a thin film solar cell. Further, an object of the present invention is to provide an indium film which is formed by sputtering of the indium sputtering target to prevent formation of indium hillocks and to improve the film quality and to have in-plane uniformity of the indium film.

本發明人等，著眼於在銦膜成膜時出現銦小丘形成的防止上，能夠藉由改善銦對於下底膜之銅鎵膜，或者，銅或鉬膜之濕潤性來解決，檢討結果，判明在銦添加鉍、銻、錫、鋅時，能夠改善該濕潤性。 The inventors of the present invention have focused on the prevention of formation of indium hillocks during film formation of an indium film, and can solve the problem by improving the wettability of indium to the copper-gallium film of the underlying film or the copper or molybdenum film. It was found that the wettability can be improved when yttrium, lanthanum, tin, and zinc are added to indium.

於是，以銦作為主成分，製作出種種少量添加了從鉍、銻、錫、鋅選擇而來的元素之銦濺鍍靶，採用該等的銦濺鍍靶，以直流(DC)濺鍍，把銦膜成膜化後，確認可以得到銦膜的濕潤性改善，且小丘並未形成、具有面內均一性之銦膜。 Then, using indium as a main component, various indium sputtering targets having elements selected from ruthenium, osmium, tin, and zinc were prepared, and these indium sputtering targets were used for direct current (DC) sputtering. After the indium film was formed into a film, it was confirmed that an indium film having an in-plane uniformity was not formed, and the indium film was not formed.

從而，本發明係由上述知見所得到的，為解決前述課題而有以下較佳構成型態。 Accordingly, the present invention has been made in view of the above-described findings, and has the following preferred configuration in order to solve the above problems.

(1)一種銦濺鍍靶，其特徵係含有合計0.5~10.0原子%之從鉍、銻、錫、鋅選擇而來1種以上的元素，殘部具有由銦及不可避免不純物所構成的成分組成。 (1) An indium sputtering target characterized in that it contains 0.5 to 10.0 atom% of a total of one or more elements selected from ruthenium, osmium, tin, and zinc, and the residue has a composition consisting of indium and unavoidable impurities. .

(2)如前述(1)記載之銦濺鍍靶，其中，濺鍍靶中的氧濃度為0.04質量%以下。 (2) The indium sputtering target according to the above (1), wherein the oxygen concentration in the sputtering target is 0.04% by mass or less.

(3)如前述(1)記載之銦濺鍍靶，其中，濺鍍靶中之含從鉍、銻、錫、鋅選擇而來1種以上之合金相的最大粒徑為50μm以下。 (3) The indium sputtering target according to the above (1), wherein the maximum particle diameter of the alloy phase selected from the group consisting of ruthenium, osmium, tin, and zinc is 50 μm or less.

(4)一種CIGS太陽電池製造用銦膜，其特徵係含有合計0.5~10.0原子%之從鉍(Bi)、銻(Sb)、錫(Sn)、鋅(Zn)選擇而來1種以上的元素，殘部具有由銦及不可避免不純物所構成的成分組成。 (4) An indium film for producing a CIGS solar cell, which is characterized in that it is selected from the group consisting of bismuth (Bi), bismuth (Sb), tin (Sn), and zinc (Zn) in a total amount of 0.5 to 10.0 atom%. The element and the residue have a composition composed of indium and unavoidable impurities.

在上述本發明的型態的銦濺鍍靶(以下，簡稱本發明之銦濺鍍靶)，添加從鉍、銻、鋅選擇而來1種以上的元素方面，合計設為含有0.5~10.0原子%，而限定該添加量範圍之理由是因為，該添加量多過10.0原子%時，會使CIGS系薄膜太陽電池的轉換效率降低，另一方面，該添加量未滿0.5原子%時，則對於膜中的銦小丘發生，亦即，島狀銦的發生無法抑制的緣故。 In the above-described indium sputtering target of the present invention (hereinafter referred to as the indium sputtering target of the present invention), one or more elements selected from lanthanum, cerium, and zinc are added, and the total amount is 0.5 to 10.0 atoms. %, and the reason for limiting the range of the added amount is that when the amount of addition exceeds 10.0 atom%, the conversion efficiency of the CIGS-based thin film solar cell is lowered. On the other hand, when the added amount is less than 0.5 atom%, the amount is less than 0.5 atom%. The occurrence of indium hillocks in the film, that is, the occurrence of island indium cannot be suppressed.

此外，濺鍍靶中的含從鉍、銻、錫、鋅選擇而來1種以上的元素之合金相(例如，該等元素的1種與銦之化合物(BiIn2、Bi3In5、BiIn、InSb)或者，鋅與銻之化合物或各元素間之固溶體等。以下，簡稱添加元素含有合金相)之最大粒徑為50μm以下。在此，在採用添加從鉍、銻、錫、鋅選擇而來1種以上的元素之銦濺鍍靶進行直流(DC)濺鍍時，添加元素含有合金相的粒徑大小會是發生異常放電、結節的主要原因，但，最大粒徑為50μm以下的話，則不會發生過度的異常放電。 Further, an alloy phase containing one or more elements selected from ruthenium, osmium, tin, and zinc in the sputtering target (for example, a compound of one of these elements and indium (BiIn 2 , Bi 3 In 5 , BiIn) InSb) or a solid solution of a compound of zinc and lanthanum or each element, etc. Hereinafter, simply referred to as an additive phase containing an alloy phase, the maximum particle diameter is 50 μm or less. Here, when direct current (DC) sputtering is performed using an indium sputtering target in which one or more elements selected from yttrium, lanthanum, tin, and zinc are added, the particle size of the alloy containing the added element may be abnormal discharge. The main cause of nodules, however, if the maximum particle size is 50 μm or less, excessive abnormal discharge does not occur.

再者，濺鍍靶中的氧含有量，在濺鍍後是靶表面龜裂 的發生原因、抑制濺鍍時發生的異常放電等方面，最好是盡可能的少，本發明中，則是把氧含有量設定在0.04質量%以下。進而，更好是氧含有量在0.03質量%以下。 Furthermore, the oxygen content in the sputtering target is the target surface crack after sputtering. It is preferable that the cause of the occurrence and the occurrence of abnormal discharge occurring during sputtering are as small as possible. In the present invention, the oxygen content is set to 0.04% by mass or less. Further, it is more preferable that the oxygen content is 0.03 mass% or less.

如以上方式，本發明之銦濺鍍靶之特徵係含有合計0.5~10.0原子%之從鉍(Bi)、銻(Sb)、錫(Sn)、鋅(Zn)選擇而來1種以上的元素、殘部具有由銦及不可避免不純物所構成的成分組成；採用該銦濺鍍靶來進行濺鍍的話，則能夠形成含有合計0.5~10.0原子%之從鉍、銻、錫、鋅選擇而來1種以上的元素、殘部具有由銦及不可避免不純物所構成的成分組成之銦膜，藉由添加從鉍、銻、錫、鋅選擇而來1種以上的元素，來改善膜質、得到均一的銦膜，對於CIGS系化合物薄膜太陽電池的光吸收層的形成是有效的，並且，也可以適用於線上(in-line)方式濺鍍，有助於薄膜太陽電池的生產性提升。 As described above, the indium sputtering target of the present invention is characterized by containing a total of one or more elements selected from the group consisting of bismuth (Bi), bismuth (Sb), tin (Sn), and zinc (Zn) in a total amount of 0.5 to 10.0 atomic percent. The residual portion is composed of a component composed of indium and unavoidable impurities. When the indium sputtering target is used for sputtering, it is possible to form a total of 0.5 to 10.0 atomic percent from lanthanum, cerium, tin, and zinc. An indium film composed of a component composed of indium and inevitable impurities, and an element having at least one element selected from the group consisting of yttrium, lanthanum, tin, and zinc is added to improve the film quality and obtain uniform indium. The film is effective for the formation of a light absorbing layer of a CIGS-based compound thin film solar cell, and can also be applied to in-line sputtering to contribute to the productivity improvement of the thin film solar cell.

1‧‧‧銦(In) 1‧‧‧Indium (In)

2‧‧‧銦-鉍(In-Bi)化合物 2‧‧‧In-Bi compounds

圖1係圖示針對含有鉍(Bi)之濺鍍靶，用電子顯微鏡所取得之COMPO像之例。 Fig. 1 is a view showing an example of a COMPO image obtained by an electron microscope for a sputtering target containing bismuth (Bi).

其次，針對本發明之銦濺鍍靶及其製造方法、還有銦膜，按照實施例具體說明於以下。 Next, the indium sputtering target of the present invention, a method for producing the same, and an indium film will be specifically described below based on examples.

〔實施例〕 [Examples]

首先，為了製造銦濺鍍靶，準備作為靶製造原料之銦(純度4N以上)、鉍(純度4N以上)、銻(純度4N以上)、錫(純度4N以上)、鋅(純度4N以上)等。在此，有關鉍、銻、錫、鋅，作為製造原料雖然可以是錠塊，但因為溶解容易度的緣故，還是準備粉末的。如以下表1所示，分別秤量銦、與作為添加元素之鉍、銻、錫、鋅等各粉末。又，在表1僅顯示添加元素的量(質量%)，而銦的量由於是其殘部所以並不表示出來。 First, in order to manufacture an indium sputtering target, indium (purity of 4N or more), yttrium (purity of 4N or more), yttrium (purity of 4N or more), tin (purity of 4N or more), zinc (purity of 4N or more), and the like are prepared as target production materials. . Here, although tantalum, niobium, tin, and zinc may be ingots as a raw material for production, powders are prepared because of ease of dissolution. As shown in the following Table 1, each of the indium and the respective powders such as cerium, lanthanum, tin, and zinc as the additive elements were weighed. Further, in Table 1, only the amount (% by mass) of the additive element is shown, and the amount of indium is not shown because it is a residual portion.

其次，把已秤量的各原料粉末放入碳製坩堝，於真空中，利用高頻誘導加熱進行加熱、予以溶解。又，也可以取代在真空中加熱，而在大氣中或者非氧化性空氣下加熱。接著，在將各添加元素溶解時點下的溫度保持五分鐘之後，鑄入預先設有堰堤之徑長125mm的銅背襯板(backing plate)上。為了提升鑄造後之與背襯板的密接性，銅背襯板表面最好是預先用進行鑄入的組成的銦合金浸濕。在此，冷卻後，取下堰堤之後，以機械加工，整理成指定形狀，製作出實施例1~29的銦濺鍍靶。又，本實施例，係在溶解銦之後，於銅背襯板上予以鑄造，但也可以藉由預先在銅背襯板上配置銦原料、加熱銅背襯板，而把銦溶解，之後，使之凝固並製作出銦濺鍍靶。 Next, each of the weighed raw material powders is placed in a carbon crucible, and heated and dissolved by high-frequency induction heating in a vacuum. Further, instead of heating in a vacuum, it may be heated in the air or under non-oxidizing air. Next, while the temperature at the time of dissolving each additive element was maintained for five minutes, it was cast on a copper backing plate having a diameter of 125 mm which was previously provided with a bank. In order to improve the adhesion to the backing plate after casting, the surface of the copper backing plate is preferably wetted with an indium alloy of a composition cast in advance. Here, after cooling, the bank was removed, and the indium sputtering target of Examples 1 to 29 was produced by mechanical processing and finishing into a predetermined shape. Further, in the present embodiment, after indium is dissolved, it is cast on a copper backing plate, but indium may be dissolved by disposing an indium raw material on a copper backing plate in advance and heating the copper backing plate. It is solidified and an indium sputtering target is produced.

〔比較例〕 [Comparative Example]

此外，為了跟本發明之實施例做比較，以以下表2所示方式，利用跟實施例之場合同樣的手法，分別製作出不含添加元素之僅有銦的比較例1及2之銦濺鍍靶、添加鉍：0.05原子%的比較例3之銦濺鍍靶、添加鋅：0.07原子%的比較例4之銦濺鍍靶、添加銻：0.07原子%的比較例5之銦濺鍍靶、與添加錫：0.05原子%的比較例6之銦濺鍍靶。 Further, in order to compare with the examples of the present invention, in the same manner as in the case of the embodiment, the indium splashes of Comparative Examples 1 and 2 containing only indium containing no additive elements were produced in the same manner as in the following Table 2. Plating target, addition yttrium: 0.05 at% of the indium sputtering target of Comparative Example 3, zinc: 0.07 atom% of the indium sputtering target of Comparative Example 4, and ytterbium: 0.07 atom% of the indium sputtering target of Comparative Example 5 Indium sputtering target of Comparative Example 6 with addition of tin: 0.05 at%.

製作出的實施例及比較例之銦濺鍍靶的靶基本特性，靶組織的平均粒徑：200μm以下、表面粗度Ra：3μm以下、比電阻：10-1Ω‧cm以下。其次，針對實施例1~29及比較例3~6的銦濺鍍靶，測定添加元素含有合金相的最大粒徑。其測定方法係如以下。 The target basic characteristics of the prepared indium sputtering target of the examples and the comparative examples were as follows: the average particle diameter of the target structure was 200 μm or less, the surface roughness Ra was 3 μm or less, and the specific resistance was 10 -1 Ω·cm or less. Next, with respect to the indium sputtering targets of Examples 1 to 29 and Comparative Examples 3 to 6, the maximum particle diameter of the alloy phase in which the additive element was contained was measured. The measurement method is as follows.

<添加元素含有合金相的最大粒徑測定方法> <Method for Measuring Maximum Particle Size of Additive Element Containing Alloy Phase>

將製作出的濺鍍靶的表面(旋盤加工面)以王水蝕刻1分鐘左右，用純水洗淨後，將根據電子微探儀(EPMA)的映射分析，以倍率200倍、於表面上的任意5處進行觀測。在看不到明確的組織之場合下，追加進行王水的蝕刻。在此，從EPMA之1影像觀察到的添加元素成分之中，把關於最大領域的最大徑設為添加元素含有合金相的最大粒徑。其測定結果顯示於以下的表1。 The surface of the produced sputtering target (rotating surface of the rotary disk) is etched with aqua regia for about 1 minute, washed with pure water, and analyzed according to the mapping of the electronic micro-detector (EPMA) at a magnification of 200 times on the surface. Observe at any 5 places. When the clear organization is not visible, the etching of the aqua regia is additionally performed. Here, among the additive element components observed from the EPMA image 1, the maximum diameter in the largest region is defined as the maximum particle diameter of the alloy phase contained in the additive element. The measurement results are shown in Table 1 below.

又，作為參考例，針對含有5原子%鉍的銦濺 鍍靶，將以電子顯微鏡(SEM)取得的COMPO像的影像顯示於圖1。根據EPMA的元素分布像本來是彩色像，但為了以變換成黑白像之照片來顯示，而在該照片中，愈白表示鉍元素的濃度愈高。具體而言，如圖1的影像，有關銦及鉍之COMPO像，可以在顯示灰色的銦質地中，觀察到灰白色部分的銦-鉍化合物分散分布的樣子。又，對灰白色部分，箭頭顯示「銦-鉍化合物」。 Further, as a reference example, indium splashing containing 5 atom% of ytterbium The target of the plating, the image of the COMPO image obtained by an electron microscope (SEM) is shown in FIG. The elemental distribution according to EPMA is originally a color image, but is displayed in order to be converted into a black-and-white image, and in this photograph, the whiter is the higher the concentration of the yttrium element. Specifically, as shown in the image of FIG. 1, the COMPO image of indium and bismuth can be observed in the gray indium texture in the distribution of the indium-bismuth compound in the off-white portion. Further, in the off-white portion, the arrow shows "indium-antimony compound".

<氧濃度之測定> <Measurement of oxygen concentration>

從製作出的濺鍍靶的表面進行1g左右樣本抽樣，將表面以王水蝕刻1分鐘左右，用純水洗淨後，利用氣體分析來測定氧濃度。 A sample of about 1 g was sampled from the surface of the produced sputtering target, and the surface was etched with aqua regia for about 1 minute, washed with pure water, and then analyzed for oxygen concentration by gas analysis.

<XRD繞射測定結果的解析> <Analysis of XRD diffraction measurement results>

將製作的濺鍍靶的表面利用日本理學電氣(股)製XRD裝置(RINT-Ultima/PC)於2θ=5~80°的範圍予以測定。在表1，把由鉍、銻、錫、鋅添加元素單體而來的峰值出現之場合設為「有」，未出現之場合設為「無」。 The surface of the produced sputtering target was measured in the range of 2θ=5 to 80° using an XRD apparatus (RINT-Ultima/PC) manufactured by Nippon Science & Technology Co., Ltd. In Table 1, the case where the peak of the elemental monomer added by yttrium, lanthanum, tin, and zinc is present is "Yes", and the case where it does not appear is "None".

其次，採用上述實施例1~29及比較例1~6之銦濺鍍靶，按照以下的成膜條件，進行形成銦膜的試驗。銦膜的膜厚係300~500nm。 Next, using the indium sputtering targets of the above Examples 1 to 29 and Comparative Examples 1 to 6, the test for forming an indium film was carried out in accordance with the following film formation conditions. The film thickness of the indium film is 300 to 500 nm.

<成膜條件> <film formation conditions>

‧基板：玻璃基板 ‧Substrate: glass substrate

‧基板尺寸：20mm見方 ‧Substrate size: 20mm square

‧電源：DC500W ‧Power supply: DC500W

‧全壓：0.15Pa ‧ Full pressure: 0.15Pa

‧濺鍍氣體：氬=30sccm ‧ Sputtering gas: argon = 30sccm

‧靶-基板(TS)距離：70mm ‧Target-substrate (TS) distance: 70mm

藉由按照上述成膜條件之成膜試驗，如以下作法，測定異常放電回數，進行觀察該測定後的表面狀態。該測定結果顯示於以下表3及表4之「異常放電(回/h)」欄與「濺鍍後靶表面龜裂之有無」欄。 The film formation test according to the above film formation conditions was carried out, and the number of abnormal discharges was measured as follows, and the surface state after the measurement was observed. The measurement results are shown in the "Abnormal discharge (return / h)" column and "The presence or absence of cracks on the target surface after sputtering" in Tables 3 and 4 below.

<異常放電回數之測定> <Measurement of abnormal discharge count>

在上述條件下進行12小時的濺鍍，利用DC電源裝置所具備的Arc計數功能來計測異常放電的回數。之後，開放濺鍍室，確認室內的粉粒(particle)。 Under the above conditions, sputtering was performed for 12 hours, and the number of abnormal discharges was measured by the Arc counting function of the DC power supply device. After that, the sputtering chamber is opened to confirm the particles in the room.

<觀察濺鍍後的靶表面狀態> <Observing the surface state of the target after sputtering>

觀察異常放電回數測定後的靶表面，把濺蝕部(erosion)凹凸龜裂之場合記為龜裂「有」、把沒有龜裂之場合記為龜裂「無」。 The surface of the target after the measurement of the number of abnormal discharges was observed, and the case where the erosion was cracked was described as "cracking", and the case where no crack was present was referred to as "cracking".

測定依上述成膜條件所得到的銦膜的膜厚，再者，針對該銦膜的表面，確認小丘(島狀態)之有無。該觀察結果顯示於表3及表4之「膜厚(nm)」欄、與「銦小丘有無」欄。 The film thickness of the indium film obtained by the film formation conditions was measured, and the presence or absence of a hillock (island state) was confirmed about the surface of the indium film. The observation results are shown in the column of "film thickness (nm)" and "in the presence of indium hillocks" in Tables 3 and 4.

<小丘之評價方法> < evaluation method of Xiaoqiu>

取出得到的銦膜，用場發射型掃瞄電子顯微鏡(FE-SEM)來確認膜表面有無銦小丘。把在銦膜出現銦小丘者記為「有」，沒出現者記為「無」。 The obtained indium film was taken out, and a field emission type scanning electron microscope (FE-SEM) was used to confirm the presence or absence of indium hillocks on the surface of the film. Those who have indium hills in the indium film are referred to as "Yes", and those who do not appear as "None".

根據以上的表3，以採用實施例1~29的銦濺鍍靶之濺鍍所成膜的銦膜，任一例皆可確認沒有銦小丘，可以得到平坦且均一的銦膜。此外可知，在採用實施例1、3、4、8、10、11、15、16、18、21~24、25、26之銦濺鍍靶進行濺鍍之場合下，由於添加元素含有合金相的最大粒徑小，所以皆無發生異常放電。又，在採用實施例2、3、5~9、12~14、17、19、20、27~29之銦濺鍍靶進行濺鍍之場合下，因添加元素含有合金相的最大粒徑大，而發生異常放電，但是，這並沒有影響到成膜，而仍得到均一的銦膜。 According to the above Table 3, it was confirmed that the indium film formed by the sputtering using the indium sputtering target of Examples 1 to 29 was free of indium hillocks, and a flat and uniform indium film was obtained. In addition, it can be seen that in the case of sputtering using the indium sputtering targets of Examples 1, 3, 4, 8, 10, 11, 15, 16, 18, 21-24, 25, 26, the additive element contains the alloy phase. The maximum particle size is small, so no abnormal discharge occurs. Further, in the case of sputtering using the indium sputtering targets of Examples 2, 3, 5 to 9, 12 to 14, 17, 19, 20, and 27 to 29, the maximum particle diameter of the alloy phase due to the additive element is large. An abnormal discharge occurred, but this did not affect the film formation, but still obtained a uniform indium film.

另一方面，比較例1、2之銦濺鍍靶，在依先前技術之場合、採用該等來進行成膜時，由於在靶中並未含添加元素，而發生銦小丘。此外，比較例3的銦濺鍍靶方面，添加元素鉍的量較少、比較例4的銦濺鍍靶方面，添加元素鋅的量較少、比較例5的銦濺鍍靶方面，添加元 素銻的量較少、而比較例6的銦濺鍍靶方面，添加元素錫的量較少，因而，在濺鍍時，雖沒見到異常放電的出現，卻有銦小丘發生。採用比較例1~6的銦濺鍍靶被形成的銦膜，任一例皆未見到膜質改善。 On the other hand, in the indium sputtering targets of Comparative Examples 1 and 2, when the film formation was carried out by the above-described techniques, the indium hillocks were generated because the target did not contain an additive element. Further, in the indium sputtering target of Comparative Example 3, the amount of the added element lanthanum was small, and in the case of the indium sputtering target of Comparative Example 4, the amount of the added element zinc was small, and the indium sputtering target of Comparative Example 5 was added. The amount of the elemental bismuth was small, and the amount of the elemental tin added was small in the indium sputtering target of Comparative Example 6. Therefore, in the case of sputtering, although the occurrence of abnormal discharge was not observed, indium hillocks occurred. The indium film formed by the indium sputtering targets of Comparative Examples 1 to 6 was used, and no improvement in film quality was observed in any of the examples.

如以上，確認根據本發明之，用含有合計0.5~10.0原子%之從鉍、銻、錫、鋅選擇而來1種以上的元素、殘部具有由銦及不可避免不純物所構成的成分組成之銦濺鍍靶而被成膜的銦膜，係含有合計0.5~10.0原子%之從鉍、銻、錫、鋅選擇而來1種以上的元素，殘部具有由銦及不可避免不純物所構成的成分組成，膜質被改善，可以得到均一的銦膜。可知根據本發明之銦膜正是適宜形成CIGS系薄膜太陽電池的光吸收層。 As described above, it is confirmed that indium containing at least one element selected from the group consisting of ruthenium, osmium, tin, and zinc and having a residue consisting of indium and unavoidable impurities is contained in an amount of 0.5 to 10.0 atomic % in total. The indium film formed by sputtering the target is composed of yttrium, lanthanum, tin, and zinc in a total amount of 0.5 to 10.0 atom%, and the remaining portion has a composition of indium and unavoidable impurities. The film quality is improved, and a uniform indium film can be obtained. It is understood that the indium film according to the present invention is a light absorbing layer suitable for forming a CIGS-based thin film solar cell.

〔產業上利用可能性〕 [Industrial use possibility]

藉由利用硒化法，來提供適於形成由銅-銦-鎵-硒四元系合成膜所構成的光吸收層之因濺鍍靶，能夠使具備該光吸收層的太陽電池之性能提升。 By using a selenization method to provide a sputtering target suitable for forming a light absorbing layer composed of a copper-indium-gallium-selenium quaternary composite film, the performance of a solar cell having the light absorbing layer can be improved. .

1‧‧‧銦(In) 1‧‧‧Indium (In)

2‧‧‧銦-鉍(In-Bi)化合物 2‧‧‧In-Bi compounds

Claims (4)

一種銦濺鍍靶，其特徵係：含有合計0.5~10.0原子%之從鉍(Bi)、銻(Sb)、錫(Sn)、鋅(Zn)選擇而來之1種以上的元素，殘部具有由銦及不可避免不純物所構成的成分組成。 An indium sputtering target characterized by containing a total of one or more elements selected from the group consisting of bismuth (Bi), bismuth (Sb), tin (Sn), and zinc (Zn) in a total amount of 0.5 to 10.0 atom%, and the residue has It consists of components consisting of indium and unavoidable impurities. 如申請專利範圍第1項記載之銦濺鍍靶，其中濺鍍靶中的氧濃度為0.04質量%以下。 The indium sputtering target according to the first aspect of the invention, wherein the oxygen concentration in the sputtering target is 0.04% by mass or less. 如申請專利範圍第1項記載之銦濺鍍靶，其中濺鍍靶中之含從鉍、銻、錫、鋅選擇而來的1種以上之合金相的最大粒徑為50μm以下。 The indium sputtering target according to the first aspect of the invention, wherein the maximum particle diameter of the one or more alloy phases selected from the group consisting of ruthenium, osmium, tin, and zinc in the sputtering target is 50 μm or less. 一種CIGS太陽電池製造用銦膜，其特徵係：含有合計0.5~10.0原子%之從鉍(Bi)、銻(Sb)、錫(Sn)、鋅(Zn)選擇而來1種以上的元素，殘部具有由銦及不可避免不純物所構成的成分組成。 An indium film for producing a CIGS solar cell, characterized in that it contains one or more elements selected from the group consisting of bismuth (Bi), bismuth (Sb), tin (Sn), and zinc (Zn) in a total amount of 0.5 to 10.0 atom%. The residue has a composition composed of indium and unavoidable impurities.
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