TW201638348A - Copper-gallium alloy sputtering target - Google Patents
Copper-gallium alloy sputtering target Download PDFInfo
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- TW201638348A TW201638348A TW105108862A TW105108862A TW201638348A TW 201638348 A TW201638348 A TW 201638348A TW 105108862 A TW105108862 A TW 105108862A TW 105108862 A TW105108862 A TW 105108862A TW 201638348 A TW201638348 A TW 201638348A
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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
- C23C14/22—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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C9/00—Alloys based on copper
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Abstract
Description
本發明涉及一種銅-鎵合金濺射靶材。尤其是，本發明涉及一種在形成作為薄膜太陽能電池層的光吸收層的銅-銦-鎵-硒(Cu-In-Ga-Se，以下，記為CIGS)四元合金薄膜時所使用的銅-鎵合金濺射靶材。 The present invention relates to a copper-gallium alloy sputtering target. In particular, the present invention relates to a copper used in forming a copper-indium-gallium-selenium (Cu-In-Ga-Se, hereinafter referred to as CIGS) quaternary alloy film as a light absorbing layer of a thin film solar cell layer. - Gallium alloy sputtering target.
近年，作為薄膜太陽能電池的高光電轉換效率的CIGS系太陽能電池在量產上正有所進展。CIGS系薄膜太陽能電池通常具有將背電極、光吸收層、緩衝層以及透明電極等順次積層的結構。作為該光吸收層的製造方法、蒸鍍法和硒化法是公知的。以蒸鍍法製造的太陽能電池具有高轉換效率的優點，但具有成膜速度低、成本高、低生產性的缺點，硒化法則適用於產業上的大規模生產。 In recent years, CIGS-based solar cells, which have high photoelectric conversion efficiency as thin film solar cells, are making progress in mass production. A CIGS-based thin film solar cell generally has a structure in which a back electrode, a light absorbing layer, a buffer layer, a transparent electrode, and the like are sequentially laminated. A method for producing the light absorbing layer, a vapor deposition method, and a selenization method are known. The solar cell manufactured by the vapor deposition method has the advantages of high conversion efficiency, but has the disadvantages of low film formation speed, high cost, and low productivity, and the selenization method is suitable for industrial mass production.
硒化法的簡要工序如下。首先，在鹼石灰玻璃基板上形成鉬電極層，在其上濺射沉積銅-鎵層和銦層後，通過硒化氫氣體下的高溫處理形成CIGS層。在由該硒化法形成CIGS層的形成工序中濺射沉澱銅-鎵層時，使用了銅-鎵合金濺射靶材。 The brief procedure of the selenization method is as follows. First, a molybdenum electrode layer is formed on a soda lime glass substrate, and after depositing a copper-gallium layer and an indium layer thereon, a CIGS layer is formed by high temperature treatment under hydrogen selenide gas. When a copper-gallium layer is sputter-deposited in the formation process of forming a CIGS layer by this selenization method, a copper-gallium alloy sputtering target is used.
作為濺射靶材的形狀，有平板形和圓筒形狀。圓筒形靶材，由於通過以圓柱軸線為中心進行旋轉而使整個表面被侵蝕，因此材料的利用率比平板形靶材高，而且由於通過連續改變電漿照射表面而能夠有效冷卻，因此可維持高輸出，提高量產性。然而，圓筒形靶材與平板形靶材相比，由於形狀複雜而製造難度高，製造時發生開裂和缺損的危險性變高。如果在濺射中發生開裂或缺損，由此產生的碎片和裂紋而成為顆粒和異常放電發生的原因。此外，具有在運輸或濺射過程中不易破損的高強度也是對平板形靶材的額外要求。 As the shape of the sputtering target, there are a flat plate shape and a cylindrical shape. In the cylindrical target, since the entire surface is eroded by rotating around the cylinder axis, the utilization of the material is higher than that of the flat-shaped target, and since it can be effectively cooled by continuously changing the surface of the plasma irradiation, it can be effectively cooled. Maintain high output and increase mass production. However, compared with a flat-shaped target, a cylindrical target is difficult to manufacture due to a complicated shape, and the risk of cracking and chipping at the time of manufacture becomes high. If cracking or chipping occurs in sputtering, the resulting chips and cracks become the cause of the occurrence of particles and abnormal discharge. In addition, having high strength that is not easily broken during transportation or sputtering is an additional requirement for flat-plate targets.
其中，作為銅-鎵合金靶材的製造方法，熔解鑄造法和粉末 燒結法是公知的。粉末燒結法中存在不可避免的空孔。空孔不僅造成異常放電，也使高密度化變得困難，成為在切削或濺射時產生開裂和缺損的原因。日本專利公開第2008-138232號公報(專利文獻1)中揭露了為防止造成開裂的偏析，將高濃度鎵粉末和低濃度鎵粉末混合並燒結、形成兩相組織的方法，但工藝複雜且成本高。 Among them, as a manufacturing method of a copper-gallium alloy target, a melt casting method and a powder Sintering methods are well known. There are inevitable voids in the powder sintering process. The voids cause not only abnormal discharge but also high density, which causes cracking and chipping during cutting or sputtering. Japanese Patent Publication No. 2008-138232 (Patent Document 1) discloses a method of mixing and sintering a high-concentration gallium powder and a low-concentration gallium powder to prevent two-phase structure in order to prevent segregation caused by cracking, but the process is complicated and costly. high.
另一方面，關於熔解鑄造法，日本專利公開第2000-073163號公報(專利文獻2)中記載了：通過熔解法將鎵的組成分設為15重量%-70重量%而鑄造的銅-鎵合金；還記載了作為該銅-鎵合金的製造方法，利用具有加熱單元和冷卻單元的鑄型，控制溫度使其達到不產生脆性開裂和偏析的冷卻速度，通過熔解法進行鑄造的方法。由於通過該方法得到的銅-鎵合金不具有脆性和偏析，因此成型容易且能夠加工成任意形狀。 On the other hand, in the melt-casting method, Japanese Patent Publication No. 2000-073163 (Patent Document 2) describes a copper-gallium cast by a melting method in which the composition of gallium is 15% by weight to 70% by weight. An alloy is also described as a method for producing the copper-gallium alloy by casting a mold having a heating unit and a cooling unit, controlling the temperature to a cooling rate without causing brittle cracking and segregation, and casting by a melting method. Since the copper-gallium alloy obtained by this method does not have brittleness and segregation, it is easy to mold and can be processed into an arbitrary shape.
日本專利公開第2013-76129號公報(專利文獻3)中記載了：通過熔解鑄造形成為圓筒的、鈣(Ca)濃度為27wt%以上且30wt%以下的銅-鎵合金的濺射靶材。也記載了該濺射靶材的組織在平行地切割所述濺射靶材的凝固面的切面中為等軸狀的特徵。還記載了該濺射靶材品質高且可量產。 Japanese Patent Publication No. 2013-76129 (Patent Document 3) discloses a sputtering target of a copper-gallium alloy having a calcium (Ca) concentration of 27% by weight or more and 30% by weight or less which is formed into a cylinder by melt casting. . It is also described that the structure of the sputtering target is equiaxed in a cut surface in which the solidification surface of the sputtering target is cut in parallel. It is also described that the sputtering target is high in quality and mass-produced.
【專利文獻】 [Patent Literature]
【專利文獻1】日本專利公開第2008-138232號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-138232
【專利文獻2】日本專利公開第2000-73163號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-73163
【專利文獻3】日本專利公開第2013-76129號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-76129
基於製造圓筒形靶材，考慮到熔解鑄造法比粉末燒結法更適用，但上述任何文獻中關於靶材的強度的研究都不充分。 Based on the manufacture of a cylindrical target, it is considered that the melt casting method is more suitable than the powder sintering method, but the research on the strength of the target in any of the above documents is insufficient.
專利文獻2中雖然記載了控制溫度使其達到不產生脆性開裂和偏析的冷卻速度，但僅對冷卻速度的控制，不能控制引起濺射時的異常放電的縮孔的產生。因為，在澆鑄金屬液體的鑄造方法中，在凝固過程中保持一定的凝固速度是困難的，即使使其從鑄型底部定向凝固，在鑄型 上部，由於釋放的凝固潛熱使凝固速度變小，也會產生較多縮孔。而且，專利文獻2中記載了將冷卻速度控制在1.0×10-1℃/sec~1.5×10-2℃/sec的範圍內，但由於冷卻速度慢，以該冷卻速度得到的結晶組織為等軸晶。等軸晶不具有高的強度。此外，專利文獻2中沒有關於圓筒形靶材的記載。 Patent Document 2 describes that the temperature is controlled so as to achieve a cooling rate that does not cause brittle cracking and segregation. However, the control of the cooling rate cannot control the occurrence of shrinkage cavities that cause abnormal discharge during sputtering. Because, in the casting method of casting a metal liquid, it is difficult to maintain a certain solidification speed during solidification even if it is directionally solidified from the bottom of the mold, in the mold. In the upper part, due to the latent heat of solidification released, the solidification speed becomes smaller, and more shrinkage holes are generated. Further, Patent Document 2 describes that the cooling rate is controlled within a range of 1.0 × 10 -1 ° C / sec to 1.5 × 10 - 2 ° C / sec, but the cooling rate is slow, and the crystal structure obtained at the cooling rate is equal. Axial crystal. Equiaxial crystals do not have high strength. Further, Patent Document 2 does not describe the cylindrical target.
專利文獻3中雖然具體地記載了圓筒形靶材，但是由於其與專利文獻2相同，結晶組織為等軸晶，不能得到具有足夠強度的靶材。 Although a cylindrical target is specifically described in Patent Document 3, since it is the same as Patent Document 2, the crystal structure is equiaxed, and a target having sufficient strength cannot be obtained.
本發明是鑒於上述情況而產生的，將提供一種具有高強度的鈣比例高的銅-鎵合金濺射靶材作為課題。此外，特別是將提供一種為圓筒形的高強度的銅-鎵合金濺射靶材作為課題。 The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a copper-gallium alloy sputtering target having a high calcium ratio with high strength. Further, in particular, a cylindrical high-strength copper-gallium alloy sputtering target is provided as a problem.
本發明人為解決上述課題進行了深入研究，發現了銅-鎵合金為柱狀晶，且通過將ζ相的(112)面的取向率控制在25%~60%內，即使是鎵比例高的銅-鎵合金也易於表現出高強度，從而完成了本發明。 The present inventors have conducted intensive studies to solve the above problems, and found that a copper-gallium alloy is a columnar crystal, and the orientation ratio of the (112) plane of the ζ phase is controlled within 25% to 60%, even if the ratio of gallium is high. The copper-gallium alloy is also liable to exhibit high strength, thereby completing the present invention.
因此，本發明的一個態樣為，一種柱狀晶的銅-鎵合金濺射靶材，其含有含量為25.0原子%以上且29.5原子%以下的鎵，且餘量由銅和不可避免的雜質構成，其特徵在於，用X射線衍射中的ζ相的(100)面、(002)面、(101)面、(102)面、(110)面、(200)面、(112)面、(201)面和(004)面的各衍射峰的測定強度分別除以JCPDS卡片編號44-1117中所記載的所述各衍射峰對應的結晶面的標準強度後得到的值的總和作為(A)，並且，用通過X射線衍射的ζ相的(112)面的衍射峰強度除以JCPDS卡片編號44-1117中所記載的(112)面的衍射峰標準強度後的值作為(B)時，通過(B)/(A)求得的ζ相的(112)面的取向率為25%~60%。 Therefore, an aspect of the present invention is a columnar crystal copper-gallium alloy sputtering target containing gallium in an amount of 25.0 atom% or more and 29.5 atom% or less, and the balance being copper and inevitable impurities The configuration is characterized by using (100) plane, (002) plane, (101) plane, (102) plane, (110) plane, (200) plane, (112) plane of the ζ phase in X-ray diffraction, The sum of the measured intensities of the diffraction peaks of the (201) plane and the (004) plane is divided by the standard intensity of the crystal plane corresponding to each of the diffraction peaks described in JCPDS card No. 44-1117 as (A). And the value of the diffraction peak intensity of the (112) plane of the ζ phase by X-ray diffraction divided by the standard intensity of the diffraction peak of the (112) plane described in JCPDS card number 44-1117 is taken as (B) The orientation ratio of the (112) plane of the ζ phase obtained by (B)/(A) is 25% to 60%.
本發明所涉及的濺射靶材的另一個態樣，相對密度為99.0~100%。 Another aspect of the sputtering target according to the present invention has a relative density of 99.0 to 100%.
本發明所涉及的濺射靶材的另一個態樣，所述不可避免的雜質的含氧量為50質量ppm以下，所述不可避免的雜質的含碳量為30質量ppm以下。 In another aspect of the sputtering target according to the present invention, the unavoidable impurity has an oxygen content of 50 ppm by mass or less, and the unavoidable impurity has a carbon content of 30 ppm by mass or less.
進一步地，本發明所涉及的濺射靶材的另一個方態樣，為板狀或圓筒形狀。 Further, another aspect of the sputtering target according to the present invention is a plate shape or a cylindrical shape.
進一步地，本發明所涉及的濺射靶材的另一個態樣，為圓 筒形狀。 Further, another aspect of the sputtering target according to the present invention is a circle Cartridge shape.
進一步地，在本發明所涉及的濺射靶材的另一個態樣，通過鑄造來形成。 Further, another aspect of the sputtering target according to the present invention is formed by casting.
通過本發明，可提供一種具有高強度的鎵比例高的銅-鎵合金濺射靶材。此外，特別是可提供一種為圓筒形之由銅-鎵合金製成具有高強度的銅-鎵合金濺射靶材。具體地，可提供一種在鎵含量為25.0原子%~29.5原子%的銅-鎵合金中抗彎強度高的濺射靶材。本發明所涉及的濺射靶材為圓筒形時，其效果被更顯著地表現出來。本發明所涉及的濺射靶材搬運或濺射時不易破損，實用性優異。 According to the present invention, a copper-gallium alloy sputtering target having a high strength and a high proportion of gallium can be provided. Further, in particular, a copper-gallium alloy sputtering target made of a copper-gallium alloy having a high strength can be provided. Specifically, a sputtering target having a high bending strength in a copper-gallium alloy having a gallium content of 25.0 atom% to 29.5 atom% can be provided. When the sputtering target according to the present invention has a cylindrical shape, the effect is more prominently exhibited. The sputtering target according to the present invention is less likely to be damaged during conveyance or sputtering, and is excellent in practicability.
20‧‧‧鑄型 20‧‧‧ casting
30‧‧‧立式連續鑄造裝置 30‧‧‧Vertical continuous casting device
31‧‧‧坩堝 31‧‧‧坩埚
32‧‧‧鑄芯 32‧‧‧ casting core
33‧‧‧水冷銅套 33‧‧‧Water-cooled copper sleeve
34‧‧‧引錠 34‧‧‧ lead
36‧‧‧冷卻介質探針***口 36‧‧‧ Cooling medium probe insertion port
38‧‧‧熔融金屬 38‧‧‧ molten metal
39‧‧‧鑄件(空心坯) 39‧‧‧ castings (hollow billets)
42‧‧‧惰性氣體導入裝置 42‧‧‧Inert gas introduction device
43‧‧‧熔融金屬溫度測定用熱電偶 43‧‧‧ Thermocouple for measuring molten metal temperature
44‧‧‧坩堝溫度測定用熱電偶 44‧‧‧坩埚 Thermocouple for temperature measurement
45‧‧‧加熱裝置 45‧‧‧ heating device
46‧‧‧冷卻介質探針 46‧‧‧ Cooling medium probe
47‧‧‧拉拔裝置 47‧‧‧Drawing device
48‧‧‧夾送輥 48‧‧‧Pinch roller
50‧‧‧重力鑄造裝置 50‧‧‧Gravity casting device
51‧‧‧坩堝 51‧‧‧坩埚
52‧‧‧中間包 52‧‧‧Tundish
53‧‧‧鑄型 53‧‧‧Mold
第1圖是銅-鎵系合金的狀態圖。 Fig. 1 is a state diagram of a copper-gallium alloy.
第2圖是本發明所涉及的銅-鎵合金濺射靶材剖面的微觀組織的一個例子。 Fig. 2 is a view showing an example of the microstructure of a cross section of a copper-gallium alloy sputtering target according to the present invention.
第3圖是現有技術中銅-鎵合金濺射靶材剖面的微觀組織的一個例子。 Fig. 3 is an example of the microstructure of a cross section of a copper-gallium alloy sputtering target in the prior art.
第4圖是由EPMA得到的本發明所涉及的銅-鎵合金濺射靶剖面的背散射電子像(COMPO像)的一個例子(倍率：50倍)。 Fig. 4 is an example of a backscattered electron image (COMPO image) of a cross section of a copper-gallium alloy sputtering target according to the present invention obtained by EPMA (magnification: 50 times).
第5圖是由EPMA得到的現有技術中銅-鎵合金濺射靶剖面的背散射電子像(COMPO像)的一個例子(倍率：50倍)。 Fig. 5 is an example of a backscattered electron image (COMPO image) of a cross section of a prior art copper-gallium alloy sputtering target obtained by EPMA (magnification: 50 times).
第6圖是由X射線衍射測得的本發明所涉及的銅-鎵合金濺射靶剖面的衍射峰的一個例子(倍率：50倍)。 Fig. 6 is an example of a diffraction peak of a cross section of a copper-gallium alloy sputtering target according to the present invention measured by X-ray diffraction (magnification: 50 times).
第7圖是由X射線衍射測得的現有技術中銅-鎵合金濺射靶剖面的衍射峰的一個例子(倍率：50倍)。 Fig. 7 is an example of a diffraction peak of a cross section of a prior art copper-gallium alloy sputtering target measured by X-ray diffraction (magnification: 50 times).
第8圖是示出實施例中使用的立式連續鑄造裝置的結構的示意圖。 Fig. 8 is a schematic view showing the structure of a vertical continuous casting apparatus used in the embodiment.
第9圖是示出比較例中使用的重力鑄造裝置的結構的示意圖。 Fig. 9 is a schematic view showing the structure of a gravity casting apparatus used in a comparative example.
從第1圖的銅-鎵系合金的狀態圖可知，銅(α)相鎵含量為0~20.6原子%、β相鎵含量為19.3原子%~27.5原子%、ζ相鎵含量為20.5%~22.5原子%、γ相鎵含量為29.5原子%~34.7原子%、γ 1相鎵含量為29.8原子%~37.4原子%、γ 2相鎵含量為33.9原子%~37.7原子%、γ 3相鎵含量為37.5原子%~42.7原子%等。 It can be seen from the state diagram of the copper-gallium alloy in Fig. 1 that the copper (α) phase gallium content is 0 to 20.6 atom%, the β phase gallium content is 19.3 atom% to 27.5 atom%, and the germanium phase gallium content is 20.5%. 22.5 atom%, gamma phase gallium content is 29.5 atom% to 34.7 atom%, gamma 1 phase gallium content is 29.8 atom% to 37.4 atom%, γ2 phase gallium content is 33.9 atom% to 37.7 atom%, γ3 phase gallium content It is 37.5 atom% to 42.7 atom%.
(組成分) (composition)
本發明所涉及的銅-鎵合金濺射靶材在一個實施方式中，其組成分為：含有25.0原子%以上且29.5原子%以下的鎵，且餘量由銅和不可避免的雜質構成。鎵的含量雖然是根據形成製造CIGS系太陽能電池時所必需的銅-鎵合金濺射膜的要求而確定的，但是本發明的一個特徵在於，較高地設定鎵的含量。從銅-鎵系的狀態圖可看出，隨著鎵的含量變高，ζ相中γ相的比例增加，但由於γ相比ζ相脆，因此難以確保強度。本發明中，由於適當控制晶體結構和這兩相中具有較高延展性的ζ相的(112)面的取向率，即使鎵的含量較高，也能成功地得到高的強度。通過銅-鎵系的狀態圖，鎵的含量為27.5原子%以上時，γ相佔據優勢，因此，根據本發明，特別是當鎵的含量為27.5原子%以上時，明顯地表現出強度提高的效果。 In one embodiment, the copper-gallium alloy sputtering target according to the present invention has a composition of gallium containing 25.0 atom% or more and 29.5 atom% or less, and the balance is composed of copper and unavoidable impurities. Although the content of gallium is determined in accordance with the requirements for forming a copper-gallium alloy sputter film which is necessary for manufacturing a CIGS-based solar cell, one feature of the present invention is that the content of gallium is set high. As can be seen from the state diagram of the copper-gallium system, as the content of gallium becomes higher, the proportion of the γ phase in the ζ phase increases, but since γ is brittle compared to ζ phase, it is difficult to ensure strength. In the present invention, since the crystal structure and the orientation ratio of the (112) plane of the ζ phase having high ductility in the two phases are appropriately controlled, even if the content of gallium is high, high strength can be successfully obtained. When the content of gallium is 27.5 atom% or more, the γ phase is dominant by the state diagram of the copper-gallium system. Therefore, according to the present invention, particularly when the content of gallium is 27.5 atom% or more, the strength is remarkably improved. effect.
本發明所涉及的銅-鎵合金濺射靶材在另一個實施方式中，不可避免的雜質的氧含量為50質量ppm以下，較佳為30質量ppm以下。基於這樣的構成，通過減少成為濺射靶材的開裂起點的氧化物、以及含碳微粒與碳元素的化合物等，能夠提高濺射靶材的強度。 In another embodiment of the copper-gallium alloy sputtering target according to the present invention, the oxygen content of the unavoidable impurities is 50 ppm by mass or less, preferably 30 ppm by mass or less. With such a configuration, the strength of the sputtering target can be improved by reducing the oxide which is the starting point of the sputtering target and the compound containing carbon fine particles and carbon.
(晶體結構) (Crystal structure)
本發明所涉及的銅-鎵合金濺射靶材的特徵在於，其為柱狀晶。在一個實施方式中，可具有由鈣固溶於銅中的γ相或ζ相混合組成的柱狀晶。由於形成柱狀晶，與等軸晶相比能夠具有更高的強度。通過第2圖及第3圖所示出的金相組織的宏觀觀察，可看見線狀的晶界，由此可確認柱狀晶。此外，本發明所涉及的銅-鎵合金為γ相和ζ相的混合相，這是可從銅-鎵系的狀態圖得到的。僅為γ相時硬而脆，通過與相對韌性的ζ相混合成為混合相，可得到韌性組織。 The copper-gallium alloy sputtering target according to the present invention is characterized in that it is a columnar crystal. In one embodiment, there may be a columnar crystal composed of a mixture of γ phase or yttrium phase in which calcium is dissolved in copper. Due to the formation of columnar crystals, it is possible to have higher strength than equiaxed crystals. By the macroscopic observation of the metallographic structure shown in Fig. 2 and Fig. 3, a linear grain boundary can be seen, whereby columnar crystals can be confirmed. Further, the copper-gallium alloy according to the present invention is a mixed phase of a γ phase and a ζ phase, which is obtained from a state diagram of a copper-gallium system. It is hard and brittle only in the γ phase, and a tough structure can be obtained by mixing with a relatively tough ζ phase to form a mixed phase.
(組織) (organization)
利用EPMA的背散射電子像(COMPO像)觀察本發明所涉 及的銅-鎵合金濺射靶材的剖面的微觀組織，可確認如第4圖及第5圖所示的兩相組織(第4圖及第5圖中，銅-鎵合金的鎵濃度為28原子%)。第4圖及第5圖的黑色部分為ζ相，白色部分為γ相。 Using the backscattered electron image (COMPO image) of EPMA to observe the invention The microstructure of the cross section of the copper-gallium alloy sputtering target can be confirmed as the two-phase structure shown in Fig. 4 and Fig. 5 (in Figs. 4 and 5, the gallium concentration of the copper-gallium alloy is 28 atom%). The black portions in Figs. 4 and 5 are the ζ phase, and the white portion is the γ phase.
(晶體取向及晶體面的取向率) (crystal orientation and orientation ratio of crystal face)
用X射線衍射中的ζ相的(100)面、(002)面、(101)面、(102)面、(110)面、(200)面、(112)面、(201)面和(004)面的各衍射峰的測定強度分別除以JCPDS卡片編號44-1117中所記載的所述各峰對應的結晶面的標準強度後得到的值的總和作為(A)，並且，用通過X射線衍射的ζ相的(112)面的衍射峰強度除以JCPDS卡片編號44-1117中記載的(112)面的衍射峰標準強度後的值作為(B)時，通過(B)/(A)求得的ζ相的(112)面的取向率為25%~60%。以下示出該取向率的計算公式。 The (100) plane, the (002) plane, the (101) plane, the (102) plane, the (110) plane, the (200) plane, the (112) plane, the (201) plane and the (ζ) of the ζ phase in X-ray diffraction. 004) The measured intensity of each diffraction peak of the surface is divided by the standard intensity of the crystal face corresponding to each peak described in JCPDS card number 44-1117, respectively, as (A), and When the diffraction peak intensity of the (112) plane of the 衍射-ray diffraction is divided by the standard intensity of the diffraction peak of the (112) plane described in JCPDS card number 44-1117, (B), (B)/(A) The orientation ratio of the (112) plane of the obtained ζ phase is 25% to 60%. The calculation formula of the orientation ratio is shown below.
(112)面的取向率：(B)/(A)={(112)面測定強度/(112)面標準強度}/{(100)面測定強度/(100)面標準強度+(002)面測定強度/(002)面標準強度+(101)面測定強度/(101)面標準強度+(102)面測定強度/(102)面標準強度+(110)面測定強度/(110)面標準強度+(200)面測定強度/(200)面標準強度+(112)面測定強度/(112)面標準強度+(201)面測定強度/(201)面標準強度+(004)面測定強度/(004)面標準強度}×100%。 Orientation rate of (112) plane: (B) / (A) = {(112) surface measurement intensity / (112) surface standard strength} / {(100) surface measurement intensity / (100) surface standard strength + (002) Surface measurement strength / (002) surface standard strength + (101) surface measurement intensity / (101) surface standard strength + (102) surface measurement strength / (102) surface standard strength + (110) surface measurement intensity / (110) surface Standard Strength + (200) Surface Measurement Strength / (200) Surface Standard Strength + (112) Surface Measurement Strength / (112) Surface Standard Strength + (201) Surface Measurement Strength / (201) Surface Standard Strength + (004) Surface Measurement Strength / (004) surface standard strength} × 100%.
若ζ相的(112)面的取向率小於25%，則產生濺射靶材的抗彎強度降低的問題。此外，本發明中ζ相的(112)面的取向率典型地為60%以下。 If the orientation ratio of the (112) plane of the ζ phase is less than 25%, there is a problem that the bending strength of the sputtering target is lowered. Further, in the present invention, the orientation ratio of the (112) plane of the ζ phase is typically 60% or less.
第6圖示出了通過X射線衍射測定本發明所涉及的銅-鎵合金濺射靶材剖面的衍射峰的一個例子。此外，第7圖示出了通過X射線衍射測定現有技術的銅-鎵合金濺射靶剖面的衍射峰的一個例子。 Fig. 6 is a view showing an example of measurement of a diffraction peak of a cross section of a copper-gallium alloy sputtering target according to the present invention by X-ray diffraction. Further, Fig. 7 shows an example of the measurement of the diffraction peak of the cross section of the prior art copper-gallium alloy sputtering target by X-ray diffraction.
(相對密度) (Relative density)
通常，使燒結件的相對密度在95%以上為目標。這是由於，如果相對密度低，濺射過程中內部空孔露出時，則由以空孔周邊為起點的飛濺和異常放電會對膜引起粉塵粒子的產生和提前產生表面凹凸化，就容易引起以表面突起(Nodule)為起點的異常放電等。鑄件的相對密度大致可達到100%，其結果是，具有能夠抑制產生濺射中的不同的粒子的效果。 這是鑄件的一個主要優點。由於本發明所涉及的銅-鎵合金濺射靶材可通過鑄造來製造，因此能夠具有高的相對密度。例如，本發明所涉及的銅-鎵合金濺射靶材在一個實施方式中，其相對密度能夠達到99.0%以上，較佳99.5%以上，進一步較佳100%，例如能夠達到99~100%。 Generally, it is a target to make the relative density of the sintered member 95% or more. This is because if the relative density is low and the internal pores are exposed during the sputtering process, splashing and abnormal discharge starting from the periphery of the pores may cause generation of dust particles and premature surface unevenness of the film, which may easily occur. Abnormal discharge starting from a surface protrusion (Nodule). The relative density of the casting can be approximately 100%, and as a result, it is possible to suppress the occurrence of different particles in sputtering. This is a major advantage of castings. Since the copper-gallium alloy sputtering target according to the present invention can be produced by casting, it can have a high relative density. For example, in one embodiment, the copper-gallium alloy sputtering target according to the present invention has a relative density of 99.0% or more, preferably 99.5% or more, further preferably 100%, for example, 99 to 100%.
(抗彎強度) (bending strength)
本發明所涉及的銅-鎵合金濺射靶材在一個實施方式中，遵從JIS R1601：2008標準測得的3點彎曲強度為350MPa以上。本發明所涉及的銅-鎵合金濺射靶材在一個較佳的實施方式中，遵從JIS R1601：2008標準測得的3點彎曲強度為360MPa以上。本發明所涉及的銅-鎵合金濺射靶材在一個更佳的實施方式中，遵從JIS R1601：2008標準測得的3點彎曲強度為370MPa以上。本發明所涉及的銅-鎵合金濺射靶材在一個更佳的實施方式中，遵從JIS R1601：2008標準測得的3點彎曲強度為380MPa以上。本發明所涉及的銅-鎵合金濺射靶材在典型的實施方式中，遵從JIS R1601：2008標準測得的3點彎曲強度為350~410MPa以上。 In one embodiment, the copper-gallium alloy sputtering target according to the present invention has a 3-point bending strength measured in accordance with JIS R1601:2008 standard of 350 MPa or more. In a preferred embodiment of the copper-gallium alloy sputtering target according to the present invention, the 3-point bending strength measured in accordance with JIS R1601:2008 is 360 MPa or more. In a more preferred embodiment of the copper-gallium alloy sputtering target according to the present invention, the 3-point bending strength measured in accordance with JIS R1601:2008 is 370 MPa or more. In a more preferred embodiment of the copper-gallium alloy sputtering target according to the present invention, the 3-point bending strength measured in accordance with JIS R1601:2008 is 380 MPa or more. In a typical embodiment of the copper-gallium alloy sputtering target according to the present invention, the three-point bending strength measured in accordance with JIS R1601:2008 standard is 350 to 410 MPa or more.
本發明所涉及的銅-鎵合金濺射靶材，例如可作為板狀或圓筒形狀而提供。此外，由於具有高強度，易於加工成所要求的形狀。 The copper-gallium alloy sputtering target according to the present invention can be provided, for example, in a plate shape or a cylindrical shape. In addition, due to its high strength, it is easy to process into the desired shape.
(鑄造法) (casting method)
對本發明所涉及的銅-鎵合金濺射靶材的合適的製造方法的例子進行說明。本發明所涉及的銅-鎵合金濺射靶材，例如可使用如第8圖所示之具有高頻感應加熱裝置、石墨坩堝和水冷探針的結構的立式連續鑄造裝置30進行製造。在石墨坩堝31內熔化靶材原料，將熔融金屬38澆鑄到設置於坩堝底部、與引錠34一起拉拔的鑄型20內，並進行連續冷卻，由此可連續製造銅-鎵合金的鑄件(空心坯)39。根據引錠34的形狀，可使鑄件39的形狀變化。例如，如果將引錠設為圓筒形狀，則可得到圓筒形的鑄件39。如果將引錠34設為平板狀，則可得到平板狀的鑄件39。對得到的鑄件39進一步進行機械加工和拋光，也可得到所要求的形狀的銅-鎵合金濺射靶材。 An example of a suitable method for producing a copper-gallium alloy sputtering target according to the present invention will be described. The copper-gallium alloy sputtering target according to the present invention can be produced, for example, by using a vertical continuous casting apparatus 30 having a structure of a high-frequency induction heating device, a graphite crucible, and a water-cooled probe as shown in Fig. 8. The target material is melted in the graphite crucible 31, and the molten metal 38 is cast into the mold 20 which is placed at the bottom of the crucible and drawn together with the ingot 34, and is continuously cooled, whereby the casting of the copper-gallium alloy can be continuously manufactured. (hollow blank) 39. The shape of the casting 39 can be changed according to the shape of the starter 34. For example, if the starter is formed into a cylindrical shape, a cylindrical casting 39 can be obtained. When the starter 34 is formed into a flat shape, a flat casting 39 can be obtained. The obtained casting 39 is further machined and polished to obtain a copper-gallium alloy sputtering target of a desired shape.
水冷銅套33作為使鑄造空間從外周側冷卻的冷卻部，被設置於坩堝31的外周側。此時，由於形成了冷卻介質不直接與熔融金屬38接觸的結構，即使發生金屬液洩露也不會存在水蒸氣***的危險。坩堝31中設置有導入惰性氣體的惰性氣體導入部42，使熔融金屬38內的氧分壓降低。 The water-cooled copper sleeve 33 is provided on the outer peripheral side of the crucible 31 as a cooling portion for cooling the casting space from the outer peripheral side. At this time, since the structure in which the cooling medium is not directly in contact with the molten metal 38 is formed, there is no risk of water vapor explosion even if the molten metal leaks. The inert gas introduction portion 42 into which the inert gas is introduced is provided in the crucible 31 to lower the partial pressure of oxygen in the molten metal 38.
坩堝31的外周設置有加熱裝置45。坩堝31的壁部設置有坩堝溫度控制用熱電偶44。用來測定從坩堝31向鑄造空間供給熔融金屬38的熔融金屬供給部位的熔融金屬溫度的熔融金屬溫度測定用熱電偶43，在收納於特定的保護管內的狀態下，設置成通過貫通柱狀的鑄芯32的上表面而形成的熱電偶保護管***口，並到達熔融金屬供給部位。用於從內周側冷卻鑄造空間的水等多根冷卻介質探針46，從冷卻介質探針***口36呈同心圓狀***到鑄芯32的內部。立式連續鑄造裝置30通過使直接從金屬熔化爐供給到鑄型20及配置於鑄型20內側的鑄芯32之間的熔融金屬38冷卻並凝固，形成鑄件39，利用拉拔裝置47從鑄型20及鑄芯32拉拔引錠34，從而進行連續鑄造得到鑄件。 A heating device 45 is provided on the outer circumference of the crucible 31. The wall portion of the crucible 31 is provided with a thermocouple 44 for temperature control. The thermocouple 43 for measuring the temperature of the molten metal for measuring the temperature of the molten metal in the molten metal supply portion of the molten metal 38 from the crucible 31 is placed in a columnar state in a state of being housed in a specific protective tube. The thermocouple formed by the upper surface of the casting core 32 protects the tube insertion opening and reaches the molten metal supply portion. A plurality of cooling medium probes 46, such as water for cooling the casting space from the inner circumferential side, are inserted concentrically into the interior of the casting core 32 from the cooling medium probe insertion opening 36. The vertical continuous casting apparatus 30 cools and solidifies the molten metal 38 which is directly supplied from the metal melting furnace to the mold 20 and the casting core 32 disposed inside the mold 20, thereby forming the casting 39, which is cast from the casting by the drawing device 47. The mold 20 and the casting core 32 pull the spindle 34 to perform continuous casting to obtain a casting.
其中，在控制晶體結構和晶體生長方向、進一步防止縮孔、確保強度的基礎上，控制鑄件的拉拔速度及凝固介面上的冷卻速度[℃/sec]是很重要的。通過提高拉拔速度，促進定向凝固，可生長柱狀晶。此外，ζ相也受到冷卻速度的影響，當定向凝固中的冷卻速度高時，通過細長且微小的ζ相的急速生長，可獲得晶體不易開裂之優點。 Among them, in order to control the crystal structure and crystal growth direction, further prevent shrinkage, and ensure strength, it is important to control the drawing speed of the casting and the cooling rate [°C/sec] on the solidification interface. Columnar crystals can be grown by increasing the drawing speed and promoting directional solidification. In addition, the ζ phase is also affected by the cooling rate. When the cooling rate in the directional solidification is high, the crystal is not easily cracked by the rapid growth of the elongated and minute ζ phase.
具體地，較佳將拉拔速度設置為30~120mm/min，更佳設置為60~120mm/min，進一步較佳設置為90~120mm/min。此外，將銅-鎵合金的凝固溫度±50℃的冷卻速度平均設置為1.7~14.5℃/sec。較佳將該冷卻速度設置為3.3~14.5℃/sec，更佳設置為5.0~14.5℃/sec。 Specifically, the drawing speed is preferably set to 30 to 120 mm/min, more preferably 60 to 120 mm/min, and further preferably set to 90 to 120 mm/min. Further, the cooling rate of the solidification temperature of the copper-gallium alloy at ±50 ° C was set to 1.7 to 14.5 ° C / sec on average. Preferably, the cooling rate is set to 3.3 to 14.5 ° C / sec, more preferably 5.0 to 14.5 ° C / sec.
可以一邊重複拉拔裝置的驅動和停止一邊進行拉拔操作。本發明中，拉拔速度是指從相對於驅動和停止的全部時間、拉拔後的鑄件的長度算出的值。可通過控制拉拔裝置內的夾送輥48的旋轉速度來使拉拔速度變化。當驅動和停止的平衡差時，即使以相同的拉拔速度，也可能得不到所要求的組織，因此驅動時間和停止時間可被設置為，例如驅動時間/停止時間=0.1~0.5，典型地可以設置為0.15~0.4。此外，可改變拉拔速度來控制冷卻速度。凝固介面的冷卻速度(℃/sec)=[溫度梯度(℃/mm)]×[拉拔速度(mm/min)]/60(sec)。該式的含義為，在溫度梯度為一定時，冷卻速度與拉拔速度成比例增大。溫度梯度由鑄型和鑄芯中***的熱電偶的測溫距離和它們的溫度差求得。具體為，用直線連接測量點進行插補，製作曲線圖(橫軸：熱電偶位置；縱軸：溫度)，求得熔點±50℃範圍的溫度梯 度。 The drawing operation can be performed while repeatedly driving and stopping the drawing device. In the present invention, the drawing speed is a value calculated from the entire time of driving and stopping, and the length of the cast after drawing. The drawing speed can be varied by controlling the rotational speed of the pinch roller 48 in the drawing device. When the balance between the drive and the stop is poor, even if the same drawing speed is not obtained, the required tissue may not be obtained, so the driving time and the stop time may be set to, for example, the driving time/stop time = 0.1 to 0.5, typically The ground can be set to 0.15~0.4. In addition, the drawing speed can be changed to control the cooling rate. Cooling rate of the solidification interface (°C/sec) = [temperature gradient (°C/mm)] × [drawing speed (mm/min)] / 60 (sec). The meaning of this formula is that the cooling rate increases in proportion to the drawing speed when the temperature gradient is constant. The temperature gradient is determined by the temperature measurement distance of the mold and the thermocouple inserted in the core and their temperature difference. Specifically, the measurement points are connected by straight lines for interpolation, and a graph (horizontal axis: thermocouple position; vertical axis: temperature) is prepared, and a temperature ladder having a melting point of ±50 ° C is obtained. degree.
以下，舉出實施例以更好地理解本發明及其優點，但本發明不受這些實施例的限定。 The present invention is hereinafter described in order to better understand the present invention and its advantages, but the invention is not limited by these examples.
使用如第8圖所示之具有高頻感應加熱線圈、石墨坩堝和水冷探針的結構的立式連續鑄造裝置，製造了外徑159mm、厚度14mm、高度650mm的圓筒形銅-鎵合金濺射靶材。 A cylindrical copper-gallium alloy splash having an outer diameter of 159 mm, a thickness of 14 mm, and a height of 650 mm was produced using a vertical continuous casting apparatus having a structure of a high frequency induction heating coil, a graphite crucible, and a water-cooled probe as shown in FIG. Shoot the target.
將各組成分的銅-鎵合金原料35kg導入坩堝內，在氬氣氣氛中將坩堝內加熱到1100℃。該高溫加熱的目的是使設置於坩堝底部的圓筒狀的引錠與銅-鎵合金熔融金屬熔接。 35 kg of a copper-gallium alloy raw material of each component was introduced into a crucible, and the crucible was heated to 1,100 ° C in an argon atmosphere. The purpose of this high-temperature heating is to weld a cylindrical ingot provided on the bottom of the crucible to the copper-gallium alloy molten metal.
原料熔化後，將熔融金屬溫度降低到960℃，當熔融金屬溫度與坩堝溫度穩定時，開始拉拔引錠。通過拉出引錠，連續地拉出了凝固的圓筒狀的鑄件。拉拔模式為，對拉拔裝置驅動0.5秒、停止2.5秒，如此反復地運行，通過使頻率變化，而使拉拔速度變化，從而使冷卻速度變化。表1示出了冷卻速度。拉拔時，為防止在凝固介面附近產生縮孔，將拉拔速度限制在120mm/min以下以使冷卻速度不會過大。此外，該冷卻速度(℃/sec)可通過公式：溫度梯度(℃/mm)×拉拔速度(mm/min)/60(sec)而變得清楚，求得該溫度梯度時，連接圖表中凝固溫度+50℃的點和凝固溫度-50℃的點，除以它們之間的位置差(mm)，從而求得。表1示出得到的銅-鎵合金的各鎵含量(原子%)。 After the raw material is melted, the temperature of the molten metal is lowered to 960 ° C, and when the temperature of the molten metal and the temperature of the crucible are stabilized, the ingot is started to be drawn. The solidified cylindrical casting is continuously drawn by pulling out the ingot. The drawing mode is such that the pulling device is driven for 0.5 second and stopped for 2.5 seconds, and the operation is repeated. The frequency is changed to change the drawing speed, thereby changing the cooling rate. Table 1 shows the cooling rate. When drawing, in order to prevent the occurrence of shrinkage cavities near the solidification interface, the drawing speed is limited to 120 mm/min or less so that the cooling rate is not excessive. In addition, the cooling rate (°C/sec) can be made clear by the formula: temperature gradient (°C/mm)×drawing speed (mm/min)/60 (sec), and when the temperature gradient is obtained, the graph is connected. The point at which the solidification temperature is +50 ° C and the point at which the solidification temperature is -50 ° C are obtained by dividing the position difference (mm) between them. Table 1 shows the respective gallium contents (atomic %) of the obtained copper-gallium alloy.
<晶體結構> <crystal structure>
拋光與凝固方向和圓筒的中心軸方向平行的剖面，用硝酸和鹽酸腐蝕，通過目視及實體顯微鏡進行了觀察。如第2圖及第3圖所示，從圓筒狀鑄錠的外周側及內周側的散熱部分凝固並生長的晶界在板厚度的中央附近相互碰撞的位置判斷為柱狀晶，晶界呈斑點狀分佈的位置判斷為等軸晶。(這裡，散熱部分指與鑄錠接觸的鑄型、鑄芯以及冷卻空間。) A section parallel to the direction of solidification and the direction of the central axis of the cylinder was polished, and it was observed by visual observation and a stereoscopic microscope by etching with nitric acid and hydrochloric acid. As shown in Fig. 2 and Fig. 3, the position where the grain boundary solidified and grown by the heat radiating portion on the outer peripheral side and the inner peripheral side of the cylindrical ingot collides with each other in the vicinity of the center of the plate thickness is determined as a columnar crystal. The position where the boundary is distributed in a spot shape is judged to be equiaxed crystal. (Here, the heat dissipation part refers to the mold, the core, and the cooling space that are in contact with the ingot.)
<晶體取向> <crystal orientation>
用水砂紙對試料進行濕式拋光至#2400，進行乾燥成為測定試料。用理學電機(株)社製RINT-2200，在管球：銅，管電壓：40kV，管 電流：40mA，掃描範圍(2θ)：20°~100°，狹縫大小：發散(DS)[mm]、防散射(SS)[mm]、接收(RS)[mm]，測定步驟(2θ)：0.02°，掃描速度：4°/min的條件下進行了X射線衍射。 The sample was wet-polished to #2400 with water sandpaper, and dried to obtain a measurement sample. RINT-2200 manufactured by Rigaku Electric Co., Ltd., in the tube ball: copper, tube voltage: 40kV, tube Current: 40 mA, scan range (2θ): 20°~100°, slit size: divergence (DS) [mm], anti-scatter (SS) [mm], reception (RS) [mm], measurement step (2θ) X-ray diffraction was carried out under the conditions of 0.02° and scanning speed: 4°/min.
<微觀組織> <Microstructure>
用EPMA(日本電子製，裝置名：XJA-8500F)的背散射電子像(COMPO像)觀察了與圓筒的中心軸方向垂直的剖面的微觀組織。黑色部分為ζ相，白色部分為γ相。 The microstructure of the cross section perpendicular to the central axis direction of the cylinder was observed by a backscattered electron image (COMPO image) of EPMA (manufactured by JEOL Ltd., device name: XJA-8500F). The black part is the ζ phase and the white part is the γ phase.
<不可避免的雜質中氧、碳含量> <Inevitable impurities in oxygen and carbon content>
對於得到的構成濺射靶材的銅-鎵合金，通過紅外吸收法(LECO社製，裝置名：CS6000)測定O的濃度，通過紅外吸收法(LECO社制，裝置名：CS844)測定C的濃度。 The copper-gallium alloy constituting the sputtering target was measured for the concentration of O by an infrared absorption method (manufactured by LECO Co., Ltd., device name: CS6000), and C was measured by an infrared absorption method (manufactured by LECO Co., Ltd., device name: CS844). concentration.
<相對密度> <relative density>
通過阿基米德法測定得到的濺射靶材的密度，求出相對於由組成分確定的理論密度的百分比(%)，作為相對密度。 The density of the obtained sputtering target was measured by the Archimedes method, and the percentage (%) with respect to the theoretical density determined from the composition was determined as the relative density.
<抗彎強度> <bending strength>
遵從JIS R1601：2008標準測定了得到的濺射靶材的3點彎曲強度。將試驗夾具設置為3p-30。從各靶材切出5個試驗片進行抗彎強度測定。將沿靶材的長度方向切出的板材作為試驗片，沿與長度方向垂直的方向施加壓力進行測定。長度方向是指靶材的安裝方向，即背板和背襯管的方向。 The 3-point bending strength of the obtained sputtering target was measured in accordance with JIS R1601:2008 standard. Set the test fixture to 3p-30. Five test pieces were cut out from each target to measure the bending strength. A plate cut out along the longitudinal direction of the target was used as a test piece, and pressure was measured in a direction perpendicular to the longitudinal direction. The length direction refers to the direction in which the target is mounted, that is, the direction of the backing plate and the backing tube.
利用如第9圖所示之具有石墨坩堝51、中間包52以及鑄型53的重力鑄造裝置50，製造外徑為162mm、厚度為18mm、高度為630mm的圓筒形的銅-鎵合金濺射靶材。將44kg的銅-鎵合金原料(銅的純度為4N、鎵的純度為4N)導入坩堝51中，將鑄造裝置50內設為10Pa左右的真空氣氛，加熱至1300℃。之後，經過中間包52將坩堝51內的熔融金屬澆入鑄型中。 A cylindrical copper-gallium alloy sputtering having an outer diameter of 162 mm, a thickness of 18 mm, and a height of 630 mm was produced by using the gravity casting apparatus 50 having the graphite crucible 51, the tundish 52, and the mold 53 as shown in Fig. 9. Target. 44 kg of a copper-gallium alloy raw material (a purity of copper of 4N and a purity of gallium of 4N) was introduced into the crucible 51, and the inside of the casting apparatus 50 was set to a vacuum atmosphere of about 10 Pa, and heated to 1300 °C. Thereafter, the molten metal in the crucible 51 is poured into the mold through the tundish 52.
由於從中間包52澆入鑄型的熔融金屬在鑄型底部飛濺，鑄錠的下部會殘留空孔。此外，由於隨著從鑄型底部散熱在上方凝固的推進，被釋放的凝固潛熱積累，導致鑄錠上部也多有發生縮孔的傾向。因此，評 價質量時，從距鑄錠的底部100~350mm的位置取樣。 Since the molten metal poured into the mold from the tundish 52 splashes at the bottom of the mold, voids remain in the lower portion of the ingot. Further, since the latent heat of solidification is accumulated as the heat is solidified from the bottom of the mold, the latent heat of solidification is accumulated, and there is a tendency for the upper portion of the ingot to shrink. Therefore, the review For the price, the sample is taken from a position of 100 to 350 mm from the bottom of the ingot.
比較例2~5中，冷卻速度通過監測***鑄型的熱電偶(設置在距底面300mm和600mm的位置)的溫度變化並繪製溫度vs時間的曲線圖而求得。在澆鑄的熔融金屬的溫度下降的過程，釋放凝固潛熱，圖上的溫度梯度變緩，隨著該潛熱的散去溫度梯度再次變陡。將示出了如上所述變化的曲線的拐點的切線斜率作為該熱電偶位置的冷卻速度[℃/sec]。因此，冷卻速度是各熱電偶位置的測定值。表1中記載的冷卻速度記載了得到的測定值的平均值。 In Comparative Examples 2 to 5, the cooling rate was obtained by monitoring the temperature change of the thermocouple inserted into the mold (set at positions of 300 mm and 600 mm from the bottom surface) and plotting the temperature vs. time. During the process of temperature drop of the cast molten metal, the latent heat of solidification is released, and the temperature gradient on the graph becomes gentle, and the temperature gradient becomes steep again as the latent heat is dispersed. The tangent slope of the inflection point of the curve shown as described above will be shown as the cooling rate [°C/sec] of the thermocouple position. Therefore, the cooling rate is a measured value of each thermocouple position. The cooling rate described in Table 1 describes the average value of the obtained measured values.
關於得到的圓筒形的濺射靶材，與之前同樣，評價了其晶體結構、晶體取向、相對密度以及抗彎強度。 Regarding the obtained cylindrical sputtering target, the crystal structure, crystal orientation, relative density, and bending strength were evaluated in the same manner as before.
表1示出了試驗條件及評價結果。此外，由X射線衍射測定的ζ相的各面的取向率示於表2。表2中記載的ζ相的(112)面的取向率是，用X射線衍射中的ζ相的(100)面、(002)面、(101)面、(102)面、(110)面、(200)面、(112)面、(201)面和(004)面的各衍射峰的測定強度分別除以JCPDS卡片編號44-1117中所記載的所述各峰對應的結晶面的標準強度後得到的值的總和作為(A)，並且，用通過X射線衍射的ζ相的(112)面的衍射峰強度除以JCPDS卡片編號44-1117中所記載的(112)面的衍射峰標準強度後的值作為(B)時，通過(B)/(A)求得的值。 Table 1 shows the test conditions and evaluation results. Further, the orientation ratios of the respective faces of the ζ phase measured by X-ray diffraction are shown in Table 2. The orientation ratio of the (112) plane of the ζ phase described in Table 2 is the (100) plane, the (002) plane, the (101) plane, the (102) plane, and the (110) plane of the ζ phase in X-ray diffraction. The measurement intensity of each of the diffraction peaks of the (200) plane, the (112) plane, the (201) plane, and the (004) plane is divided by the standard of the crystal plane corresponding to each peak described in JCPDS card number 44-1117. The sum of the values obtained after the intensity is (A), and the diffraction peak intensity of the (112) plane of the ζ phase by X-ray diffraction is divided by the diffraction peak of the (112) plane described in JCPDS card number 44-1117. The value obtained by (B)/(A) when the value after the standard strength is (B).
ζ相的(112)面的取向率與比較例相比，其值較大的實施例1~6的濺射靶材的抗彎強度高。金屬組織中的ζ相聚集在特定的面取向，同時擴散深入到其外部存在的γ相中，由此可得到單相中所得不到的強度的提高。即通過韌性組織連接脆性組織，或通過相反的情況，利用ζ相的韌性來彌補γ相的脆性的效果，單相時的脆性和硬度低很難反映在抗彎強度上。此外，由於比較例2~5重力鑄造中冷卻速度較低，其雖然柱狀晶，但是ζ相的(112)面的取向率小，因此不能得到高的抗彎強度。 The orientation ratio of the (112) plane of the ζ phase was higher than that of the comparative examples, and the sputtering targets of Examples 1 to 6 having a large value had high bending strength. The ζ phase in the metal structure is concentrated in a specific plane orientation while diffusing deep into the γ phase existing outside thereof, whereby an improvement in strength which is not obtained in a single phase can be obtained. That is, the brittle structure is connected by the ductile structure, or the opposite is used, and the toughness of the γ phase is utilized to compensate for the brittleness of the γ phase, and the brittleness and hardness at the single phase are hard to be reflected in the bending strength. Further, in the comparative examples 2 to 5, the cooling rate in the gravity casting was low, and although the columnar crystal was formed, the orientation ratio of the (112) plane of the ζ phase was small, so that high bending strength could not be obtained.
[表1]
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