TWI499680B - Manufacture of pure copper plate and pure copper plate - Google Patents

Manufacture of pure copper plate and pure copper plate Download PDF

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TWI499680B
TWI499680B TW100104285A TW100104285A TWI499680B TW I499680 B TWI499680 B TW I499680B TW 100104285 A TW100104285 A TW 100104285A TW 100104285 A TW100104285 A TW 100104285A TW I499680 B TWI499680 B TW I499680B
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pure copper
copper plate
grain boundary
rolling
ratio
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TW100104285A
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TW201139707A (en
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Toshihiro Sakai
Takahiro Takeda
Koichi Kita
Kazunari Maki
Hiroyuki Mori
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Mitsubishi Shindo Kk
Mitsubishi Materials Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/005—Copper or its alloys

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electrochemistry (AREA)
  • Physical Vapour Deposition (AREA)

Description

純銅板之製造方法及純銅板Pure copper plate manufacturing method and pure copper plate

本發明係關於一種具有良好品質之純銅板的製造方法，特別詳而言之，係有關一種具有微細的結晶組織，同時並具有適度的硬度，藉由部分再結晶化而形成雙晶組織以製造賦予高的特殊粒界長度比率之純銅板的方法，及其製造方法所製造之濺鍍用靶材或電鍍用陽極等材料之純銅板。The present invention relates to a method for producing a pure copper plate having good quality, and more particularly to a method for producing a bicrystal structure by partially recrystallizing a fine crystal structure while having moderate hardness. A method of imparting a high specific grain boundary length ratio of a pure copper plate, and a pure copper plate of a material such as a sputtering target or a plating anode manufactured by the method of manufacturing the same.

本案係依據2010年2月9日所申請之特願2010-26453號，主張優先權，此處授用其內容。This case is based on the special request 2010-26453, which was applied for on February 9, 2010, and claims priority. The content is hereby granted.

純銅板一般係使純銅錠熱間壓延或熱間鍛造之後，實施冷間壓延或冷間鍛造，其後，藉由實施變形矯正或用以再結晶化之熱處理來製造。如此之純銅板係以鋸切割、切削加工、壓紋加工、冷間鍛造等加工成所希望的形狀而使用，但為減少加工時之小缺損，亦要求結晶粒徑小。A pure copper plate is generally subjected to cold rolling or cold forging after hot rolling or hot forging of a pure copper ingot, and thereafter, by performing deformation correction or heat treatment for recrystallization. Such a pure copper plate is used for processing into a desired shape by saw cutting, cutting, embossing, cold forging, etc., but in order to reduce small defects during processing, it is also required to have a small crystal grain size.

又，以上述的方法所製造之純銅板係在最近使用來作為半導體元件的配線材料用濺鍍靶。可使用Al(比阻抗3.1μΩ‧cm左右)作為半導體元件的配線材料，但伴隨最近之配線的微細化，進一步阻抗低的銅配線(比阻抗1.7μΩ‧cm左右)被實用化。此銅配線之形成製程係於接觸孔或配線溝的凹部形成Ta/TaN等之擴散阻隔層後，常電鍍銅，為進行此電鍍，就基底層(shield層)濺鍍純銅成膜。Moreover, the pure copper plate manufactured by the above method is a sputtering target for wiring materials which has recently been used as a semiconductor element. Al (a specific impedance of about 3.1 μΩ and a thickness of ‧ cm) can be used as a wiring material for a semiconductor element. However, with the recent miniaturization of wiring, a copper wiring having a lower impedance (a specific impedance of about 1.7 μΩ·cm) is put into practical use. This copper wiring forming process is performed by forming a diffusion barrier layer such as Ta/TaN in a recess of a contact hole or a wiring trench, and then electroplating copper. To perform this plating, a pure copper film is formed by sputtering a base layer (shield layer).

一般，以4N(純度99.99%以上：除去氣體成分)左右的電氣銅作為粗金屬而藉由濕式或乾式的高純度化製程，製造5N(純度99.999%以上)~6N(純度99.9999%以上)的純度之高純度銅，再以上述方法形成純銅板，進一步，加工成所希望的形狀後使用來作為濺鍍靶。為製作電阻低之濺鍍膜，使濺鍍靶中之雜質含量抑制至一定值以下，又，用以合金化所添加之元素亦必須降至一定程度以下，為得到濺鍍膜厚之均一性，必須抑制濺鍍靶之結晶粒徑及結晶配向性的參差不齊。In general, 5N (purity of 99.999% or more) to 6N (purity of 99.9999% or more) is produced by a wet or dry high purity process using 4N (purity of 99.99% or more: gas component removal) as the crude metal. The pure copper of high purity is formed into a pure copper plate by the above method, and further processed into a desired shape and used as a sputtering target. In order to produce a low-resistance sputtering film, the content of impurities in the sputtering target is suppressed to a certain value or less, and the element added for alloying must also be reduced to a certain level or less. In order to obtain uniformity of the thickness of the sputtering film, it is necessary to obtain uniformity of the thickness of the sputtering film. The crystal grain size and crystal orientation of the sputtering target are suppressed from being uneven.

工業上製造如此之濺鍍用純鍍靶材的習知方法，於專利文獻1中已揭示一種得到濺鍍用銅靶材的方法，其係使純度為99.995%以上之純銅錠進行熱間加工，其後，以900℃以下之溫度進行燒結，繼而，以40%以上之壓延率實施冷間壓延後，以500℃以下之溫度進行再結晶燒結，俾實質上具有再結晶組織，平均結晶粒徑為80微米以下，且維氏(Vickers)硬度為100以下。A conventional method for producing such a pure plating target for sputtering is disclosed in Patent Document 1, and a method for obtaining a copper target for sputtering is disclosed in which a pure copper ingot having a purity of 99.995% or more is subjected to hot working. Then, sintering is performed at a temperature of 900 ° C or lower, and then cold rolling is performed at a rolling ratio of 40% or more, and then recrystallization sintering is performed at a temperature of 500 ° C or lower, and the crucible has substantially recrystallized structure and average crystal grains. The diameter is 80 μm or less and the Vickers hardness is 100 or less.

又，於專利文獻2中係已揭示一種得到濺鍍用銅靶材的方法，其係使5N以上之高純度銅錠實施熱間鍛造或熱間壓延等之加工率50%以上的熱間加工後，進一步使實施冷間壓延或冷間鍛造等之加工率30%以上的冷間加工，實施350~500℃、1~2小時之熱處理，Na及K含量分別為0.1ppm以下，Fe、Ni、Cr、Al、Ca、Mg含量分別為1ppm以下，碳及氧含量分別為5ppm以下，U及Th含量分別為1ppb以下，除去氣體成分之銅的含量為99.999%以上，進一步，在濺鍍面之平均粒徑為250μm以下，平均粒徑的參差不齊為±20%以內，X線繞射強度比I(111)/I(200)在濺鍍面中為2.4以上且其參差不齊為±20%以內。Further, Patent Document 2 discloses a method for obtaining a copper target for sputtering, which is a hot-storing process in which a high-purity copper ingot of 5 N or more is subjected to hot forging or hot-rolling at a processing rate of 50% or more. After that, cold processing such as cold rolling or cold forging is performed at a processing rate of 30% or more, and heat treatment at 350 to 500 ° C for 1 to 2 hours is performed, and the contents of Na and K are respectively 0.1 ppm or less, Fe, Ni. The contents of Cr, Al, Ca, and Mg are each 1 ppm or less, the carbon and oxygen contents are each 5 ppm or less, the U and Th contents are each 1 ppb or less, and the content of copper in which the gas component is removed is 99.999% or more, and further, the sputtering surface is provided. The average particle diameter is 250 μm or less, and the unevenness of the average particle diameter is within ±20%, and the X-ray diffraction intensity ratio I(111)/I(200) is 2.4 or more in the sputtering surface and the unevenness thereof is Within ±20%.

又，在專利文獻3中係已揭示一種銅合金濺鍍靶，其係從純度6N以上之高純度銅與添加元素除去所完成之錠的表面層，而經過熱間鍛造、熱間壓延、冷間壓延、熱處理步驟所得到之含有Al 0.5~4.0wt%、Si為0.5wtppm以下之銅合金濺鍍靶，含有Sn 0.5~4.0wt%、Mn為0.5 wt ppm以下之銅合金濺鍍靶以及於此等含有選自Sb、Zr、Ti、Cr、Ag、Au、Cd、In、As之1或2以上就總量為1.0wt ppm以下。尤其，在實施例中係記載著除去所製造之錠的表面層而形成Φ 160mm×厚60mm之後，以400℃熱間鍛造而形成Φ 200mm，其後，以400℃熱間壓延而壓延至Φ 270mm×厚20mm，進而，以冷間壓延壓延至Φ 360mm×厚10mm，以500℃熱處理1小時後，急冷靶材全體而形成靶材材料。Further, Patent Document 3 discloses a copper alloy sputtering target which removes the surface layer of the completed ingot from high-purity copper having a purity of 6 N or more and an additive element, and undergoes hot forging, hot rolling, and cold. A copper alloy sputtering target containing 0.5 to 4.0 wt% of Al and 0.5 wtppm or less of Si obtained by an intercalation and heat treatment step, and a copper alloy sputtering target containing 0.5 to 4.0 wt% of Sn and 0.5 wtppm or less of Mn and These materials contain 1 or more selected from Sb, Zr, Ti, Cr, Ag, Au, Cd, In, and As, and the total amount is 1.0 wt ppm or less. In particular, in the examples, it is described that the surface layer of the produced ingot is removed to form Φ 160 mm × thickness 60 mm, and then forged at 400 ° C to form Φ 200 mm, and then rolled at 400 ° C by heat to Φ. 270 mm × thickness 20 mm, further rolled to Φ 360 mm × thickness 10 mm by cold rolling, and heat-treated at 500 ° C for 1 hour, and then quenched the entire target to form a target material.

以如此之濺鍍用銅靶材的製造方法為代表，在習知之純銅板的製造方法中係為得到均質且安定之再結晶組織，使純銅錠進行熱間鍛造或熱間壓延後，進行冷間鍛造或冷間壓延，進而實施熱處理。As a representative method for producing a copper target for sputtering, in a conventional method for producing a pure copper plate, a homogenous and stable recrystallized structure is obtained, and the pure copper ingot is subjected to hot forging or hot rolling, and then cooled. Inter-forging or cold-rolling, and further heat treatment.

先前技術文獻Prior technical literature

專利文獻Patent literature

專利文獻1：特開平11-158614號公報Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 11-158614

專利文獻2：特開平10-330923號公報Patent Document 2: Japanese Patent Publication No. Hei 10-330923

專利文獻3：特開2009-114539號公報Patent Document 3: JP-A-2009-114539

在工業上製造具有大型形狀之均質且安定的結晶組織之純銅板的習知方法中，係於純銅錠實施熱間鍛造或熱間壓延後，必須進一步實施冷間鍛造或冷間壓延、熱處理，但將前述純銅板使用於濺鍍靶、電鍍用陽極或放熱基板等時，在濺鍍靶係經長時間之濺鍍中的異常放電抑制，電鍍用陽極中係面內溶解均質性之提昇，在放熱基板係對於所謂耐熱疲勞特性之特性，很難只以微細化對應。In a conventional method for industrially producing a pure copper plate having a large-sized homogeneous and stable crystal structure, after performing hot forging or hot rolling, a cold copper forging must be further subjected to cold forging or cold rolling, heat treatment, However, when the pure copper plate is used for a sputtering target, an anode for plating, or a heat-releasing substrate, the abnormal discharge in the sputtering target is sputtered for a long period of time, and the in-plane dissolution homogeneity in the anode for plating is improved. It is difficult for the characteristics of the heat-radiating substrate to be so-called heat-resistant fatigue characteristics to be made finer.

本發明係有鑑於如此之事情者，在於提供一種尤其在濺鍍靶材料或電鍍用陽極材料之製造中，於由熱間壓延之純銅所構成的壓延板使冷間壓延的壓延率為5~24%，進一步藉由燒結而具有微細的結晶組織，同時並藉由部分再結晶化而形成雙晶組織，俾賦予高的特性粒界比率，適於濺鍍靶或電鍍用陽極的純銅板。The present invention has been made in view of the above circumstances, and provides a rolling ratio of cold rolling between a rolled sheet made of hot copper rolled between heat, particularly in a sputtering target material or an anode material for plating. 24%, further having a fine crystal structure by sintering, and forming a twin structure by partial recrystallization, and imparting a high characteristic grain boundary ratio, and is suitable for a pure copper plate for sputtering a target or an anode for plating.

本發明人等係經專心硏究之結果，發現使純銅錠為抑制結晶粒的成長在一定的條件下進行熱間壓延，為停止粒成長，以一定的條件化急冷後，藉冷間壓延、熱處理，藉由以EBSD法所測定的特殊粒界的長度比率為25%以上，可製造濺鍍時之異常放電的抑制，或抑制電鍍中之不溶性泥發生之純銅板。As a result of intensive research, the present inventors have found that a pure copper ingot is subjected to inter-heat rolling under a certain condition to suppress the growth of crystal grains, and is quenched by a certain condition after quenching the grain growth. In the heat treatment, the ratio of the length of the special grain boundary measured by the EBSD method is 25% or more, thereby suppressing the suppression of abnormal discharge during sputtering or suppressing the occurrence of insoluble mud in the plating.

本發明之純銅板的製造方法，其特徵係使純度為99.96wt%以上之純銅錠加熱至550~800℃，實施總壓延率為80%以上且壓延終了時溫度為500~700℃之熱間壓延加工後，從前述壓延終了時溫度至200℃以下之溫度以200~1000℃/分鐘之冷卻速度急速冷卻，其後，以5~24%之壓延率進行冷間壓延再進行燒結。The method for producing a pure copper plate according to the present invention is characterized in that a pure copper ingot having a purity of 99.96 wt% or more is heated to 550 to 800 ° C, and a total calendering rate of 80% or more and a temperature of 500 to 700 ° C at the end of rolling are performed. After the calendering, the temperature is cooled to a temperature of 200 ° C or lower from the end of the rolling, and the temperature is rapidly cooled at a cooling rate of 200 to 1000 ° C / min. Thereafter, the film is calendered at a rolling ratio of 5 to 24% and then sintered.

為得到微細的結晶粒，藉由熱間壓延而賦予大的能量後急冷很有效，但其時，使熱間壓延終了溫度抑制於500~700℃很重要。若熱間壓延終了溫度超過700℃，結晶粒急劇變大，其後即使急冷，亦很難得到微細的結晶粒。又，即使使熱間壓延終了溫度未達500℃，結晶粒徑之微細化的效果飽和，即使降低溫度至其以上，亦無助於微細化。又，若壓延溫度降低，為得到所希望的總壓延率，必須有過大的能量，其加工很難。繼而為使此熱間壓延終了溫度為500~700℃，使熱間壓延之開始溫度為550~800℃。In order to obtain fine crystal grains, it is effective to impart a large amount of energy by heat-to-heat rolling, and it is effective to quench the temperature. However, it is important to suppress the end-of-heat rolling temperature at 500 to 700 °C. When the temperature at the end of the hot rolling is more than 700 ° C, the crystal grains become sharply large, and even if it is quenched, it is difficult to obtain fine crystal grains. In addition, even if the temperature at the end of the hot rolling is less than 500 ° C, the effect of refining the crystal grain size is saturated, and even if the temperature is lowered to be higher than the above, it does not contribute to miniaturization. Further, if the rolling temperature is lowered, in order to obtain a desired total rolling ratio, excessive energy must be generated, and processing is difficult. Then, in order to heat the heat to a temperature of 500 to 700 ° C, the starting temperature of the inter-heat rolling is 550 to 800 ° C.

又，以此熱間壓延之總壓延率宜為80%以上，可藉由使總壓延率為80%以上之很大的能量而抑制結晶粒的增大，同時並減少其參差不齊。若總壓延率未達80%，結晶粒有變大的傾向，同時其參差不齊變大。Further, the total rolling ratio by the inter-heat rolling is preferably 80% or more, and the increase in crystal grains can be suppressed by making the total rolling rate to be a large energy of 80% or more, and the unevenness can be reduced. If the total rolling ratio is less than 80%, the crystal grains tend to become large, and the unevenness thereof becomes large.

繼而，於如此之熱間壓延終了後，以200~1000℃/分鐘之冷卻速度急冷至成為200℃以下之溫度。冷卻速度未達200℃/分鐘時，缺乏抑制結晶粒的成長之效果，即使超過1000℃/分鐘，亦無助於其以上之微細化，更佳之冷卻速度為300~600℃/分鐘的範圍。Then, after the calendering is completed in such a heat, it is rapidly cooled to a temperature of 200 ° C or lower at a cooling rate of 200 to 1000 ° C / min. When the cooling rate is less than 200 ° C /min, there is no effect of suppressing the growth of crystal grains, and even if it exceeds 1000 ° C / min, it does not contribute to the above-mentioned miniaturization, and more preferably, the cooling rate is in the range of 300 to 600 ° C / min.

若以如此之範圍的冷卻速度冷卻至200℃以下之溫度，可停止結晶粒的成長而得到微細的結晶粒者。若以超過200℃之溫度停止急冷，其後，恐藉由其高溫狀態之放置而結晶粒徐緩地成長。When the temperature is cooled to 200 ° C or lower at a cooling rate in such a range, the growth of crystal grains can be stopped to obtain fine crystal grains. When quenching is stopped at a temperature exceeding 200 ° C, the crystal grains are slowly grown by the high temperature state.

繼而，於此急冷之後，藉由進行5~24%之壓延率的冷間壓延與燒結處理，結晶粒徑微細化，同時藉由部分再結晶化而形成雙晶組織，俾可賦予高的特殊粒界比率。Then, after quenching, by performing a cold rolling and sintering treatment of a rolling ratio of 5 to 24%, the crystal grain size is refined, and a twin crystal structure is formed by partial recrystallization, and the crucible can impart a high speciality. Grain boundary ratio.

又，依本發明之製造方法所製造的純銅板，其特徵係以EBSD法所測定相對於結晶粒界的全粒界長度L之特殊粒界的全特殊粒界長度Lσ之比率(特殊粒界長度比率、Lσ/L)為25%以上。Further, the pure copper plate produced by the production method of the present invention is characterized by the ratio of the total special grain boundary length Lσ of the specific grain boundary with respect to the full grain boundary length L of the crystal grain boundary by the EBSD method (special grain boundary) The length ratio, Lσ/L) is 25% or more.

宜以EBSD法所測定之平均結晶粒徑為10~120μm，維氏(Vickers)硬度為40~90。The average crystal grain size measured by the EBSD method is 10 to 120 μm, and the Vickers hardness is 40 to 90.

尤其，藉由前述特殊粒界長度比率為25%以上，結晶粒界之整合性提高，濺鍍靶的濺鍍中之異常放電的抑制，或電鍍用陽極的面內溶解均質性之提昇的各種特性變良好。In particular, when the specific grain boundary length ratio is 25% or more, the integration of the crystal grain boundaries is improved, the abnormal discharge in the sputtering of the sputtering target is suppressed, or the in-plane dissolution homogeneity of the plating anode is improved. The characteristics are getting better.

本發明之純銅板係適宜用於濺鍍靶或電鍍用陽極。The pure copper plate of the present invention is suitably used for a sputtering target or an anode for electroplating.

如前述般，本發明之純銅板係結晶粒徑為微細，藉特殊粒界長度比率為25%以上，使用來作為濺鍍靶時，可經長時間而抑制異常放電，又，使用來作為電鍍用陽極時，面內溶解均質性提高並可抑制不溶性泥的發生。As described above, the pure copper plate of the present invention has a fine crystal grain size and a specific grain boundary length ratio of 25% or more. When used as a sputtering target, abnormal discharge can be suppressed over a long period of time, and it is used as plating. When the anode is used, the in-plane dissolution homogeneity is improved and the occurrence of insoluble mud can be suppressed.

若依本發明，可提供一種電鍍用陽極，其係結晶粒徑為微細，藉特殊粒界長度比率為25%以上，可經長時間而抑制異常放電之靶材，及面內溶解均質性提高並可抑制不溶性泥的發生。According to the present invention, it is possible to provide an anode for electroplating which has a fine crystal grain size and a ratio of a specific grain boundary length of 25% or more, which can suppress an abnormal discharge target over a long period of time, and improve in-plane dissolution homogeneity. It can also inhibit the occurrence of insoluble mud.

用以實施發生之最佳形態The best form to implement

以下，說明本發明之實施形態。Hereinafter, embodiments of the present invention will be described.

此實施形態之純銅板係銅的純度為99.96wt%以上之無氧銅、或99.99wt%以上之電子管用無氧銅。The pure copper plate of this embodiment is an oxygen-free copper having a purity of 99.96 wt% or more, or an oxygen-free copper for an electron tube of 99.99 wt% or more.

本發明之壓延板的平均結晶粒徑為10~120μm，維氏(Vickers)硬度為40~90，又，以EBSD法所測定之特殊粒界長度比率為25%以上。The rolled sheet of the present invention has an average crystal grain size of 10 to 120 μm, a Vickers hardness of 40 to 90, and a specific grain boundary length ratio of 25% or more as measured by the EBSD method.

若混入結晶粒徑超過200μm之大結晶粒，在切割加工中於表面易產生微細的小缺損，此小缺損係如圖2所示般，使材料藉切刀等切削時，於其切削方向(以箭號A所示之方向)所產生的切削痕W中，於與切削方向正交的方向以符號C所示般，為產生成筋狀的微細凹凸。若產生此小缺損，損及商品外觀。When a large crystal grain having a crystal grain size of more than 200 μm is mixed, a small small defect is likely to occur on the surface during the cutting process, and the small defect is as shown in Fig. 2, and when the material is cut by a cutter or the like, in the cutting direction thereof ( In the cutting mark W generated by the direction indicated by the arrow A, the direction perpendicular to the cutting direction is as shown by the symbol C, and the fine unevenness in the form of a rib is generated. If this small defect occurs, it will damage the appearance of the product.

又，使平均結晶粒徑未達10μm係不現實，招致製造成本增加。Further, it is unrealistic to make the average crystal grain size to be less than 10 μm, resulting in an increase in manufacturing cost.

又，藉由部分再結晶化而形成雙晶組織，特殊粒界長度比率為25%以上，結晶粒界之整合性會提昇，濺鍍靶、或電鍍用陽極等之用途很有效。Further, by forming a twin crystal structure by partial recrystallization, the specific grain boundary length ratio is 25% or more, and the integration of crystal grain boundaries is enhanced, and the use of a sputtering target or an anode for plating is effective.

結晶粒界係二次元截面觀察之結果，定義為相鄰之2個結晶間的配向為15°以上時的該結晶間之境界。特殊粒界係結晶學上依據CSL理論(Kronberg et. al.：Trans. Met. Soc. AlME. 185,501(1949)所定義之Σ值具有3≦Σ≦29之結晶粒界(對應粒界)，定義為於該粒界之固有對應部位格子方位缺陷Dq滿足Dq≦15°/Σ1/2 (D. G. Brandon：Acta. Metallurgica. Vol.14,p1479,1966)之結晶粒界。The result of observation of the cross section of the crystal grain boundary system is defined as the boundary between the crystals when the alignment between the adjacent two crystals is 15 or more. The special grain boundary system is crystallographically based on the CSL theory (Kronberg et. al.: Trans. Met. Soc. AlME. 185, 501 (1949). The enthalpy value has a crystal grain boundary of 3≦Σ≦29 (corresponding to the grain boundary). The lattice orientation defect Dq defined as the intrinsic corresponding portion of the grain boundary satisfies the crystal grain boundary of Dq ≦ 15 ° / Σ 1/2 (DG Brandon: Acta. Metallurgica. Vol. 14, p1479, 1966).

全部之結晶粒界中，若此特殊粒界長度比率高，結晶粒界的整合性提高，就純銅板之用途而言，可提昇廣為人知之濺鍍靶或電鍍用陽極、或放熱基板等的特性。In all of the crystal grain boundaries, if the ratio of the specific grain boundary length is high, the integration of the crystal grain boundaries is improved, and the characteristics of the well-known sputtering target, the plating anode, or the heat release substrate can be improved in the use of the pure copper plate. .

亦即，在濺鍍靶中係於濺鍍時之異常放電特性與結晶組織之間有關係，依材料之高純度化亦即含有雜質量的降低(特開2002-129313)、粒徑的均質性(WO03/046250)、組織之結晶配向性的抑制(特開平10-330923)等，濺鍍特性之中，顯示抑制異常放電之方法。但，在近年係為提昇生產性，尋求濺鍍率的更進一步提昇，濺鍍電壓係在於高壓化之方向。若濺鍍電壓提昇，更易引起濺鍍時之異常放電的環境，故僅習知之組織控制方法係異常放電抑制效果不充分，尋求更進一步的組織控制。That is, there is a relationship between the abnormal discharge characteristics at the time of sputtering in the sputtering target and the crystal structure, and the purity of the material is high, that is, the content of the impurities is reduced (JP-2002-129313), and the particle size is homogeneous. (WO03/046250), inhibition of crystal orientation of a structure (JP-A 10-330923), etc. Among the sputtering characteristics, a method of suppressing abnormal discharge is shown. However, in recent years, in order to improve productivity, the sputtering rate has been further improved, and the sputtering voltage is in the direction of high pressure. If the sputtering voltage is increased, it is more likely to cause an abnormal discharge environment during sputtering. Therefore, only the conventional tissue control method is insufficient in the abnormal discharge suppression effect, and further structural control is sought.

又，純銅製之電鍍用陽極材係尤其可使用於印刷電路板之貫通孔電鍍等，但陽極溶解時產生電流密度分布的不均而引起局部之導通不良，結果產生不溶性之泥，有時有關於電鍍不良或生產效率的降低。就對策而言，提高在陽極之溶解面的面內溶解均質性很有效，藉結晶粒之微細化採取對策。但，一般，粒界係較粒內易溶解，藉微細化即使陽極之面內溶解均質性提高，粒界選擇性溶解係無法避免，而可判斷出在微細化效果有極限。因而，認為抑制粒界本身之溶解性對於前述泥之發生很有效，但以往未從如此之觀點進行硏究。Further, the anode material for electroplating made of pure copper can be used for plating through-holes of a printed circuit board, etc., but when the anode is dissolved, uneven current density distribution occurs, causing local conduction failure, resulting in insoluble mud, sometimes Regarding poor plating or a reduction in production efficiency. In terms of countermeasures, it is effective to improve the in-plane dissolution homogeneity of the dissolved surface of the anode, and countermeasures are taken by miniaturization of crystal grains. However, in general, the grain boundary system is more soluble than the inside of the grain, and even if the solubility homogeneity in the surface of the anode is improved by miniaturization, the selective dissolution of the grain boundary cannot be avoided, and it can be judged that there is a limit to the effect of miniaturization. Therefore, it is considered that suppressing the solubility of the grain boundary itself is effective for the occurrence of the aforementioned mud, but it has not been studied from such a viewpoint in the past.

進而，在放熱基板中係從使用時反覆膨脹收縮，有均一的變形特性，且疲勞特性優異乃很重要。近年，在省能源化、低CO化的流行普及進展之油電混合車或太陽電池等係直交變頻器電路為不可或缺，用以使變換時產生之熱進行放熱的放熱基板，可使用純銅或低合金銅板。此等之用途係依系統之大型化的大電流化進展，施加於放熱基板之熱負擔係增大的方向。放熱基板係使用中，經常反覆熱膨脹/收縮，故尋求長期性耐熱疲勞特性。有關耐熱疲勞特性係組織之均質性很重要，但僅習知之組織的均一性提昇，係很難提高伴隨前述大電流化之疲勞特性。Further, it is important that the heat-releasing substrate is repeatedly expanded and contracted from use, has uniform deformation characteristics, and is excellent in fatigue characteristics. In recent years, electric power hybrid vehicles or solar cells, which are popular in the development of energy-saving and low-CO, are indispensable, and the exothermic substrate for exchanging heat generated during the conversion can use pure copper. Or low alloy copper plate. The use of these types is in the direction in which the heat load applied to the heat-releasing substrate increases in accordance with the progress of the large current of the system. In the use of an exothermic substrate, it is often repeated with thermal expansion/contraction, so long-term thermal fatigue resistance is sought. Regarding the heat-fatigue property, the homogeneity of the structure is important, but only the uniformity of the conventional structure is improved, and it is difficult to improve the fatigue characteristics accompanying the above-mentioned large current.

此等之課題係使平均結晶粒徑微細化，可藉結晶粒界之特殊粒界之長度比率為25%以上進行解決。亦即，在濺鍍靶中係在濺鍍面全體被均質地濺鍍，很難產生成為異常放電之原因的結晶粒界之段差，結果，異常放電次數降低。電鍍用陽極係可判斷出特殊粒界具有較一般的粒界更近似在粒內的溶解特性之性質，藉由使用提高特殊粒界比率之銅板，陽極溶解時之面內溶解均質性充分提高，可平滑地保持溶解面，故可抑制不溶性之泥的發生，所形成之電鍍膜的品質會提高。又，在放熱基板係顯示均一的變形，即使藉熱膨脹與熱收縮之反覆，亦很難產生金屬疲勞，耐熱疲勞特性提高。These problems are to refine the average crystal grain size, and the ratio of the length of the grain boundary of the grain boundary is 25% or more. In other words, in the sputtering target, the entire sputtering surface is uniformly sputtered, and it is difficult to cause a step difference in crystal grain boundaries which causes abnormal discharge, and as a result, the number of abnormal discharges is lowered. The anode for electroplating can determine that the special grain boundary has a solubility characteristic similar to that of a general grain boundary in the grain. By using a copper plate having a specific grain boundary ratio, the in-plane dissolution homogeneity at the time of anodic dissolution is sufficiently improved. Since the dissolved surface can be smoothly maintained, the occurrence of insoluble mud can be suppressed, and the quality of the formed plating film can be improved. Further, the heat-releasing substrate exhibits uniform deformation, and even if it is repeated by thermal expansion and heat shrinkage, it is difficult to cause metal fatigue and heat fatigue resistance is improved.

如此地，本發明之純銅板係藉由使特殊粒界之長度的比率為25%以上，可看到濺鍍靶之異常放電的抑制、電鍍用陽極之不溶性泥的發生抑制、在放熱基板之耐熱疲勞特性的提昇等之效果，適宜於濺鍍靶、電鍍用陽極、放熱基板等。In the pure copper plate of the present invention, the ratio of the length of the special grain boundary is 25% or more, and the suppression of the abnormal discharge of the sputtering target and the suppression of the occurrence of the insoluble mud of the anode for plating can be observed. The effect of improving the heat-resistant fatigue characteristics is suitable for a sputtering target, an anode for plating, a heat-releasing substrate, and the like.

其次，說明有關製造如此之純銅板的方法。Next, a description will be given of a method for manufacturing such a pure copper plate.

首先，使純銅錠加熱至550℃~800℃，再於複數次壓延輥之間往返運行，同時並徐緩地縮小壓延輥間之間隙，而壓延至特定厚度。以此複數次之壓延的壓延率為80%以上，壓延終了時之溫度為500~700℃。其後，以200~1000℃/分鐘之冷卻速度從壓延終了時溫度急冷至200℃以下之溫度。其後，以5~24%之壓延率進行冷間壓延，以250~600℃加熱30分鐘~2小時，俾進行燒結。First, the pure copper ingot is heated to 550 ° C ~ 800 ° C, and then run back and forth between the plurality of calender rolls, while slowly reducing the gap between the calender rolls, and rolling to a specific thickness. The rolling ratio of the rolling of the plurality of times is 80% or more, and the temperature at the end of the rolling is 500 to 700 °C. Thereafter, the temperature is rapidly cooled from a temperature at the end of the rolling to a temperature lower than 200 ° C at a cooling rate of 200 to 1000 ° C /min. Thereafter, it is subjected to cold rolling at a rolling ratio of 5 to 24%, heated at 250 to 600 ° C for 30 minutes to 2 hours, and sintered.

以一般之純銅板的製造方法在熱間壓延冷卻冷間壓延熱處理之製程中，熱間壓延係以850~900℃之高溫加工。若以如此之高溫狀態進行熱間壓延，結晶粒粗大化，故即使再急冷，亦無法使平均結晶粒徑微細化至80μm以下。Calendering between heats in a general method of manufacturing pure copper plates cool down Cold rolling In the heat treatment process, the inter-heat rolling is processed at a high temperature of 850 to 900 °C. When the inter-heat rolling is carried out in such a high temperature state, the crystal grains are coarsened, so that even if it is quenched again, the average crystal grain size cannot be made fine to 80 μm or less.

在本實施形態的製造方法中，使熱間壓延形成開始溫度為550~800℃，終了溫度為500~700℃之比較低溫狀態。若熱間壓延之終了溫度超過700℃，結晶粒急劇變大，其後即使冷卻，亦很難得到微細的結晶粒。又，即使熱間壓延終了溫度未達500℃，結晶粒徑之微細化的效果飽和，即使降低溫度至其以下，亦無助於微細化。又，若壓延溫度低，為得到所希望的總壓延率，過大的能量成為必須，其加工困難。因此，使壓延終了溫度為500~700℃。繼而，為使此熱間壓延之終了溫度為500~700℃，使熱間壓延之開始溫度為550~800℃。In the production method of the present embodiment, the heat-to-heat rolling formation start temperature is 550 to 800 ° C, and the final temperature is 500 to 700 ° C in a relatively low temperature state. When the temperature at the end of the hot rolling is more than 700 ° C, the crystal grains become sharply large, and even if it is cooled, it is difficult to obtain fine crystal grains. Further, even if the temperature at the end of the hot rolling is less than 500 ° C, the effect of refining the crystal grain size is saturated, and even if the temperature is lowered to be lower than the above, it does not contribute to miniaturization. Further, if the rolling temperature is low, in order to obtain a desired total rolling ratio, excessive energy is required, and processing is difficult. Therefore, the rolling end temperature is made 500 to 700 °C. Then, in order to heat the end of the heat to a temperature of 500 to 700 ° C, the start temperature of the inter-heat rolling is 550 to 800 ° C.

又，以此熱間壓延的壓延率宜為80%以上，藉由使壓延率為80%以上而抑制結晶粒徑的粗大化，同時並可縮小其參差不齊。從如此之觀點，宜使壓延率為80%以上。若壓延率未達80%，有結晶粒變大的傾向，同時其參差不齊變大。又，為達成前述壓延率，複數次的壓延中，最終階段的壓延，更宜使每1回的壓下率為25%以上。在熱間壓延之最後的階段使壓下率增大成25%以上，俾防止大的結晶粒的混合在一起，可全體地進一步形成整齊的微細結晶粒。宜使最終階段之壓延以此25%以上之壓下率進行1回~數回。所謂此每一回的壓下率係通過壓延輥之後的母材之板厚對通過壓延輥之前的母材之板厚的減少率(或本回之壓延輥間之間隙對前回時之壓延輥間之間隙的減少率)，總壓延率係壓延終了後的母材之板厚對壓延前的母材之減少率。亦即使通過壓延輥之前的母材之板厚為t0 ，使通過壓延輥之後的母材之板厚為t1 ，每1回之壓下率γ(%)係定義為γ=(t0 -t1 )/(t0 )×100(%)。Further, the rolling ratio by the inter-heat rolling is preferably 80% or more, and the rolling ratio is made 80% or more to suppress the coarsening of the crystal grain size, and the unevenness can be reduced. From such a viewpoint, it is preferable to make the rolling ratio 80% or more. If the rolling ratio is less than 80%, the crystal grains tend to become large, and the unevenness thereof becomes large. Further, in order to achieve the rolling ratio, it is preferable that the rolling in the final stage in the plurality of rollings is 25% or more per one time. In the final stage of the inter-heat rolling, the reduction ratio is increased to 25% or more, and the large crystal grains are prevented from being mixed together, and the fine fine crystal grains can be further formed as a whole. It is advisable to carry out the final stage of rolling at a reduction rate of 25% or more for one to several times. The reduction ratio of each of these is the reduction rate of the thickness of the base material after passing through the calendering roll to the thickness of the base material before passing through the calendering roll (or the gap between the calender rolls of the present time and the calendering roll of the preceding return) The reduction rate of the gap between the two is the reduction ratio of the thickness of the base material after the end of rolling to the base material before rolling. Even if the thickness of the base material before passing through the calender roll is t 0 , the thickness of the base material after passing through the calender roll is t 1 , and the reduction ratio γ (%) per one time is defined as γ=(t 0 -t 1 ) / (t 0 ) × 100 (%).

繼而，於如此之熱間壓延終了後，藉水冷而以200~1000℃/分鐘的冷卻速度急冷至成為200℃以下之溫度。冷卻速度未達200℃/分鐘，缺乏抑制結晶粒之成長的效果，即使超過1000℃/分鐘，亦無助於其以上之微細化。Then, after the end of the calendering in such a heat, it is rapidly cooled to a temperature of 200 ° C or lower by a cooling rate of 200 to 1000 ° C / min by water cooling. The cooling rate is less than 200 ° C / min, and there is no effect of suppressing the growth of crystal grains. Even if it exceeds 1000 ° C / min, it does not contribute to the above refinement.

若以如此之範圍的冷卻速度冷卻至200℃以下之溫度，可停止結晶粒的成長而得到微細的結晶粒者。若以超過200℃之溫度停止急冷，其後，恐藉由在其高溫狀態的放置而結晶粒徐緩地成長。When the temperature is cooled to 200 ° C or lower at a cooling rate in such a range, the growth of crystal grains can be stopped to obtain fine crystal grains. When quenching is stopped at a temperature exceeding 200 ° C, the crystal grains are slowly grown by being placed in a high temperature state.

繼而，冷間壓延係提昇硬度、強度，提高平坦度而得到良好的表面狀態，同時其後實施熱處理，而為使結晶粒界的特殊粒界之長度比率增大至25%以上，形成5~24%之壓延率。壓延率未達5%，很難得到所希望的特殊粒界比率，另外，即使超過24%，亦看不到進一步的效果。Then, the cold rolling is to increase the hardness and strength, to improve the flatness, and to obtain a good surface state, and then to perform heat treatment, and to increase the length ratio of the special grain boundary of the grain boundary to 25% or more, forming 5~ 24% rolling rate. When the rolling ratio is less than 5%, it is difficult to obtain a desired specific grain boundary ratio, and further, even if it exceeds 24%, no further effect is observed.

燒結處理係使用以冷間壓延導入之變形能量，而藉由部分再結晶化而形成雙晶組織，提昇特殊粒界長度比率。燒結溫度宜為250~600℃，只要以其加熱環境保持30~120分鐘即可。In the sintering treatment, the deformation energy introduced by cold rolling is used to form a bicrystal structure by partial recrystallization, thereby increasing the specific grain boundary length ratio. The sintering temperature should be 250~600 °C, as long as it is kept in the heating environment for 30~120 minutes.

實施例Example

其次，說明本發明之實施例。Next, an embodiment of the present invention will be described.

壓延材料係使用電子管用無氧銅(純度99.99wt%以上)的鑄造錠。壓延前之材料尺寸係寬650mm×長900mm×厚290mm，使熱間壓延以後之各條件如表1所示般組合複數而製作純銅板。又，溫度之測定係使用輻射溫度計，測定壓延板之表面溫度。The calendered material is a cast ingot of oxygen-free copper (purity of 99.99 wt% or more) for an electron tube. The material size before rolling was 650 mm in width × 900 mm in length × 290 mm in thickness, and the conditions after the inter-heat rolling were combined as shown in Table 1 to prepare a pure copper plate. Further, the temperature was measured by using a radiation thermometer to measure the surface temperature of the rolled plate.

然後，有關表1記載之純銅板，測定有關平均結晶粒徑、特殊粒界長度比率、維氏(Vickers)硬度、使用來作為濺鍍靶時之濺鍍中的異常放電次數，及使用來作為電鍍用陽極時之不溶性泥的發生量。Then, regarding the pure copper plate described in Table 1, the average crystal grain size, the specific grain boundary length ratio, the Vickers hardness, the number of abnormal discharges during sputtering used as a sputtering target, and the use were measured. The amount of insoluble mud generated when the anode for electroplating is used.

＜平均結晶粒徑、特殊粒界長度比率＞<Average crystal grain size, special grain boundary length ratio>

對於各試料，使用耐水硏磨紙、鑽石磨粒而進行機械硏磨後，使用膠體二氧化矽溶液而進行精加工硏磨。For each sample, mechanical honing was performed using water-resistant honing paper and diamond abrasive grains, and then finishing honing was performed using a colloidal cerium oxide solution.

繼而，藉EBSD測定裝置(HITACHI公司製S4300-SE、EDAX/TSL公司製OIM Data Collection)、與解析軟體(EDAX/TSL公司製OIM Data Analysis ver. 5.2)，而特定結晶粒界、特殊粒界，算出其長度，俾進行平均結晶粒徑及特殊粒界長度比率之解析。Then, the EBSD measuring device (S4300-SE manufactured by HITACHI Co., Ltd., OIM Data Collection manufactured by EDAX/TSL Co., Ltd.) and the analytical software (OIM Data Analysis ver. 5.2 manufactured by EDAX/TSL Co., Ltd.), and specific crystal grain boundaries and special grain boundaries The length was calculated, and the average crystal grain size and the specific grain boundary length ratio were analyzed.

首先，使用掃描型電子顯微鏡，對試料表面之測定範圍內的各個測定點(畫素)照射電子束，藉由以後方散射電子束繞射之方位解析，使鄰接之測定點間的方位差成為15°以上之測定點間作為結晶粒界。First, a scanning electron microscope is used to irradiate an electron beam to each measurement point (pixel) in the measurement range of the surface of the sample, and the orientation difference between the adjacent measurement points is obtained by analyzing the direction of the backscattered electron beam diffraction. Between the measurement points of 15° or more, it is a crystal grain boundary.

平均結晶粒徑(雙晶亦計數為結晶粒)的測定係從所得到之結晶粒界，算出觀察區域內之結晶粒子數，使區域面積除以結晶粒子數而算出結晶粒子面積，使其進行圓換算，形成平均結晶粒徑(直徑)。The measurement of the average crystal grain size (the crystal is also counted as crystal grains) is calculated from the obtained crystal grain boundaries, and the number of crystal particles in the observation region is calculated, and the area of the crystal particles is divided by the number of crystal particles to calculate the crystal particle area. The average crystal grain size (diameter) is formed in terms of a circle.

又，測定在測定範圍中之結晶粒界的全粒界長度L，決定鄰接之結晶粒的界面構成特殊粒界之結晶粒界的位置，同時並求出特殊粒界的全特殊粒界長度Lσ與上述所測定之結晶粒界的全粒界長度L的粒界長度比率Lσ/L，作為特殊粒界長比率。Further, the total grain boundary length L of the crystal grain boundary in the measurement range is measured, and the position of the crystal grain boundary of the adjacent grain boundary is determined, and the position of the grain boundary of the special grain boundary is determined, and the full special grain boundary length Lσ of the specific grain boundary is obtained. The grain boundary length ratio Lσ/L of the total grain boundary length L of the crystal grain boundary measured as described above is a specific grain boundary length ratio.

＜維氏(Vickers)硬度＞<Vickers hardness>

維氏(Vickers)硬度係對於沿著壓延方向(R.D.方向)的縱截面圖(T.D.方向看的面)，依據JIS(Z2244)所規定的方法進行測定。The Vickers hardness is measured in a longitudinal section (surface viewed in the direction of T.D.) along the rolling direction (R.D. direction) according to the method specified in JIS (Z2244).

＜濺鍍異常放電次數＞<sputter abnormal discharge times>

從各試料靶材部分成為直徑152mm、厚8mm的方式製作含有支撐板部分的一體型之靶材，安裝於濺鍍裝置，使腔室內之到達真空壓力為1×10-5 Pa以下，使用高純度Ar作為濺鍍氣體，使濺鍍氣體壓為0.3Pa，以直流(DC)電源，以濺鍍輸出1kW的條件進行8小時之連續濺鍍。又，使用附屬於電源之弧光計數器，而計數總異常放電次數。An integral type target including a support plate portion was prepared from a sample having a diameter of 152 mm and a thickness of 8 mm, and was attached to a sputtering apparatus to bring the vacuum pressure to 1 × 10 -5 Pa or less in the chamber, and the use was high. Purity Ar was used as a sputtering gas, and the sputtering gas pressure was 0.3 Pa, and continuous sputtering was performed for 8 hours under a condition of a sputtering current of 1 kW using a direct current (DC) power source. Also, the total number of abnormal discharges is counted using an arc counter attached to the power source.

＜陽極泥產生量＞<Anode mud production amount>

使切出成直徑270mm的圓盤狀之銅板固定於電極支撐座(實行電極面積約530cm2 )，作為陽極電極，使直徑200mm之矽晶圓作為陰極，而以下的條件進行鍍銅，採取從電鍍開始至第5片的晶圓處理時所產生的不溶性泥，測定泥產生量。又，泥產生量係回收泥後，藉乾燥後之重量測定求出。A disk-shaped copper plate cut into a diameter of 270 mm was fixed to an electrode holder (the electrode area was about 530 cm 2 ), and as a cathode electrode, a silicon wafer having a diameter of 200 mm was used as a cathode, and copper plating was performed under the following conditions. The amount of mud generated was measured from the insoluble sludge generated during the wafer processing to the fifth wafer. Further, the amount of sludge generated is obtained by recovering the sludge, and is determined by the weight measurement after drying.

電鍍液：於離子交換水中添加焦磷酸銅70g/升、焦磷酸鉀300g/升、硝酸鉀15g/升，於氨水調整成pH8.5者，電鍍條件：以液晶50℃以空氣攪拌及陰極搖動之攪拌實施，陰極電流密度：2A/dm2 ，電鍍時間：1小時/片。Electroplating solution: Add 70g/L of copper pyrophosphate, 300g/L of potassium pyrophosphate, 15g/L of potassium nitrate to ion-exchanged water, adjust to pH 8.5 in ammonia water, plating conditions: air stirring and cathode shaking at 50°C Stirring was carried out, cathode current density: 2 A/dm 2 , plating time: 1 hour/piece.

<小缺損><small defect>

使各試料形成100×2000mm之平板，其表面於切割盤使用超硬刃尖的刻入而以切痕深度0.2mm、切削速度5000m/分鐘切削加工，硏究在其切削表面的500μm四方的視野內長100μm以上之小缺損瑕疵存在幾個。Each sample was formed into a flat plate of 100×2000 mm, and the surface thereof was cut with a super-hard edge to the cutting disk with a cutting depth of 0.2 mm and a cutting speed of 5000 m/min, and a 500 μm square field of view on the cutting surface was examined. There are several small defect defects with an inner length of 100 μm or more.

此等之結果表示於表2中。The results of these are shown in Table 2.

從此表2明顯可知，以本實施例之製造方法所製造的純銅板係任一者平均結晶粒徑均為10~120μm，硬度為40~90Hv的範圍，特殊粒界長度比率為25%以上。然而，比較例之純銅板係平均結晶粒粒徑、硬度或特殊粒界長度比率超出範圍。其結果，可知在實施例之濺鍍靶中係異常放電次數極低，使用來作為電鍍用陽極時之溶解特性評估中的不溶性陽極泥的產生量亦極低。另外，在比較例中係異常放電次數較實施例多，又，陽極泥量亦增加，進一步，機械加工後之表面狀態中產生小缺損者亦被觀察到。As is apparent from the above Table 2, the pure crystal plate produced by the production method of the present embodiment has an average crystal grain size of 10 to 120 μm, a hardness of 40 to 90 Hv, and a specific grain boundary length ratio of 25% or more. However, the ratio of the average crystal grain size, hardness or special grain boundary length of the pure copper plate of the comparative example was out of range. As a result, it was found that the number of abnormal discharges in the sputtering target of the example was extremely low, and the amount of insoluble anode slime generated in the evaluation of the solubility characteristics when used as an anode for plating was extremely low. Further, in the comparative example, the number of abnormal discharges was larger than that of the examples, and the amount of anode mud was also increased. Further, small defects were observed in the surface state after machining.

以上，說明有關本發明之實施形態，但本發明係不限定於此記載，在不超出其發明之技術思想的範圍可適當變更。The embodiment of the present invention has been described above, but the present invention is not limited thereto, and can be appropriately changed without departing from the scope of the technical idea of the invention.

產業上之利用可能性Industrial use possibility

本發明之純銅板係亦可適用於濺鍍用靶材、靶材用支撐板，其他，電鍍用陽極、模具、放電電極、放熱板、吸熱體、模具、水冷板、電極、電氣用端子、匯流排、墊片、法蘭、印刷板等。The pure copper plate of the present invention can also be applied to a target for sputtering, a support plate for a target, and the like, an anode for an electroplating, a mold, a discharge electrode, a heat release plate, a heat absorbing body, a mold, a water-cooled plate, an electrode, an electrical terminal, Bus bars, gaskets, flanges, printing plates, etc.

W．．．切削痕W. . . Cutting marks

C．．．小缺損瑕疵C. . . Small defect

圖1係切削純銅板之表面時所產生的小缺損之顯微鏡照片。Figure 1 is a photomicrograph of a small defect produced when cutting the surface of a pure copper plate.

Claims (6)

一種純銅板之製造方法，其特徵係使純度為99.96wt%以上之純銅錠加熱至550~800℃，實施以熱間壓延之壓延率為80%以上且壓延終了溫度為500~700℃之熱間壓加工後，從前述壓延終了溫度至200℃以下之溫度以200~1000℃/分鐘之冷卻速度急速冷卻，其後，以5~24%之壓延率進行冷間壓延再進行燒結。A method for producing a pure copper plate, characterized in that a pure copper ingot having a purity of 99.96 wt% or more is heated to 550 to 800 ° C, and a calendering rate of 80% or more and a calendering end temperature of 500 to 700 ° C is performed. After the inter-pressure processing, the temperature is cooled from 200 ° C to 1000 ° C or less at a cooling rate of 200 to 1000 ° C / min, and then calendered at a rolling ratio of 5 to 24 % and then sintered. 一種純銅板，係藉由如申請專利範圍第1項之製造方法所製造之純銅板，其特徵係以EBSD法所測定之相對於結晶粒界的全粒界長度L之特殊粒界的全特殊粒界長度Lσ之比率(Lσ/L)為25%以上。A pure copper plate, which is a pure copper plate manufactured by the manufacturing method of the first application of the patent application, characterized by a special special grain boundary determined by the EBSD method with respect to the full grain boundary length L of the crystal grain boundary. The ratio (Lσ/L) of the grain boundary length Lσ is 25% or more. 如申請專利範圍第2項之純銅板，其中維氏(Vickers)硬度為40~90。For example, the pure copper plate of claim 2, wherein the Vickers hardness is 40-90. 如申請專利範圍第2項之純銅板，其中以EBSD法所測定之平均結晶粒徑為10~120μm。For example, the pure copper plate of the second application of the patent scope, wherein the average crystal grain size measured by the EBSD method is 10 to 120 μm. 如申請專利範圍第2項之純銅板，其係濺鍍靶材。For example, the pure copper plate of the second application of the patent scope is a sputtering target. 如申請專利範圍第2項之純銅板，其係電鍍用陽極。For example, the pure copper plate of the second application of the patent scope is an anode for electroplating.
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