WO2011099427A1 - 純銅板の製造方法及び純銅板 - Google Patents
純銅板の製造方法及び純銅板 Download PDFInfo
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- WO2011099427A1 WO2011099427A1 PCT/JP2011/052318 JP2011052318W WO2011099427A1 WO 2011099427 A1 WO2011099427 A1 WO 2011099427A1 JP 2011052318 W JP2011052318 W JP 2011052318W WO 2011099427 A1 WO2011099427 A1 WO 2011099427A1
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- rolling
- pure copper
- copper plate
- grain boundary
- temperature
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 71
- 239000010949 copper Substances 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 60
- 238000007747 plating Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 238000005477 sputtering target Methods 0.000 claims description 25
- 230000009467 reduction Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 238000005097 cold rolling Methods 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 11
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 55
- 238000005098 hot rolling Methods 0.000 abstract description 26
- 238000004544 sputter deposition Methods 0.000 abstract description 25
- 230000002159 abnormal effect Effects 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000005520 cutting process Methods 0.000 description 11
- 230000017525 heat dissipation Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000010273 cold forging Methods 0.000 description 5
- 238000005242 forging Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 241000237536 Mytilus edulis Species 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 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
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 235000020638 mussel Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000013077 target material 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001879 copper Chemical class 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
- 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
- 238000009826 distribution Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000001771 impaired effect 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the present invention relates to a method for producing a pure copper plate having a good quality, and more particularly, to having a fine crystal structure, a moderate hardness and a high special property by forming a twin crystal structure by partial recrystallization.
- the present invention relates to a method of producing a pure copper plate giving a grain boundary length ratio, and a pure copper plate of a material such as a sputtering target or a plating anode produced by the method.
- Priority is claimed on Japanese Patent Application No. 2010-26453, filed Feb. 9, 2010, the content of which is incorporated herein by reference.
- a pure copper sheet is usually produced by hot rolling or forging a pure copper ingot, cold rolling or cold forging, and then performing heat treatment for strain removal or recrystallization.
- Such a pure copper plate is processed into a desired shape by sawing, cutting, embossing, cold forging, etc. and used, but the crystal grain size is small also to reduce the amount of muffle at the time of processing. Is required.
- the pure copper plate manufactured by the above-mentioned method is used as a sputtering target for wiring materials of a semiconductor element in recent years.
- Al specific resistance: about 3.1 ⁇ ⁇ cm
- copper wiring with a specific resistance of about 1.7 ⁇ ⁇ cm
- copper is often electroplated. Sputter deposition of pure copper is performed as a layer).
- Patent Document 1 As a conventional method for industrially producing such pure copper targets for sputtering, in Patent Document 1, a pure copper ingot having a purity of 99.995 wt% or more is hot-worked and then annealed at a temperature of 900 ° C. or less And then subjected to cold rolling at a reduction ratio of 40% or more, and then recrystallization annealing at a temperature of 500 ° C. or less to have a substantially recrystallized structure and an average grain size of 80 ⁇ m or less There is disclosed a method of obtaining a copper target for sputtering which has a Vickers hardness of 100 or less.
- Patent Document 2 after subjecting a high purity copper ingot of 5N or more to hot working such as hot forging or hot rolling at a working ratio of 50% or more, it is further subjected to cold rolling or cold forging By performing cold working at a working ratio of 30% or more and performing heat treatment at 350 to 500 ° C. for 1 to 2 hours, the contents of Na and K are each 0.1 ppm or less, Fe, Ni, Cr, Al, The content of each of Ca and Mg is 1 ppm or less, the content of each of carbon and oxygen is 5 ppm or less, the content of each of U and Th is 1 ppb or less, and the content of copper excluding gas components is 99.999% or more.
- the average grain size on the sputtering surface is 250 ⁇ m or less, the dispersion of the average grain size is within ⁇ 20%, and the X-ray diffraction intensity ratio I (111) / I (200) is 2.4 or more on the sputtering surface, the dispersion is ⁇ 20 How to obtain the sputtering copper target is within is disclosed.
- Patent Document 3 the surface layer of an ingot made of high purity copper having a purity of 6 N or more and an additive element is removed, and obtained through hot forging, hot rolling, cold rolling, and heat treatment.
- a copper alloy sputtering target containing 0.5 to 4.0 wt% of Al and 0.5 wt ppm or less of Si, and a copper alloy sputtering target containing 0.5 to 4.0 wt% of Sn and Mn of 0.5 wt ppm or less There is disclosed a target and a copper alloy sputtering target containing one or more selected from Sb, Zr, Ti, Cr, Ag, Au, Cd, In, and As in a total amount of 1.0 wt ppm or less.
- the manufactured ingot after removing the surface layer of the manufactured ingot to make ⁇ 160 mm ⁇ thickness 60 mm, it is hot forged at 400 ° C. to make ⁇ 200 mm, and then hot rolled at 400 ° C. to ⁇ 270 mm ⁇ There is a description that it is rolled to a thickness of 20 mm and further cold rolled to a diameter of 360 mm and a thickness of 10 mm and heat treated at 500 ° C. for 1 hour, and then the entire target is quenched to make a target material.
- a pure copper ingot is subjected to hot forging or hot rolling in order to obtain a homogeneous and stable recrystallized structure. After that, cold forging and cold rolling are performed, and heat treatment is further performed.
- the present invention has been made in view of such circumstances, and particularly in the production of a sputtering target material and an anode material for plating, a rolling ratio of 5 to 24 in cold rolling is applied to a hot-rolled pure copper rolled plate. And a fine crystal structure by further annealing, and a high special grain boundary ratio is imparted by forming a twin crystal structure by partial recrystallization, and a pure copper plate suitable for a sputtering target or a plating anode Intended to be provided.
- the present inventors hot-rolled a pure copper ingot under certain conditions to suppress grain growth, and after quenching under certain conditions to stop grain growth.
- the length ratio of special grain boundaries measured by EBSD method is set to 25% or more, thereby suppressing abnormal discharge at the time of sputtering and suppressing the generation of insoluble slime during plating. It has been found that a pure copper plate can be produced.
- a pure copper ingot having a purity of 99.96 wt% or more is heated to 550 ° C. to 800 ° C., and the rolling reduction is 80% or more and the temperature at the end of rolling is 500 to 700 C., then rapidly quench at a cooling rate of 200 to 1000.degree. C./min from the temperature at the end of rolling to a temperature of 200.degree. C. or less, and then at a rolling reduction of 5 to 24%. It is characterized by cold rolling and annealing.
- the hot rolling end temperature 500 to 700.degree.
- the hot rolling finish temperature exceeds 700 ° C.
- the crystal grains become large rapidly, and it is difficult to obtain fine crystal grains even if the quenching is performed thereafter.
- the hot rolling finish temperature is less than 500 ° C.
- the effect of refining the crystal grain size is saturated, and lowering the temperature beyond that does not contribute to refining.
- the rolling temperature is low, excessive energy is required to obtain a desired total rolling reduction, and the processing is difficult.
- the starting temperature of hot rolling is set to 550 to 800 ° C.
- the total rolling ratio by hot rolling it is preferable to set the total rolling ratio by hot rolling to 80% or more, and it is possible to suppress the increase of the crystal grains and reduce the variation by the large energy which makes the total rolling ratio 80% or more.
- the total rolling reduction is less than 80%, the crystal grains tend to be large, and the variation thereof becomes large.
- quenching is performed at a cooling rate of 200 to 1000 ° C./min until the temperature reaches 200 ° C. or less. If the cooling rate is less than 200 ° C./min, the effect of suppressing the growth of crystal grains is poor, and if it exceeds 1000 ° C./min, it does not contribute to further miniaturization.
- a more preferable cooling rate is in the range of 300 to 600 ° C./min.
- the pure copper sheet produced by the production method of the present invention has a ratio of the total special grain boundary length L.sub. ⁇ of the special grain boundary to the total grain boundary length L of the grain boundary measured by the EBSD method (special grain boundary length It is characterized in that the ratio (L.sigma./L) is 25% or more. It is further preferable that the average crystal grain size measured by EBSD method is 10 to 120 ⁇ m and the Vickers hardness is 40 to 90. In particular, when the special grain boundary length ratio is 25% or more, the consistency of the crystal grain boundaries is improved to suppress abnormal discharge during sputtering of the sputtering target, and in-plane dissolution uniformity of the plating anode. The various properties such as the improvement of the property are improved.
- the pure copper plate of the present invention is preferably used as a sputtering target or an anode for plating.
- the pure copper plate of the present invention has a fine crystal grain diameter and a special grain boundary length ratio of 25% or more, when used as a sputtering target, it causes abnormal discharge over a long time.
- in-plane dissolution uniformity can be improved and generation of insoluble slime can be suppressed.
- the target and the in-plane dissolution homogeneity which can suppress abnormal discharge over a long time because the crystal grain size is fine and the special grain boundary length ratio is 25% or more It is possible to provide an anode for plating capable of improving and suppressing the generation of insoluble slime.
- the pure copper plate of this embodiment is an oxygen-free copper having a purity of 99.96 wt% or more of copper, or an oxygen-free copper for an electron tube of 99.99 wt% or more.
- the average grain size of the rolled sheet of the present invention is 10 to 120 ⁇ m, the Vickers hardness is 40 to 90, and the special grain boundary length ratio measured by EBSD method is 25% or more.
- a grain boundary is defined as a boundary between two adjacent crystals when the orientation between two adjacent crystals is 15 ° or more as a result of two-dimensional cross-sectional observation.
- the special grain boundary is a crystal grain having a crystallographically defined CSL theory (Kronberg et. Al .: Trans. Met. Soc. AIME, 185, 501 (1949)) with ⁇ value 3 ⁇ ⁇ ⁇ 29.
- Grain corresponding to the grain boundary (corresponding grain boundary) in which the intrinsic corresponding site lattice orientation defect Dq in the grain boundary satisfies Dq ⁇ 15 ° / ⁇ 1/2 (DGBrandon: Acta. Metallurgica. Vol. 14, p1479, 1966) It is defined as a world. If the length ratio of the special grain boundary is high among all the grain boundaries, the consistency of the grain boundaries is improved, and a sputtering target, an anode for plating, a heat dissipation substrate, etc. widely known as a pure copper plate application The characteristics of can be improved.
- the heat dissipation substrate repeats expansion and contraction at the time of use, it is important to have uniform deformation characteristics and to be excellent in fatigue characteristics.
- direct and alternating inverter circuits are indispensable in hybrid cars and solar cells, etc., which are popularized by the trend of energy saving and CO reduction, and pure copper or low alloy as a heat dissipation substrate to dissipate heat generated at the time of conversion. Copper plate is used.
- the increase in system size leads to an increase in current, and the heat load on the heat dissipation substrate tends to increase.
- the thermal radiation substrate is required to have a thermal fatigue property over a long period of time because thermal expansion / contraction is constantly repeated during use.
- the homogeneity of the structure is important for the heat-resistant fatigue characteristics, it is difficult to improve the fatigue characteristics associated with the increase in current only by the improvement of the uniformity of the conventional structure.
- the pure copper plate of the present invention suppresses abnormal discharge in the sputtering target, suppresses the generation of insoluble slime in the plating anode, and increases the heat resistance of the heat dissipation substrate by setting the length ratio of the special grain boundary to 25% or more. An effect such as improvement of fatigue characteristics can be observed, and is suitable for a sputtering target, an anode for plating, a heat dissipation substrate and the like.
- a pure copper ingot is heated to 550 ° C. to 800 ° C., and while the plate is reciprocated between rolling rolls a plurality of times, the gap between the rolling rolls is gradually reduced and rolling is performed to a predetermined thickness.
- the rolling ratio by the multiple rolling is set to 80% or more, and the temperature at the end of rolling is set to 500 to 700.degree.
- quenching is performed at a cooling rate of 200 to 1000 ° C./min until the temperature at the end of rolling reaches a temperature of 200 ° C. or less.
- it is cold-rolled at a rolling ratio of 5 to 24% and annealed by heating at 250 to 600 ° C. for 30 minutes to 2 hours.
- Hot rolling is processed at a high temperature of 850 to 900 ° C. in the process of hot rolling ⁇ cooling ⁇ cold rolling ⁇ heat treatment by a conventional method of producing a pure copper sheet.
- the crystal grains become coarsened, and therefore, even if this is quenched, the average crystal grain size can not be refined to 80 ⁇ m or less.
- hot rolling is performed at a relatively low temperature state where the start temperature is 550 to 800 ° C. and the end temperature is 500 to 700 ° C.
- the end temperature of the hot rolling exceeds 700 ° C.
- the crystal grains become large rapidly, and it is difficult to obtain fine crystal grains even if the quenching is performed thereafter.
- the hot rolling finish temperature is less than 500 ° C.
- the effect of refining the crystal grain size is saturated, and lowering the temperature below that does not contribute to refining.
- the rolling end temperature is set to 500 to 700.degree.
- the start temperature of the hot rolling is set to 550 to 800 ° C.
- the rolling ratio it is preferable to set the rolling ratio to 80% or more as the rolling ratio in the hot rolling, and by setting the rolling ratio to 80% or more, coarsening of the crystal grain size can be suppressed and the variation can be reduced. From such a viewpoint, it is preferable to set the rolling reduction to 80% or more. When the rolling reduction is less than 80%, the crystal grains tend to be large, and the variation thereof becomes large. In addition, for rolling at the final stage among a plurality of times of rolling performed to achieve the rolling reduction, it is more preferable to set the rolling reduction per one pass to 25% or more. By increasing the rolling reduction to 25% or more at the final stage of hot rolling, the mixture of large crystal grains is prevented, and it is possible to obtain fine crystal grains that are more uniform as a whole.
- the final stage rolling may be performed in one to several passes at a rolling reduction of 25% or more.
- the rolling reduction per pass means the reduction rate of the thickness of the base material after passing through the rolling roll relative to the thickness of the base material before passing through the rolling roll (or the current pass relative to the gap between the rolling rolls in the previous pass).
- the reduction rate of the gap between the rolling rolls), and the total rolling reduction rate is the reduction rate of the thickness of the base material after the end of rolling relative to the base material before rolling.
- water quenching is performed at a cooling rate of 200 to 1000 ° C./min until the temperature reaches 200 ° C. or less. If the cooling rate is less than 200 ° C./min, the effect of suppressing the growth of crystal grains is poor, and if it exceeds 1000 ° C./min, it does not contribute to further miniaturization.
- the cooling rate is less than 200 ° C./min, the effect of suppressing the growth of crystal grains is poor, and if it exceeds 1000 ° C./min, it does not contribute to further miniaturization.
- By cooling to a temperature of 200 ° C. or less at a cooling rate in such a range it is possible to stop the growth of crystal grains and obtain fine crystal grains. If quenching is stopped at a temperature exceeding 200 ° C., then there is a risk that crystal grains will gradually grow by being left at the high temperature state.
- cold rolling improves hardness and strength, improves flatness, and obtains a good surface state
- heat treatment is performed, so that the length ratio of special grain boundaries of grain boundaries is 25%. It is performed to increase the above, and the rolling reduction is 5 to 24%. If the rolling reduction is less than 5%, it is difficult to obtain the desired special grain boundary ratio, while if it exceeds 24%, no further effect is observed.
- Annealing treatment is performed to form a twin crystal structure by partial recrystallization and improve the length ratio of special grain boundaries using strain energy introduced by cold rolling.
- the annealing temperature is preferably 250 to 600 ° C., and the heating atmosphere may be maintained for 30 to 120 minutes.
- a rolling material As a rolling material, a cast ingot of oxygen free copper (purity 99.99 wt% or more) for an electron tube was used. The dimensions of the material before rolling were width 650 mm ⁇ length 900 mm ⁇ thickness 290 mm, and a plurality of conditions after hot rolling were combined as shown in Table 1 to produce a pure copper plate. Moreover, the measurement of temperature was performed by measuring the surface temperature of a rolling board using a radiation thermometer.
- an electron beam is irradiated to an individual measurement point (pixel) within the measurement range of the sample surface using a scanning electron microscope, and an orientation difference between adjacent measurement points is determined by orientation analysis by backscattered electron beam diffraction.
- Grain boundaries were defined between measurement points where the temperature was 15 ° or more.
- the average crystal grain size twins are also counted as crystal grains
- the number of crystal grains in the observation area is calculated from the obtained grain boundaries, the area area is divided by the number of crystal grains, and the crystal grain area is calculated.
- the average crystal grain size was calculated by calculating it and converting it into a circle.
- the total grain boundary length L of the grain boundary in the measurement range is measured, and the position of the grain boundary where the interface of the adjacent grain constitutes the special grain boundary is determined, and all the special grain boundaries of the special grain boundary
- the grain boundary length ratio L ⁇ / L between the length L ⁇ and the total grain boundary length L of the grain boundary measured as described above is determined as a special grain boundary length ratio.
- ⁇ Vickers hardness> The Vickers hardness was measured by a method defined in JIS (Z2244) with respect to a longitudinal cross section (plane viewed in the T.D. direction) along the rolling direction (R.D. direction).
- ⁇ Sputter abnormal discharge count> An integrated target including a backing plate part is manufactured from each sample so that the target part has a diameter of 152 mm and a thickness of 8 mm, attached to a sputtering apparatus, and the ultimate vacuum pressure in the chamber is 1 ⁇ 10 -5 Pa or less, sputtering Continuous sputtering was performed for 8 hours using high purity Ar as a gas, a sputtering gas pressure of 0.3 Pa, and a direct current (DC) power supply under the conditions of a sputtering output of 1 kW. In addition, the total number of abnormal discharges was counted using an arcing counter attached to the power supply.
- DC direct current
- a copper plate cut into a disk shape with a diameter of 270 mm is fixed to the electrode holder (execution electrode area: about 530 cm 2 ) and used as an anode electrode, and a silicon wafer with a diameter of 200 mm is used as a cathode. Copper plating is performed under the following conditions. The insoluble slime generated when processing the first wafer was collected, and the amount of slime generated was measured. The amount of slime generation was determined by weight measurement after drying and drying the slime.
- Plating solution 70 g / l of copper pyrophosphate, 300 g / l of potassium pyrophosphate, 15 g / l of potassium nitrate, added to ion exchange water, and adjusted to pH 8.5 with aqueous ammonia, Plating conditions: air agitation at a liquid temperature of 50 ° C. and agitation by cathode oscillation, Cathode current density: 2 A / dm 2 , Plating time: 1 hour / plate.
- Each sample is a flat plate of 100 ⁇ 2000 mm, and the surface is cut with a milling cutter using a carbide cutting tool with a cutting depth of 0.2 mm and a cutting speed of 5000 m / min, within a 500 ⁇ m square field of view of the cutting surface It was examined how many mussels with a length of 100 ⁇ m or more were present. The results are shown in Table 2.
- the pure copper plates manufactured by the manufacturing method of this example all have an average crystal grain size of 10 to 120 ⁇ m, a hardness of 40 to 90 Hv, and special grains.
- the field length ratio is 25% or more.
- the average grain size, hardness or special grain boundary length ratio is out of the range.
- the pure copper plate of the present invention is applicable to a sputtering target and a backing plate for the target, and further, an anode for plating, a mold, a discharge electrode, a heat sink, a heat sink, a mold, a water cooling plate, an electrode, an electric terminal,
- the invention can also be applied to bus bars, gaskets, flanges, printing plates and the like.
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Abstract
Description
本願は、2010年2月9日に出願された特願2010-26453号に基づき優先権を主張し、その内容をここに援用する。
このような範囲の冷却速度にて200℃以下の温度まで冷却すれば結晶粒の成長を停止して微細な結晶粒のものを得ることができる。200℃を超える温度で急冷を止めてしまうと、その後、その高温状態での放置によって徐々に結晶粒が成長するおそれがある。
そしてこの急冷の後に、5~24%の圧延率の冷間圧延と焼鈍処理をすることによって、結晶粒径が微細化すると共に、部分再結晶化によって双晶組織を形成させることにより高い特殊粒界比率を付与することができる。
また、EBSD法にて測定した平均結晶粒径が10~120μmであり、ビッカース硬さは40~90であるとなおよい。
特に、前記特殊粒界長さ比率が25%以上であることにより、結晶粒界の整合性が向上して、スパッタリングターゲットのスパッタ中での異常放電の抑制や、めっき用アノードの面内溶解均質性の向上といった各種特性が良好になる。
前述したように、本発明の純銅板は、結晶粒径が微細であり、特殊粒界長さ比率が25%以上であることにより、スパッタリングターゲットとして用いた場合、長時間に渡って異常放電を抑制することができ、まためっき用アノードとして用いた場合、面内溶解均質性が向上し不溶性スライムの発生を抑制することができる。
この実施形態の純銅板は、銅の純度が99.96wt%以上の無酸素銅、又は99.99wt%以上の電子管用無酸素銅である。
本発明の圧延板の平均結晶粒径は10~120μmとされ、ビッカース硬さは40~90であり、またEBSD法にて測定した特殊粒界長さ比率が25%以上とされる。
また、平均結晶粒径を10μm未満とするのは現実的でなく、製造コスト増を招く。
結晶粒界は、二次元断面観察の結果、隣り合う2つの結晶間の配向が15°以上となっている場合の当該結晶間の境界として定義される。特殊粒界は、結晶学的にCSL理論(Kronberg et.al.: Trans. Met. Soc. AIME, 185, 501 (1949))に基づき定義されるΣ値で3≦Σ≦29を有する結晶粒界(対応粒界)であって、当該粒界における固有対応部位格子方位欠陥Dqが Dq≦15°/Σ1/2 (D.G.Brandon:Acta.Metallurgica. Vol.14,p1479,1966)を満たす結晶粒界として定義される。
すべての結晶粒界のうち、この特殊粒界の長さ比率が高いと、結晶粒界の整合性が向上して、純銅板の用途として広く知られるスパッタリングターゲットやめっき用アノード、あるいは放熱基板等の特性を向上させることが出来る。
このように本発明の純銅板は、特殊粒界の長さ比率を25%以上とすることにより、スパッタリングターゲットにおける異常放電の抑制、めっき用アノードにおける不溶性スライムの発生の抑制、放熱基板での耐熱疲労特性の向上等の効果が見られ、スパッタリングターゲット、めっき用アノード、放熱基板等に好適である。
まず、純銅のインゴットを550℃~800℃に加熱し、これを複数回圧延ロールの間に往復走行させながら徐々に圧延ロール間のギャップを小さくして、所定の厚さまで圧延する。この複数回の圧延による圧延率は80%以上とされ、圧延終了時の温度は500~700℃とされる。その後、圧延終了時温度から200℃以下の温度になるまで200~1000℃/minの冷却速度にて急冷する。その後、5~24%の圧延率で冷間圧延し、250~600℃で30分~2時間加熱することにより焼鈍する。
このような範囲の冷却速度にて200℃以下の温度まで冷却すれば結晶粒の成長を停止して微細な結晶粒のものを得ることができる。200℃を超える温度で急冷を止めてしまうと、その後、その高温状態での放置によって徐々に結晶粒が成長するおそれがある。
焼鈍処理は、冷間圧延で導入した歪エネルギーを用いて、部分再結晶化によって双晶組織を形成させ特殊粒界長さ比率を向上させるために行う。焼鈍温度は250~600℃が好ましく、その加熱雰囲気で30~120分間、保持すればよい。
圧延素材は、電子管用無酸素銅(純度99.99wt%以上)の鋳造インゴットを用いた。圧延前の素材寸法は幅650mm×長さ900mm×厚さ290mmとし、熱間圧延以降の各条件を表1に示すように複数組み合わせて純銅板を作製した。また、温度の測定は放射温度計を用い、圧延板の表面温度を測定することにより行った。
各試料について、耐水研磨紙、ダイヤモンド砥粒を用いて機械研磨を行った後、コロイダルシリカ溶液を用いて仕上げ研磨を行った。
そして、EBSD測定装置(HITACHI社製 S4300-SE,EDAX/TSL社製 OIM Data Collection)と、解析ソフト(EDAX/TSL社製 OIM Data Analysis ver.5.2)によって、結晶粒界、特殊粒界を特定し、その長さを算出することにより、平均結晶粒径及び特殊粒界長さ比率の解析を行った。
平均結晶粒径(双晶も結晶粒としてカウントする)の測定は、得られた結晶粒界から、観察エリア内の結晶粒子数を算出し、エリア面積を結晶粒子数で割って結晶粒子面積を算出し、それを円換算することにより平均結晶粒径(直径)とした。
また、測定範囲における結晶粒界の全粒界長さLを測定し、隣接する結晶粒の界面が特殊粒界を構成する結晶粒界の位置を決定するとともに、特殊粒界の全特殊粒界長さLσと、上記測定した結晶粒界の全粒界長さLとの粒界長比率Lσ/Lを求め、特殊粒界長さ比率とした。
ビッカース硬さは、圧延方向(R.D.方向)に沿う縦断面(T.D.方向に見た面)に対して、JIS(Z2244)に規定される方法により測定した。
各試料からターゲット部分が直径152mm、厚さ8mmとなるようにバッキングプレート部分を含めた一体型のターゲットを作製しスパッタ装置に取り付け、チャンバー内の到達真空圧力を1×10-5Pa以下、スパッタガスとして高純度Arを用い、スパッタガス圧を0.3Paとし、直流(DC)電源にて、スパッタ出力1kWの条件で8時間の連続スパッタを行った。また、電源に付属するアーキングカウンターを用いて、総異常放電回数をカウントした。
直径270mmの円盤状に切り出した銅板を電極ホルダーに固定(実行電極面積約530cm2)しアノード電極とし、直径200mmのシリコンウエハをカソードとして、以下の条件にて銅めっきを行い、めっき開始から5枚目までのウエハを処理した際に発生する不溶性スライムを採取し、スライム発生量を測定した。尚、スライム発生量は、スライムを回収後、乾燥させた後の重量測定により求めた。
めっき液:イオン交換水に、ピロリン酸銅 70g/l、ピロリン酸カリウム 300g/l、硝酸カリウム 15g/lを添加し、アンモニア水にてpH8.5に調整したもの、
めっき条件:液温50℃で空気攪拌およびカソード揺動による攪拌実施、
カソード電流密度:2A/dm2、
めっき時間:1時間/枚。
各試料を100×2000mmの平板とし、その表面をフライス盤で超硬刃先のバイトを用いて切込み深さ0.2mm、切削速度5000m/分で切削加工し、その切削表面の500μm四方の視野内において長さ100μm以上のムシレ疵が何個存在したかを調べた。
これらの結果を表2に示す。
C ムシレ疵
Claims (6)
- 純度が99.96wt%以上である純銅のインゴットを、550~800℃に加熱して、熱間圧延の圧延率が80%以上で圧延終了温度が500~700℃である熱間圧加工を施した後に、前記圧延終了温度から200℃以下の温度になるまで200~1000℃/分の冷却速度にて急冷し、その後、5~24%の圧延率で冷間圧延して焼鈍することを特徴とする純銅板の製造方法。
- 請求項1に記載の製造方法によって製造された純銅板であって、EBSD法にて測定した結晶粒界の全粒界長さLに対する特殊粒界の全特殊粒界長さLσの比率(L/Lσ)が25%以上であることを特徴とする純銅板。
- ビッカース硬さが40~90であることを特徴とする請求項2記載の純銅板。
- EBSD法で測定した平均結晶粒径が10~120μmであることを特徴とする請求項2に記載の純銅板。
- スパッタリングターゲットであることを特徴とする請求項2に記載の純銅板。
- めっき用アノードであることを特徴とする請求項2に記載の純銅板。
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CN103572227A (zh) * | 2012-07-30 | 2014-02-12 | 株式会社Sh铜业 | 溅射用铜靶材以及溅射用铜靶材的制造方法 |
CN103572227B (zh) * | 2012-07-30 | 2017-07-07 | 株式会社Sh铜业 | 溅射用铜靶材以及溅射用铜靶材的制造方法 |
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KR20170036813A (ko) | 2017-04-03 |
JP4869415B2 (ja) | 2012-02-08 |
KR20120125248A (ko) | 2012-11-14 |
TW201139707A (en) | 2011-11-16 |
JP2011162835A (ja) | 2011-08-25 |
KR102079855B1 (ko) | 2020-02-20 |
TWI499680B (zh) | 2015-09-11 |
CN102712987B (zh) | 2014-08-06 |
CN102712987A (zh) | 2012-10-03 |
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