TW201139706A - Pure copper plate production method, and pure copper plate - Google Patents
Pure copper plate production method, and pure copper plate Download PDFInfo
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- TW201139706A TW201139706A TW100104284A TW100104284A TW201139706A TW 201139706 A TW201139706 A TW 201139706A TW 100104284 A TW100104284 A TW 100104284A TW 100104284 A TW100104284 A TW 100104284A TW 201139706 A TW201139706 A TW 201139706A
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- pure copper
- copper plate
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 69
- 238000005096 rolling process Methods 0.000 claims abstract description 56
- 238000001816 cooling Methods 0.000 claims abstract description 34
- 238000004544 sputter deposition Methods 0.000 claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 6
- 238000009830 intercalation Methods 0.000 claims description 3
- 230000002687 intercalation Effects 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000005098 hot rolling Methods 0.000 abstract description 16
- 238000005097 cold rolling Methods 0.000 abstract description 13
- 238000010273 cold forging Methods 0.000 abstract description 8
- 238000005242 forging Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003490 calendering Methods 0.000 description 23
- 235000013339 cereals Nutrition 0.000 description 23
- 238000005477 sputtering target Methods 0.000 description 17
- 230000002159 abnormal effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000017525 heat dissipation Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013142 Disinhibition Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- 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
Landscapes
- 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)
Abstract
Description
201139706 六、發明說明: 【發明所屬之技術領域】 本發明關於一種具有良好品質之純銅板的製造方法, 特別詳細地,關於一種與具有微細的組織一起,藉由部分 地再結晶化而形成雙晶組織,而賦予高特殊粒界比率之純 銅板的製造方法,以及一種適用於由該製造方法所製造的 濺鍍用銅靶素材或鍍敷用陽極素材等之純銅板。 本案係以2010年2月9日申請的特願2010-26455號爲基 礎而主張優先權,在此援用其內容。 【先前技術】 純銅板通常係藉由將純銅的鑄錠熱間壓延或熱間锻造 後,施予冷間壓延或冷間锻造,然後施予消除應力或再結 晶化用的熱處理而製造。如此的純銅板係經由鋸子切斷、 切削加工、壓花加工、冷間锻造等加工成所欲的形狀而使 用,爲了減少加工時的擠裂或變形,要求結晶粒徑小,結 晶組織中的殘留應力小。 又,上述方法所製造的純銅板,在最近係作爲半導體 元件的配線材料用之濺鍍靶使用。作爲半導體元件的配線 材料,向來使用A1 (比電阻3.1 μΩ · cm左右),惟隨著最 近配線的微細化,更低電阻的銅配線(比電阻1 . 7 μΩ · cm 左右)係實用化。作爲此銅配線的形成製程,多在接觸孔 或配線溝的凹部形成Ta/TaN等的擴散障壁層後將銅電鍍, 進行將純銅濺鑛成膜以作爲用於進行此電鑛的基底層(種 -5- 201139706 子層)。 通常,以4N (純度99.99%以上:排除氣體成分)程度 的電解銅當作粗金屬’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’藉由上述方法使其成爲純銅板,再加 工成所欲的形狀後,作爲濺鍍靶使用。爲了製作低電阻的 濺鍍膜,將濺鍍靶中的雜質含量抑制在—定値以下’而且 必須將合金化用的添加元素降低至一定程度以下,爲了得 到濺鍍膜厚的均勻性,必須抑制濺鍍靶的結晶粒徑及結晶 配向性的偏差。 作爲工業上製造如此濺鍍用純銅靶的習知方法,專利 文獻1中揭示將純度爲9 9,99 5 wt%以上之純銅的鑄錠熱加工 ,然後在900°C以下的溫度進行退火,接著以40%以上的壓 延率施予冷間壓延後,在500°C以下的溫度進行再結晶退 火,而得到實質上具有再結晶組織,平均結晶粒徑爲80微 米以下,而且維氏硬度爲100以下之濺鍍用銅靶的方法。 又’專利文獻2中揭示對5N以上的高純度銅鑄錠施予 熱間锻造或熱間壓延等的加工率50%以上之熱加工後,再 進行冷間壓延或冷間锻造等的加工率3 0 %以上之冷加工, 在3 5 0〜5〇(TC實施1〜2小時的熱處理,而得到Na及K含量 各自爲O.lppm以下,Fe、Ni、Cr、Al、Ca、Mg含量各自 爲lppm以下,碳及氧含量各自爲5ppm以下,u及Th含量各 自爲Ippb以下,去除氣體成分後的銅含量爲99.999%以上 ’更且濺鍍面的平均粒徑爲250μιη以下,平均粒徑的偏差201139706 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a pure copper plate having good quality, and in particular, relates to a double formed by partially recrystallizing together with a fine structure A method for producing a pure copper plate having a high specific grain boundary ratio, and a pure copper plate suitable for use in a copper target material for sputtering or an anode material for plating produced by the production method. The case is based on the purpose of the special request 2010-26455, which was filed on February 9, 2010, and the content is claimed here. [Prior Art] A pure copper plate is usually produced by subjecting a pure copper ingot to hot rolling or hot forging, applying cold rolling or cold forging, and then applying heat treatment for stress relief or recrystallization. Such a pure copper plate is used to be processed into a desired shape by sawing, cutting, embossing, cold forging, etc., in order to reduce cracking or deformation during processing, it is required to have a small crystal grain size and a crystal structure. The residual stress is small. Further, the pure copper plate produced by the above method has recently been used as a sputtering target for a wiring material of a semiconductor element. As a wiring material for a semiconductor element, A1 (a specific resistance of about 3.1 μΩ · cm) has been used. However, the copper wiring of a lower resistance (a specific resistance of about 1. 7 μΩ · cm) is put into practical use as the nearest wiring is miniaturized. As a forming process of the copper wiring, copper is electroplated by forming a diffusion barrier layer such as Ta/TaN in a recess of a contact hole or a wiring trench, and sputtering of pure copper is performed to form a base layer for performing the electric ore ( Kind-5- 201139706 sublayer). Usually, 4N (purity of 99.999% or more) to 6N (purity of 99.9999% or more) is produced by using 4N (purity of 99.99% or more: gas component exclusion) electrolytic copper as a crude metal 'by a wet or dry high purity process' The purity of the high-purity copper 'is made into a pure copper plate by the above method, and is processed into a desired shape, and then 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 below - and the additive element for alloying must be reduced to a certain level or less. In order to obtain uniformity of the thickness of the sputtering film, sputtering must be suppressed. The deviation of the crystal grain size and crystal orientation of the target. As a conventional method for industrially producing such a pure copper target for sputtering, Patent Document 1 discloses that an ingot of pure copper having a purity of 99,99 5 wt% or more is thermally processed, and then annealed at a temperature of 900 ° C or lower. Subsequently, the inter-cold rolling is performed at a rolling ratio of 40% or more, and then recrystallization annealing is performed at a temperature of 500 ° C or lower to obtain a substantially recrystallized structure, and the average crystal grain size is 80 μm or less, and the Vickers hardness is 100. The following method of sputtering a copper target. Further, Patent Document 2 discloses that a high-purity copper ingot of 5 N or more is subjected to hot working such as hot forging or hot-rolling, and the processing rate of cold rolling or cold forging is 3 0% or more of cold working, at 305 to 5 〇 (TC is subjected to heat treatment for 1 to 2 hours, and Na and K contents are each 0.1 ppm or less, and Fe, Ni, Cr, Al, Ca, and Mg contents are each Lppm 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 copper content after removing the gas component is 99.999% or more. Further, the average particle diameter of the sputtering surface is 250 μm or less, and the average particle diameter is deviation
-6- 201139706 爲±20%以內’ X射線繞射強度比i ( 1 1 1 ) /1 ( 200 )在濺鍍 面爲2.4以上且其偏差爲±20 %以內之濺鍍用銅靶的方法。 又,專利文獻3中揭示一種去除由純度6N以上的高純 度銅與添加元素所形成的鑄錠之表面層,經由熱間锻造、 熱間壓延、冷間壓延、熱處理步驟所得,含有0.5〜 4.0wt%的Al,Si爲0.5wtppm以下之銅合金濺鍍靶,一種含 有0.5〜4.0wt%的Sn,Μη爲0.5wtppm以下之銅合金濺鍍靶 ,以及一種在此等中含有總量爲1 .Owtppm以下的由Sb、Zr 、Ti、Cr、Ag、Au、Cd、In、As所選出的1或2個以上之 銅合金濺鍍靶。特別地,實施例中記載在去除所製造的鑄 銳之表面層而成爲<t»160mmx厚度60mm後,於400°C熱間鍛 造而成爲φ2 00ηιηι,然後於40(TC熱間壓延而壓延到(j>270mm X厚度20mm爲止,再進行冷間壓延而壓延到φ360ιηπιχ厚度 10mm爲止,於500°C熱處理1小時後,將靶全體急速冷卻而 成爲靶素材。 如以這樣的濺鍍用銅靶之製造方法爲代表,在以往的 純銅板之製造方法中,爲了得到均質且安定的再結晶組織 ,將純銅鑄錠熱間鍛造或熱間壓延後,進行冷間鍛造或冷 間壓延,再施予熱處理。 先前技術文獻 專利文獻 專利文獻1 :特開平1 1 - 1 5 86 1 4號公報 專利文獻2 :特開平1 0-3 30923號公報 201139706 專利文獻3 :特開2009- 1 1 45 3 9號公報 【發明內容】 發明所欲解決的問題 於工業上製造大型形狀的具有均質且安定的結晶組織 之純銅板的習知方法中,對純銅鑄錠施予熱間鍛造或熱間 壓延後,必須更施予冷間锻造或冷間壓延、熱處理,但對 於濺鍍靶的高輸出之濺鍍所致的異常放電之抑制、鍍敷用 陽極的均質溶解性之提高以及散熱基板的耐熱疲勞特性, 僅微細化係難以對應。 本發明係鑒於如此的情事而完成者,提供一於熱間锻 造或熱間壓延後無需進一步施予冷間锻造或冷間壓延及其 後的熱處理之純銅板的製造方法,以及提供一藉由與具有 由該製造方法所得之微細組織一起部分地再結晶化使雙晶 組織形成,而具有高特殊粒界比率之銅板,尤其適用於濺 鍍用銅靶素材或鍍敷用陽極等之純銅板。 解決問題的手段 本發明者們進行專心致力的檢討,結果發現:不依賴 以往的方,其係在藉由將純銅的鑄錠熱間锻造或熱間壓延 後,進行冷間锻造或冷間壓延、其後的熱處理,而促進再 結晶化,得到微細且均質的結晶粒之以往方法,而藉由對 純銅的鑄錠,爲了抑制結晶粒之成長,在一定的條件下熱 間壓延,藉由部分再結晶化而促進雙晶組織的形成,而且-6- 201139706 Method for sputtering copper target with a X-ray diffraction intensity ratio of i (1 1 1 ) /1 ( 200 ) with a sputtering surface of 2.4 or more and a deviation of ±20 % or less . Further, Patent Document 3 discloses a surface layer of an ingot formed by removing high-purity copper and an additive element having a purity of 6 N or more, and is obtained by hot forging, hot rolling, cold rolling, and heat treatment, and contains 0.5 to 4.0. A wt% Al, Si is a copper alloy sputtering target of 0.5 wtppm or less, a copper alloy sputtering target containing 0.5 to 4.0 wt% of Sn, and a Μη of 0.5 wtppm or less, and a total amount of 1 in this case One or two or more copper alloy sputtering targets selected from Sb, Zr, Ti, Cr, Ag, Au, Cd, In, As below Owtppm. In particular, in the examples, it is described that after the surface layer of the cast sharp produced is removed to have a thickness of <t»160 mmx and a thickness of 60 mm, it is forged at 400 ° C to be φ 2 00 ηιηι, and then calendered at 40 (TC heat rolling). (j> 270mm X thickness: 20mm, and then cold rolling, rolling to φ360ιηπι thickness 10mm, heat treatment at 500 °C for 1 hour, the target is rapidly cooled to become a target material. Such a copper for sputtering In the conventional method for producing a pure copper plate, in order to obtain a homogeneous and stable recrystallized structure, a pure copper ingot is hot forged or heat-rolled, and then subjected to cold forging or cold rolling, and then cold rolling is performed. In the case of the heat treatment, the prior art is disclosed in Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In the conventional method of industrially manufacturing a large-sized pure copper plate having a homogeneous and stable crystal structure, hot forging is performed on a pure copper ingot or After hot rolling, it is necessary to apply cold forging or cold rolling and heat treatment, but the suppression of abnormal discharge due to high output sputtering of the sputtering target, the improvement of the homogeneous solubility of the plating anode, and the heat dissipation substrate The heat-resistant fatigue property is difficult to cope with only the micronization. The present invention has been made in view of such circumstances, and provides a heat treatment between hot forging or hot rolling without further application of cold forging or cold rolling and subsequent heat treatment. A method for producing a pure copper plate, and a copper plate having a high specific grain boundary ratio by partially recrystallizing together with the fine structure obtained by the production method, and is particularly suitable for copper for sputtering A pure copper plate such as a target material or an anode for plating. The means for solving the problem The present inventors conducted a dedicated review and found that it is not dependent on the conventional side, and it is forged or hot by ingot of pure copper. After the inter-calendering, a conventional method of performing cold forging or cold rolling and subsequent heat treatment to promote recrystallization to obtain fine and homogeneous crystal grains By the ingot of copper, in order to suppress the growth of crystal grains, under certain conditions of heat between the rolling part by recrystallization and promote the formation of twins tissue, and
-8- 201139706 按照需要爲了停止粒成長,在一定的條件化下急速冷卻, 可製造更微細且具有高特殊粒界比率之金屬組織的純銅板 〇 本發明之純銅板的製造方法之特徵爲:將純度爲 99.96wt%以上的純銅之鑄錠加熱到550°C〜80(TC,總壓延 率爲85 %以上、壓延結束時溫度爲500〜700t,而且施予 每1道次壓延(one pass)的壓下率爲5〜24%之精整熱間 壓延有1道次(one pass)以上的熱間壓延加工,且特徵爲 :按照需要,可以200°C〜l〇〇〇°C/min的冷卻速度,自前述 壓延結束時的溫度急速冷卻至200°C以下的溫度爲止。 爲了得到結晶粒爲微細,藉由部分的再結晶化促進行 雙晶組織的形成,而提高特殊粒界比率之組織,重要的是 熱間壓延的結束步驟之精整熱間壓延的溫度(以下稱爲壓 延結束溫度),與精整熱間壓延的每1道次之壓下率。於 精整熱間壓延中,當壓延結束溫度未達5 00°C,或其每1道 次的壓下率未達5 %時,部分地再結晶化係不充分發生,另 外當壓延結束溫度超過70(TC,或每1道次之壓下率爲25% 以上時,精整熱間壓延中的動態再結晶係變成支配因素, 難以隨著部分地再結晶化所致的雙晶組織之形成而得到高 特殊粒界比率。而且,爲了使此壓延結束溫度成爲5 00〜 7〇〇°C,熱間壓延開始溫度可爲550〜800°C。 又,此熱間壓延所致的總壓延率宜爲8 5 %以上,由於 總壓延率爲85%以上,可抑制結晶粒徑的粗大化,同時可 減小該粒徑的偏差。總壓延率若未達8 5 %,則結晶粒徑有 -9 - 201139706 變大的傾向,同時該粒徑的偏差變大。 另外,藉由以5〜24 %進行熱間壓延的精整熱間壓延之 每1道次的壓下率,而促進雙晶組織的形成,成爲已提高 特殊粒界比率的組織,提高結晶粒界的整合性,結晶組織 變成微細且均勻。又,在上述精整熱間壓延,只要是於 5 00〜7 00°C的範圍中,每1道次的壓下率爲5〜24%,進行 至少1道次的壓延加工即可,但亦可連續複數道次而壓延 加工。特別地,藉由進行複數道次重複壓延,可更促進雙 晶組織的形成。如此所製造的純銅板係有效於濺鍍靶、鍍 敷用陽極、散熱基板等的用途。 而且,在如此的熱間壓延結束後,可更以200〜 1 000°C/min的冷卻速度,急速冷卻至20(TC以下的溫度爲止 。冷卻速度未達200°C/min時,缺乏抑制結晶粒的成長之效 果,即使超過1 000 °C/min,也無助於其以上的粒成長抑制 效果。更佳的冷卻速度爲300〜600°C/ min的範圍。 若以如此範圍的冷卻速度進行冷卻直到20(TC以下的 溫度爲止,則可停止結晶粒的成長,而得到微細的結晶粒 者。另一方面,若以超過2 00 °C的溫度停止急速冷卻,則 其後由於在該高溫狀態的放置,有結晶粒會徐徐成長之虞 〇 又,由本發明的製造方法所製造的純銅板之特徵爲: 以EBSD法所測定的特殊粒界的全特殊粒界長度La對結晶 粒界的全粒界長度L之比率(La/L)爲55 %以上。 由於此特殊粒界的頻率爲高到55%以上,而提高結晶-8- 201139706 In order to stop grain growth and to rapidly cool under certain conditions, a pure copper plate having a finer metal structure having a high specific grain boundary ratio can be produced. The method for producing a pure copper plate of the present invention is characterized by: The ingot of pure copper having a purity of 99.96 wt% or more is heated to 550 ° C to 80 (TC, the total rolling ratio is 85% or more, the temperature at the end of rolling is 500 to 700 t, and the rolling is performed once per pass (one pass The reduction ratio of 5 to 24% of the finishing heat is one-pass or more hot-rolling processing, and is characterized by: 200 ° C to l ° ° C / as needed The cooling rate of min is rapidly cooled from the temperature at the end of the rolling to a temperature of 200 ° C or lower. In order to obtain fine crystal grains, the formation of a twin crystal structure is promoted by partial recrystallization, and the grain boundary is improved. The ratio of the structure of the ratio is the temperature at which the finishing heat is rolled in the end step of the hot rolling (hereinafter referred to as the rolling end temperature), and the rolling reduction rate per one pass of the finishing heat rolling. Inter-calendering, when the calendering end temperature is not At 5 00 ° C, or when the reduction rate per pass is less than 5%, partial recrystallization is not sufficient, and when the calendering end temperature exceeds 70 (TC, or reduction rate per pass) When it is 25% or more, the dynamic recrystallization system in the calendering between the heat and the heat becomes a dominant factor, and it is difficult to obtain a high specific grain boundary ratio with the formation of the twin crystal structure due to partial recrystallization. The calendering end temperature is 500 to 7 〇〇 ° C, and the hot intercalation starting temperature can be 550 to 800 ° C. Further, the total calendering rate due to the intercalation calendering is preferably 85 % or more, due to the total rolling ratio. 85% or more can suppress the coarsening of the crystal grain size and reduce the variation of the particle diameter. If the total rolling rate is less than 85 %, the crystal grain size tends to be -9 - 201139706, and the grain The deviation of the diameter is increased. In addition, the formation ratio of the twin crystal structure is promoted by the rolling reduction ratio of the hot rolling between 5 and 24%, and the specific grain boundary ratio is increased. The organization improves the integration of the crystal grain boundaries, and the crystal structure becomes fine and uniform. Calendering between heat and heat, as long as it is in the range of 5 00 to 7 00 ° C, the reduction ratio per pass is 5 to 24%, and at least one pass of rolling can be performed, but it is also possible to continue the plurality of passes. In particular, the rolling process can be further promoted by repeating rolling in a plurality of passes. The pure copper plate thus produced is effective for use in a sputtering target, an anode for plating, a heat dissipation substrate, and the like. Further, after such heat-to-heat rolling is completed, it can be rapidly cooled to a temperature of 20 (TC or lower) at a cooling rate of 200 to 1 000 ° C / min. When the cooling rate is less than 200 ° C / min, there is a lack of suppression. The effect of growth of crystal grains, even if it exceeds 1 000 °C/min, does not contribute to the above-mentioned grain growth inhibition effect. A more preferable cooling rate is in the range of 300 to 600 ° C / min. When cooling is performed at a cooling rate of such a range up to 20 (temperatures below TC), the growth of crystal grains can be stopped, and fine crystal grains can be obtained. On the other hand, rapid cooling is stopped at a temperature exceeding 200 °C. Then, since the crystal grains are gradually grown due to the high temperature state, the pure copper plate produced by the production method of the present invention is characterized by: a special grain of a special grain boundary measured by the EBSD method. The ratio of the boundary length La to the total grain boundary length L (La/L) of the grain boundary is 55 % or more. Since the frequency of this special grain boundary is as high as 55% or more, the crystallization is improved.
S -10- 201139706 粒界的整合性,濺鍍靶的濺鍍特性、在鍍敷用陽極的溶解 性及板材的變形特性等之各種特性係變良好。 本發明的純銅板係適用於濺鍍用靶。 特別地,由於藉由部分地再結晶化以形成雙晶組織, 而具有高特殊粒界比率,故即使在高輸出下的濺鍍中,也 可抑制異常放電的發生。 發明的效果 若依照本發明,可製造一種純銅板,其具有微細且均 勻的結晶粒,適用於製造即使在高輸出下也不易發生異常 放電的濺鍍用銅靶素材或發揮均勻溶解性的鍍敷用陽極素 材等。 【實施方式】 實施發明的形態 以下說明本發明的實施形態。 此實施形態的純銀板係銅純度爲99.96wt%以上的無氧 銅或99.99wt%以上的電子管用無氧銅。 又’以EBSD法所求得的平均結晶粒徑爲1〇〜200μιη, 較佳爲80μηι,而且以EBSD法所測定的特殊粒界的全特殊 粒界長.度La對結晶粒界的全粒界長度L之比率(Lct/L)爲 55%以上。 又’若粒徑超過200μηι的大結晶粒混入,則切削加工 中在表面容易發生微細的擠裂。此擠裂係如第1圖中所示 -11 - 201139706 ,以銑刀等切削素材時,在其切削方向(箭號A所示的方 向)所發生的切削痕W之中,於與切削方向正交的方向中 發生如符號C所示之筋狀的微細凹凸。若發生此擠裂,則 會損害商品外觀。 使平均結晶粒徑成爲未達1 Ομηι者係不符現實,導致製 造成本的增加。 又,藉由使特殊粒界的長度比率成爲55%以上,而提 高結晶粒界的整合性,有效於濺鑛靶、鍍敷用陽極、散熱 基板等的用途。 結晶粒界係二次元截面觀察的結果,定義爲相鄰2個 結晶間之配向成爲1 5 °以上時的該結晶間之邊界。特殊粒 界係結晶學上以 CSL理論(1<:1'0115616131.:7^3118.1^61 Soc. ΑΙΜΕ,185,501 (1 949))爲基礎所定義的Σ値爲具有 3 $ Σ客29的結晶粒界(對應粒界),定義爲該粒界的固有 對應部位晶格方位缺陷Dq滿足〇9$15°/11/2(0,0· Brandon : Acta. Metallurgica. Vol. 14,P1479,1966)之結 晶粒界。 於全部的結晶粒界之中,此特殊粒界的長度比率若高 ,則結晶粒界的整合性升高,可提商作爲純銅板之用途廣 泛已知的濺鍍靶或鍍敷用陽極、或散熱基板等之特性。 即,於濺鍍靶中.,濺鍍時的異常放電特性與結晶組織 之間係有關係,藉由素材的高純度化,即雜質含量的減低 (特開 2002- 1 293 1 3 )、粒徑的均質性(W003/046250 )、 組織的結晶配向性之控制(特開平1 0-330923 )等,而在S -10- 201139706 The integration of the grain boundary, various characteristics such as the sputtering characteristics of the sputtering target, the solubility of the plating anode, and the deformation characteristics of the plate material are improved. The pure copper plate of the present invention is suitable for use in a target for sputtering. In particular, since it is partially recrystallized to form a twin structure, and has a high specific grain boundary ratio, even in the sputtering at a high output, the occurrence of abnormal discharge can be suppressed. Advantageous Effects of Invention According to the present invention, it is possible to produce a pure copper plate having fine and uniform crystal grains, which is suitable for producing a copper target material for sputtering which is less likely to cause abnormal discharge even at a high output or plating which exhibits uniform solubility. Apply anode material, etc. [Embodiment] Mode for Carrying Out the Invention Hereinafter, an embodiment of the present invention will be described. The pure silver plate of this embodiment is copper-free copper having a purity of 99.96 wt% or more, or oxygen-free copper for an electron tube of 99.99 wt% or more. Further, the average crystal grain size obtained by the EBSD method is 1 〇 to 200 μmη, preferably 80 μηι, and the total grain boundary length of the special grain boundary determined by the EBSD method is La to the whole grain of the grain grain boundary. The ratio of the length L of the boundary (Lct/L) is 55% or more. Further, when large crystal grains having a particle diameter of more than 200 μm are mixed, fine cracking tends to occur on the surface during cutting. This squeezing system is as shown in Fig. -11 - 201139706. When cutting materials such as a milling cutter, the cutting marks W occurring in the cutting direction (the direction indicated by the arrow A) are in the cutting direction. In the orthogonal direction, the rib-like fine unevenness as shown by the symbol C occurs. If this cracking occurs, it will damage the appearance of the product. It is not realistic to make the average crystal grain size less than 1 Ομηι, resulting in an increase in the production cost. In addition, the ratio of the length of the special grain boundary is 55% or more, thereby improving the integration of the crystal grain boundary, and is effective for applications such as a sputtering target, an anode for plating, and a heat dissipation substrate. The result of observation of the cross section of the grain boundary of the crystal grain boundary is defined as the boundary between the crystals when the alignment between two adjacent crystals is 15 or more. The crystallographic system of the special grain boundary is defined by the CSL theory (1<:1'0115616131.:7^3118.1^61 Soc. ΑΙΜΕ, 185, 501 (1 949)) as having 3 $ 2929 The crystal grain boundary (corresponding to the grain boundary) is defined as the inherent orientation of the grain boundary. The lattice orientation defect Dq satisfies 〇9$15°/11/2 (0,0· Brandon: Acta. Metallurgica. Vol. 14, P1479, Crystal grain boundary of 1966). Among all the crystal grain boundaries, if the length ratio of the special grain boundary is high, the integration of the crystal grain boundaries is increased, and the sputtering target or the plating anode widely used as a pure copper plate can be extracted. Or characteristics of a heat sink substrate, etc. In other words, in the sputtering target, the abnormal discharge characteristics at the time of sputtering are related to the crystal structure, and the purity of the material is reduced, that is, the impurity content is reduced (JP-2002- 293 1 3), The homogeneity of the diameter (W003/046250), the control of the crystal orientation of the structure (Special Kaiping 1 0-330923), etc.
S -12- 201139706 濺鏟特性之中顯示抑制異常放電之手段。然而近年來爲了 提高生產性,要求濺鑛速率的進一步提高,濺鏟電壓朝向 高電壓化。若濺鍍電壓升高,則成爲濺鍍時的異常放電更 容易發生的環境’故僅藉由以往的組織控制手法,異常放 電抑止效果係不充分,而要求進一步的組織控制。 又’純銅製的鍍敷用陽極材係特別用於印刷配線板的 貫通孔鍍敷等’但在陽極溶解時發生電流密度分布的不均 ’而引起局部的導通不良,結果發生不溶性的黏渣(slime )’與鍍敷不良或生產效率的降低有關聯。作爲對策,提 高陽極的溶解面之面內溶解均質性者係有效,採取結晶粒 之微細化的對策。然而,一般而言粒界係比粒內容易溶解 ,即使藉由微細化來提高陽極的面內溶解均質性,也無法 避免粒界選擇地溶解,得知微細化效果係有限度。因此, 判斷抑制粒界本身的溶解性者,對於前述黏渣的發生係有 效,然而以往並沒有對如此的觀點進行檢討。 再者’於散熱基板中,由於在使用時重複膨脹收縮, 故重要的是具有均一的變形特性,而且疲勞特性優異。近 年來,於隨著節能化、低CO化的潮流而進行普及的混合動 力車或太陽能電池等中,直·交流反相電路係不可欠缺, 爲了散逸變換時所產生的熱,使用純銅或低合金銅板當作 散熱基板。聆此等用途中,由於系統的大型化而往大電流 化進展,對散熱基板所施加的熱負荷係有增大的傾向。散 熱基板由於在使用中經常重複地熱膨脹/收縮,故要求長 期的耐熱疲勞特性。關於耐熱疲勞特性,組織的均質性係 -13- 201139706 重要,但以往僅提高組織的均勻性,係難以改善前述大電 流化所伴隨的疲勞特性。 此等問題係可藉由使結晶粒界的特殊粒界之長度比率 成爲55%以上而解決。即,於濺鍍靶中,由於在濺鍍面全 體上均勻地濺鍍,故成爲異常放電的原因之結晶粒界的階 梯差係不易發生,結果減低異常放電的次數。關於鍍敷用 陽極,判斷特殊粒界係具有比一般粒界還接近粒內的溶解 特性之性質,藉由使用已提高特殊粒界比率的銅板,由於 陽極溶解時的面內溶解均質性係明顯提高,將溶解面保持 平滑,故可抑制不溶性的黏渣之發生,所形成的鍍敷膜之 品質升高。又,於散熱用途基板材料中,顯示均一的變形 特性,即使重複的熱膨脹/收縮,也不易發生金屬疲勞, 而改善疲勞特性。 如此地藉由使特殊粒界的長度比率成爲5 5 %以上,而 改善濺鍍靶的濺鍍特性、鍍敷用陽極素材的溶解性、其它 作爲銅板的變形特性等之各種特性,有效於濺鍍靶、鍍敷 用陽極、散熱基板等的用途。 其次說明製造如此的純銅板之方法。 此製造方法係將純銅的鑄錠熱間壓延,使該熱間壓延 道次滿足指定條件的精壓而結束後,視需要進行急速冷卻 的單純製程。 具體地,將純銅的鑄錠加熱到5 5 0 °C〜8 0 0 °C,一邊使 其複數次地在壓延輥之間往復行進,一邊徐徐地減小壓延 輥間的間隙,壓延到指定的厚度爲止。此複數次的壓延所S -12- 201139706 The splash shovel feature shows the means to suppress abnormal discharge. However, in recent years, in order to improve productivity, it is required to further increase the sputtering rate, and the shovel voltage is directed toward a high voltage. When the sputtering voltage is increased, the abnormal discharge is more likely to occur during sputtering. Therefore, only the conventional tissue control method is insufficient, and the abnormal discharge suppressing effect is insufficient, and further tissue control is required. In addition, the anode material for plating made of pure copper is used for the through-hole plating of a printed wiring board, etc., but the unevenness of the current density distribution occurs when the anode is dissolved, causing local conduction failure, resulting in insoluble slag. (slime)' is associated with poor plating or reduced production efficiency. As a countermeasure, it is effective to improve the in-plane solubility homogeneity of the dissolution surface of the anode, and to take measures to refine the crystal grains. However, in general, the grain boundary system is more soluble than the inside of the grain, and even if the in-plane dissolution homogeneity of the anode is improved by miniaturization, the grain boundary cannot be selectively dissolved, and the effect of miniaturization is limited. Therefore, it is judged that the solubility of the grain boundary itself is suppressed, and the occurrence of the above-mentioned slag is effective. However, such a viewpoint has not been reviewed in the past. Further, in the heat-dissipating substrate, since expansion and contraction are repeated at the time of use, it is important to have uniform deformation characteristics and excellent fatigue characteristics. In recent years, in hybrid vehicles or solar cells that have been popularized with the trend of energy saving and low CO, straight-and-AC inverter circuits are indispensable, and in order to dissipate heat generated during conversion, pure copper or low is used. The alloy copper plate serves as a heat sink substrate. In such applications, the current has increased due to the increase in size of the system, and the thermal load applied to the heat-dissipating substrate tends to increase. The heat-dissipating substrate requires long-term thermal fatigue resistance because it is often repeatedly thermally expanded/contracted during use. Regarding the thermal fatigue resistance, the homogeneity of the structure is important. However, in the past, only the uniformity of the structure was improved, and it was difficult to improve the fatigue characteristics accompanying the above-described large current. These problems can be solved by making the ratio of the length of the special grain boundary of the crystal grain boundary to 55% or more. In other words, in the sputtering target, since the sputtering surface is uniformly sputtered uniformly, the step of the crystal grain boundary which is a cause of abnormal discharge is less likely to occur, and as a result, the number of abnormal discharges is reduced. Regarding the anode for plating, it is judged that the special grain boundary system has a property closer to the solubility characteristic in the grain than the general grain boundary, and by using a copper plate having a higher grain boundary ratio, the in-plane dissolution homogeneity at the time of anodic dissolution is remarkable. The improvement is to keep the dissolved surface smooth, so that the occurrence of insoluble slag can be suppressed, and the quality of the formed plating film is increased. Further, in the substrate material for heat dissipation use, uniform deformation characteristics are exhibited, and even if repeated thermal expansion/contraction occurs, metal fatigue is less likely to occur, and fatigue characteristics are improved. By setting the length ratio of the special grain boundary to 55 % or more, the sputtering characteristics of the sputtering target, the solubility of the anode material for plating, and other characteristics such as deformation characteristics of the copper plate are improved, and the sputtering is effective. Applications such as plating targets, anodes for plating, and heat dissipation substrates. Next, a method of manufacturing such a pure copper plate will be described. This manufacturing method is a simple process in which the ingot of pure copper is heat-calendered, and the hot-rolling pass is subjected to the refining pressure of the specified condition, and then rapidly cooled as needed. Specifically, the ingot of pure copper is heated to 550 ° C to 80 ° C, and the gap between the calender rolls is gradually reduced and rolled to a designated number while repeatedly reciprocating between the calender rolls. The thickness is up. This multiple calendering station
S • 14 - 201139706 致的總壓延率爲85%以上’熱間壓延的結束步驟之精整熱 間壓延的壓延結束溫度爲500〜700 °C ’前述精整熱間壓延 中的每1道次之壓下率爲5〜24% ’進行1道次或複數道次連 續地壓.延加工。然後’按照需要’以2〇〇〜1 000T:/min的冷 卻速度進行急速冷卻,而由壓延結束溫度起到成爲200°C 以下的溫度爲止。 通常的純銅板之製造方法一般爲熱間壓延=>冷卻二冷 間壓延=> 熱處理之製程,該情況的熱間壓延係以8 50〜 9 0 0 °C的高溫進行加工。若在如此高溫狀態下進行熱間壓 延,由於結晶粒係粗大化,即使將其急速冷卻,也無法將 平均結晶粒徑微細化到80μπι以下。 於本實施形態的製造方法中,熱間壓延係開始溫度爲 5 5 0〜800°C,結束溫度爲5 00〜700°C之比較低溫的狀態》 熱間壓延的結束溫度若超過700°C,則結晶粒係急劇變大 ,其後即使急速冷卻也難以得到微細的結晶粒。又,即使 熱間壓延結束溫度未達500°C,結晶粒徑的微細化效果也 飽和,即使將溫度降低到其以下,也無助於微細化。因此 ’壓延結束溫度爲500〜700 °C。而且,由於此熱間壓延的 結束溫度爲500〜70(TC,故熱間壓延的開始溫度爲5 50〜 8 00°C ° 又’此熱間輯延所致的總壓延率宜爲8 5 %以上,藉由 使總壓延率成爲8 5 %以上,可抑制結晶粒徑的粗大化,同 時可減小其偏差。總壓延率若未達8 5 %,則結晶粒有變大 的傾向’同時其偏差變大。此時,於複數次的壓延之中, -15- 201139706 關於最終階段的壓延之精整熱間壓延,更佳爲使每1道次 的壓下率成爲5〜24%,進行1道次或複數道次連續地壓延 加工。藉由在熱間壓延的最後階段,使每1道次的壓下率 成爲5〜24%,可使雙晶組織的比率增大,使結晶粒界的特 殊粒界之長度比率成爲55%以上。此每1道次的壓下率係通 過壓延後的母材之板厚相對於通過壓延輥前的母材之板厚 而言的減少率(或這一道次的壓延輥間之間隙相對於上一 道次時的壓延輥間之間隙的減少率),總壓延率係壓延結 束後的母材相對於壓延前的母材之板厚減少率。即,若以 通過壓延輥前的母材之板厚爲to,以通過壓延輥後的母材 之板厚爲h,則每1道次的壓下率γ ( % )係可定義爲( (to-t, ) /t〇 ) xl 00 ( % )。 而且,於如此的熱間壓延結束後,更藉由以200〜 1 000°C/min的冷卻速度之水冷,進行急速冷卻直到成爲 2 00 °C以下的溫度,可抑制熱間壓延後的粒徑之粗大化。 冷卻速度未達200°C/min時,缺乏抑制結晶粒的成長之效果 ,而即使超過1000 °C/min,也無助於其以上的微細化。 若以如此範圍的冷卻速度進行冷卻直到200°C以下的 溫度爲止,則停止結晶粒的成長,可得到微細的結晶粒者 。若在超過2 00°C的溫度停止急速冷卻,則其後由於在高 溫狀態下放置而有結晶粒徐徐成長之虞。 實施例 其次說明本發明的實施例。S • 14 - 201139706 The total rolling rate is more than 85%. 'The end of the hot rolling is the end of the calendering. The calendering end temperature is 500~700 °C. 'The above-mentioned finishing heat rolling is performed every 1 pass. The reduction ratio is 5 to 24%. The continuous processing is performed by one pass or multiple passes. Then, 'as needed', rapid cooling is performed at a cooling rate of 2 Torr to 1 000 T:/min, and the rolling end temperature is set to a temperature of 200 ° C or lower. The usual method for producing a pure copper plate is generally hot rolling = > cooling two cold rolling = > heat treatment process, and the inter-heat rolling is processed at a high temperature of 8 50 to 900 ° C. When the inter-heat rolling is performed at such a high temperature, the crystal grain size is coarsened, and even if it is rapidly cooled, the average crystal grain size cannot be made finer to 80 μm or less. In the production method of the present embodiment, the inter-heat rolling starting temperature is 50,000 to 800 ° C, and the end temperature is in a relatively low temperature state of 500 to 700 ° C. If the end temperature of the inter-heat rolling exceeds 700 ° C Then, the crystal grain size rapidly increases, and it is difficult to obtain fine crystal grains even after rapid cooling. Further, even if the heat-to-heat rolling end temperature 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. Therefore, the calendering end temperature is 500 to 700 °C. Moreover, since the end temperature of the inter-heat rolling is 500 to 70 (TC, the starting temperature of the inter-heat rolling is 5 50 to 800 ° C ° and the total calendering rate due to the thermal interval is preferably 8 5 When the total rolling ratio is 85% or more, the coarsening of the crystal grain size can be suppressed and the variation can be reduced. If the total rolling ratio is less than 85%, the crystal grains tend to become larger. At the same time, the deviation becomes larger. At this time, among the plurality of calenderings, -15-201139706 is about the final stage of calendering, and the calendering rate is preferably 5 to 24% per one pass. Performing one or more passes in a continuous rolling process. By reducing the rolling ratio per pass to 5 to 24% in the final stage of the hot rolling, the ratio of the twin structure can be increased. The ratio of the length of the special grain boundary of the crystal grain boundary is 55% or more. The reduction ratio per pass is the rate of decrease in the thickness of the base material after rolling relative to the thickness of the base material before passing through the calender roll. (or the rate of decrease in the gap between the calender rolls in this pass relative to the gap between the calender rolls in the previous pass), The rate of decrease of the thickness of the base material after the end of rolling is compared with the thickness of the base material before rolling, that is, the thickness of the base material after passing through the calender roll is to, and the thickness of the base material after passing through the calender roll For h, the reduction ratio γ (%) per pass can be defined as ((to-t, ) /t〇) xl 00 ( % ). Moreover, after such heat-to-heat rolling is finished, It is rapidly cooled by water cooling at a cooling rate of 200 to 1 000 ° C / min until it reaches a temperature of 200 ° C or lower, which suppresses coarsening of the particle diameter after hot rolling. The cooling rate is less than 200 ° C / In the case of 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. If cooling is performed at a cooling rate of such a range up to a temperature of 200 ° C or lower, then When the growth of the crystal grains is stopped, fine crystal grains can be obtained. If the rapid cooling is stopped at a temperature exceeding 200 ° C, the crystal grains gradually grow after being placed in a high temperature state. Embodiments of the invention.
S -16 · 201139706 壓延素材係用電子管用無氧銅(純度99.99wt%以上) 的鑄銳。壓延前的素材尺寸爲寬度650mmx長度900mmx厚 度2 90mm,如表1中所示地複數組合熱間壓延及其後的冷 卻之各條件,以製作純銅板。又,溫度測定係使用輻射式 溫度計,測定壓延板的表面溫度而進行。 [表1] 熱間壓延 冷卻 開始溫度 °C 結束溫度 °C 總壓延率 % 精壓 道次 速度 〇C/min 到達溫度 °C 實 施 例 1 562 553 92 1596x3道次 209 181 2 592 583 88 10!ίχ1道次 680 193 3 616 590 92 20%χ4道次 261 185 4 637 614 92 20ϋχ3道次 472 170 5 667 634 92 10%χ3道次 940 175 6 703 654 92 24%χ2道次 236 199 7 707 664 88 15知3道次 254 192 8 713 669 92 15?ίχ3道次 254 187 9 720 676 92 20%χ2道次 516 180 10 732 691 88 5«χ3道次 264 192 11 591 534 90 18%χ5道次 無急速冷卻 12 663 621 94 20%χ2道次 無急速冷卻 13 753 635 86 1054x3道次 無急速冷卻 14 588 503 88 2256x2道次 無急速冷卻 15 728 683 96 8ίίχ2道次 無急速冷卻 16 662 621 92 16%χ4道次 無急速冷卻 17 575 538 92 mxi道次 無急速冷卻 18 559 521 92 15%x3道次 無急速冷卻 比 較 例 1 510 490 2 620 600 83 1514x2道次 528 210 3 720 661 92 1554x1道次 126 220 4 720 689 83 3054x1道次 690 180 5 820 732 83 25化2道次 281 180 6 848 760 92 20%x3道次 146 180 7 920 818 83 305U3道次 255 220 於此表1中,比較例1雖然在壓延開始溫度爲5 1 0°C ( 結束預料溫度490°C )開始壓延,但由於溫度過低,變成 過負荷狀態,而中止壓延的繼續進行。 因此,對於此比較例1以外的純銅板,測定平均結晶 -17- I:; 201139706 粒徑、特殊粒界長度比率、切削時的擠裂狀態、作爲濺鍍 靶用時的異常放電次數、作爲鍍敷陽極用時的黏渣發生量 <平均結晶粒徑、特殊粒界長度比率> 對於各試料’使用耐水硏磨紙、鑽石磨粒,進行機械 硏磨後,使用膠態矽石溶液,進行精整硏磨。 然後’藉由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),鑑定結 晶粒界、特殊粒界,算出其長度,進行平均結晶粒徑及特 殊粒界長度比率之解析。 首先’使用掃描型電子顯微鏡,對試料表面的測定範 圍內之各個測定點(畫素),照射電子射線,藉由反向散 射電子射線繞射的方位解析、,將鄰接的測定點間之方位差 成爲1 5°以上的測定點間當作結晶粒界。 平均結晶粒徑(雙晶亦當作結晶粒計數)的測定係由 所得之結晶粒界中,算出觀察範圍內的結晶粒子數,將範 圍面積除法結晶粒子數而算出結晶粒子面積,將其換算爲 圓,而成爲平均結晶粒徑(直徑)。 又’測定該測定範圍中的結晶粒界之全粒界長度L, 決定鄰接的結晶粒之界面構成特殊粒界的結晶粒界之位置 ’同時求得特殊粒界的全特殊粒界長度La與上述所測定的 結晶粒界之全粒界長度L之粒界長度比率Lcy/L,當作特殊 -18- 201139706 粒界長度比率》 <擠裂狀態> 使各試料成爲1 00 x 200 0mm的平板,對其表面,使用 銑床的超硬刀尖之刀頭,以切入深度0.1mm、切削速度 5000m/分鐘進行切削加工,在其切削表面的500μιη四方之 視野內,調查長度100μιη以上的擠裂瑕疵有幾個存在。 <濺鍍異常放電次數> 由各試料製作含有背板部分的一體型靶,以使得靶部 分成爲直徑152 mm、厚度6 mm,將該靶安裝於濺鍍裝置, 使室內的到達真空壓力成爲lxl (T5Pa以下,使用Ar作爲濺 鍍氣體,濺鑛氣體壓力爲〇.3Pa,以直流(DC)電源在濺 鍍輸出2kW的條件下實施濺鍍試驗。濺鍍係連續2小時。 其間使用附屬於電源的電弧計數器,計數由於濺鍍異常所 發生的異常放電之次數。 <陽極黏渣發生量> 將已切成直徑270mm的圓盤狀之銅板固定於電極支架 (執行電極面積約53 0cm2 )當作陽極電極,將直徑200mm 的矽晶圓當作陰極,於以下的條件下進行銅鍍敷,測定自 鍍敷開始起到處理第5片的晶圓之際所產生的不溶性黏渣 發生量。再者’黏渣係在回收後,於使乾燥後進行重量測 定。 -19- 201139706 鍍敷液:在離子交換水中,添加70g/l的焦磷酸銅、 3 00g/l焦磷酸鉀,用氨水調整至ρΗ8·5者, 鍍敷條件:在液溫50°C,藉由空氣攪拌及陰極搖動而 實施攪拌, 陰極電流密度:3A/dm2, 鍍敷時間:1小時/片。 表2中顯示此等的結果。 [表2] 平均結晶 粒徑 fi m 特贿界 長度比率 % 評價 表面狀璁 擠裂個數 異常放電次數 次 黏渣發生量 mg 實 施 例 1 58 78 1 3 4 2 63 63 2 2 5 3 60 65 2 2 6 4 55 60 2 3 5 5 60 73 1 2 7 6 56 58 1 3 5 7 71 74 0 1 4 8 70 70 0 1 4 9 66 68 0 2 4 10 73 56 0 2 6 11 102 60 2 3 3 12 123 56 2 2 5 13 145 72 2 5 6 14 85 58 1 3 4 15 196 73 3 4 5 16 166 71 3 3 5 17 9β1 60 2 6 6 18 92 68 2 4 3 比 較 例 1 一 一 一 一 - 2 95 45 5 21 16 3 136 43 4 34 15 4 90 47 5 16 20 5 88 50 5 13 12 6 157 53 5 11 13. 7 168 48 6 18 18 如由此表2可明知,以本實施例的製造方法所製造的 純銅板,係平均結晶粒徑爲1 0〜200Mm ’尤其在精壓後進 行急速冷卻的實施例1〜10中爲10〜80μπι,而且實施例皆 -20-S -16 · 201139706 The material used for the rolling is an oxygen-free copper (purity of 99.99 wt% or more). The material size before calendering was 650 mm x width 900 mm x thickness 2 90 mm, and various conditions such as heat rolling and subsequent cooling were combined as shown in Table 1 to prepare a pure copper plate. Further, the temperature measurement was carried out by measuring the surface temperature of the rolled plate using a radiant thermometer. [Table 1] Inter-calender rolling cooling start temperature °C End temperature °C Total rolling rate % Separation speed sub-speed 〇C/min Arrival temperature °C Example 1 562 553 92 1596x3 pass 209 181 2 592 583 88 10! Χ1 680 193 3 616 590 92 20 20% χ 4 261 185 4 637 614 92 20 ϋχ 3 passes 472 170 5 667 634 92 10% χ 3 passes 940 175 6 703 654 92 24% χ 2 passes 236 199 7 707 664 88 15知三道次254 192 8 713 669 92 15?ίχ3 passes 254 187 9 720 676 92 20%χ2 passes 516 180 10 732 691 88 5«χ3 passes 264 192 11 591 534 90 18%χ5 passes No rapid cooling 12 663 621 94 20% χ 2 passes no rapid cooling 13 753 635 86 1054x3 pass no rapid cooling 14 588 503 88 2256x2 pass no rapid cooling 15 728 683 96 8 ίίχ 2 passes without rapid cooling 16 662 621 92 16 %χ4 passes no rapid cooling 17 575 538 92 mxi pass no rapid cooling 18 559 521 92 15%x3 pass no rapid cooling comparison example 1 510 490 2 620 600 83 1514x2 pass 528 210 3 720 661 92 1554x1 pass 126 220 4 720 689 83 3054x1 pass 690 180 5 820 732 83 25 rounds 2 passes 281 180 6 848 760 92 20%x3 passes 146 180 7 920 818 83 305U3 pass 255 220 In Table 1, Comparative Example 1 has a rolling start temperature of 5 1 0 ° C (end expected temperature 490 ° C) The rolling is started, but since the temperature is too low, it becomes an overload state, and the calendering is continued. Therefore, for the pure copper plate other than Comparative Example 1, the average crystal -17-I:; 201139706 particle size, the specific grain boundary length ratio, the cracking state at the time of cutting, and the number of abnormal discharges when used as a sputtering target were measured. The amount of slag generated when plating an anode <average crystal grain size, special grain boundary length ratio> For each sample 'using water honing paper and diamond abrasive grains, after mechanical honing, a colloidal vermiculite solution is used. , finishing the honing. 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.) were used to identify 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. First, using a scanning electron microscope, each measurement point (pixel) in the measurement range of the surface of the sample is irradiated with an electron beam, and the orientation of the adjacent measurement points is determined by the azimuth analysis of the backscattered electron beam diffraction. The measurement point between the difference of 15 or more is regarded as a crystal grain boundary. In the measurement of the average crystal grain size (the twin crystal is also used as the crystal grain count), the number of crystal particles in the observation range is calculated from the obtained crystal grain boundaries, and the crystal particle area is calculated by dividing the number of crystal particles in the range area, and the conversion is performed. It is a circle and becomes an average crystal grain size (diameter). Further, 'the total grain boundary length L of the crystal grain boundary in the measurement range is determined, and the position of the crystal grain boundary of the special grain boundary is determined by the interface of the adjacent crystal grain', and the full special grain boundary length La of the special grain boundary is obtained. The grain boundary length ratio Lcy/L of the total grain boundary length L of the above-mentioned measured grain boundary is regarded as the special -18-201139706 grain boundary length ratio. <Squeezing state> Each sample is made to be 100 00 200 mm The flat plate is made of a super-hard cutting tip of a milling machine, and is cut at a depth of 0.1 mm and a cutting speed of 5000 m/min. In the 500 μm square of the cutting surface, the length of 100 μm or more is investigated. There are several existences of cracks. <Number of sputter abnormal discharges> An integrated target including a backing plate portion was prepared from each sample so that the target portion had a diameter of 152 mm and a thickness of 6 mm, and the target was attached to a sputtering apparatus to allow the chamber to reach a vacuum pressure. Became lxl (below T5Pa, use Ar as the sputtering gas, the sputtering gas pressure is 〇.3Pa, and perform the sputtering test with a direct current (DC) power supply at a sputtering output of 2kW. The sputtering system is continuous for 2 hours. The arc counter attached to the power source counts the number of abnormal discharges due to abnormal sputtering. <Anode slag generation amount> A disk-shaped copper plate cut into a diameter of 270 mm is fixed to the electrode holder (the electrode area is approximately 53 0cm2 ) As an anode electrode, a 200mm diameter silicon wafer was used as a cathode, and copper plating was performed under the following conditions to measure the insoluble viscosity generated from the start of plating to the processing of the fifth wafer. The amount of slag is generated. In addition, the viscous slag is recovered and the weight is measured after drying. -19- 201139706 Plating solution: 70 g/l of copper pyrophosphate and 300 g/l pyrophosphoric acid are added to the ion exchange water. Potassium, use The ammonia water was adjusted to ρΗ8·5, plating conditions: stirring was carried out at a liquid temperature of 50 ° C by air stirring and cathode shaking, cathode current density: 3 A/dm 2 , plating time: 1 hour / piece. The results are shown. [Table 2] Average crystal grain size fi m Special bribe length ratio % Evaluation Surface 璁 璁 个 异常 异常 异常 异常 异常 异常 异常 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 58 58 58 58 58 58 58 58 2 2 5 3 60 65 2 2 6 4 55 60 2 3 5 5 60 73 1 2 7 6 56 58 1 3 5 7 71 74 0 1 4 8 70 70 0 1 4 9 66 68 0 2 4 10 73 56 0 2 6 11 102 60 2 3 3 12 123 56 2 2 5 13 145 72 2 5 6 14 85 58 1 3 4 15 196 73 3 4 5 16 166 71 3 3 5 17 9β1 60 2 6 6 18 92 68 2 4 3 Compare Example 1 1111 - 2 95 45 5 21 16 3 136 43 4 34 15 4 90 47 5 16 20 5 88 50 5 13 12 6 157 53 5 11 13. 7 168 48 6 18 18 It is known that the pure copper plate produced by the production method of the present embodiment has an average crystal grain size of 10 to 200 Mm. In particular, in Examples 1 to 10 in which rapid cooling is performed after the coining, it is 10 to 80 μm, and the examples are -20-
S 201139706 特殊粒界長度比率爲5 5 %以上。相對於此,比較例的純銅 板係特殊粒界長度比率未達55%。由該結果可知,實施例 中的熱間壓延時之精壓爲5〜24%的壓下率者,係在濺鍍靶 特性評價中,濺鍍時的異常放電次數少,在鍍敷用陽極溶 解特性評價中,不溶性黏渣的發生量少。 以上雖然說明本發明之實施形態,惟本發明不受此記 載所限定,在不脫離本發明之技術思想的範圍內可適宜變 更。 例如,於熱間壓延的精壓道次排程(schedule )中, 在進行複數次的道次之際,雖然壓下率爲固定,但不受此 所拘束,只要每1道次爲5〜24%的壓下率,則每壓延道次 的壓下率亦可相異。 又,於得到高的特殊粒界比率之方面,雖然在精壓道 次結束後,不必要進行快速的冷卻,但由於在提高鑄錠內 部與表面的組織均質性之方面具有效果,故宜實施快速的 冷卻。 另外’本發明係在指定的條件下熱間壓延後,急速冷 卻至200°C以下爲止,其後不施予冷間壓延而成爲純銅板 的製品,但作爲急速冷卻後的最終精整,不妨可以冷間進 行稍微的(數%以下的壓延率之)壓延。 產業上的利用可能性 本發明的純銅板係可適用於濺鍍用靶或鍍敷用陽極、 靶用背板’此外亦可適用於模具、放電電極、散熱板、散 -21 - 201139706 熱器、模型、水冷板、電極、電用端子、匯流排、墊片、 凸緣、印刷版等。 【圖式簡單說明】 第1圖係將純銅板的表面切削時所產生的擠裂之顯微 鏡照片。 【主要元件符號說明】 w :切削痕 c:擠裂瑕疵 -22-S 201139706 Special grain boundary length ratio is more than 5 5 %. On the other hand, the pure copper plate of the comparative example had a specific grain boundary length ratio of less than 55%. From the results, it is understood that in the examples, the reduction in the hot pressing pressure is 5 to 24%, and in the evaluation of the sputtering target characteristics, the number of abnormal discharges during sputtering is small, and the anode for plating is used. In the evaluation of the dissolution characteristics, the amount of insoluble slag generated was small. The embodiments of the present invention are described above, but the present invention is not limited to the scope of the invention, and may be modified as appropriate without departing from the scope of the invention. For example, in the schedule of the hot press rolling, in the case of a plurality of passes, although the reduction ratio is fixed, it is not restricted by this, as long as each pass is 5~ With a reduction rate of 24%, the reduction rate per calendering pass can also be different. Further, in terms of obtaining a high specific grain boundary ratio, although it is not necessary to perform rapid cooling after the completion of the coining pass, it is effective in improving the homogeneity of the inside of the ingot and the surface, and therefore it is preferable to implement Fast cooling. In addition, the present invention is a product obtained by rapidly rolling to a temperature of 200 ° C or lower after being subjected to hot rolling under specified conditions, and thereafter is not subjected to cold rolling to obtain a pure copper plate, but may be a final finish after rapid cooling. A slight (calendering rate of several % or less) rolling is performed in the cold room. INDUSTRIAL APPLICABILITY The pure copper plate of the present invention can be applied to a sputtering target, a plating anode, or a target backing plate. Alternatively, it can be applied to a mold, a discharge electrode, a heat dissipation plate, and a heat sink - 201139706 , models, water-cooled plates, electrodes, electrical terminals, bus bars, gaskets, flanges, printing plates, etc. [Simple description of the drawing] Fig. 1 is a photomicrograph of the crack generated when the surface of the pure copper plate is cut. [Main component symbol description] w : Cutting marks c: Crushing 瑕疵 -22-
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