CN114939661B - Preparation method of molybdenum alloy tube target, molybdenum alloy tube target and application - Google Patents
Preparation method of molybdenum alloy tube target, molybdenum alloy tube target and application Download PDFInfo
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 66
- 238000001125 extrusion Methods 0.000 claims abstract description 62
- 239000013077 target material Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 23
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 21
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000004544 sputter deposition Methods 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims description 25
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 claims description 24
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 21
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- -1 titanium hydride Chemical compound 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000003754 machining Methods 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910052702 rhenium Inorganic materials 0.000 description 9
- 238000005086 pumping Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
- B22F5/106—Tube or ring forms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
- B22F3/162—Machining, working after consolidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
- B22F3/164—Partial deformation or calibration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/16—Both compacting and sintering in successive or repeated steps
- B22F3/164—Partial deformation or calibration
- B22F2003/166—Surface calibration, blasting, burnishing, sizing, coining
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Fluid Mechanics (AREA)
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Abstract
The application provides a preparation method of a molybdenum alloy tube target, the molybdenum alloy tube target and application, and belongs to the technical field of powder metallurgy. The target material is prepared from raw material powder through the working procedures of cold isostatic pressing, sheath, hot isostatic pressing, extrusion molding, annealing and the like, and the target material prepared by the application comprises the following components in percentage by mass: 10-30%, ti:5-25%, re:0.5 to 5 percent, M:0-15% of M is at least one of Cr, zr, ta, nb, wherein M is used for replacing part of Ti, the balance is Mo and unavoidable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 50%. The target material prepared by the method has good toughness, better deformability and fine and uniform grains. The thin film sputtered and deposited by the target material prepared by the application has more uniform thickness distribution, and can be attached on the main conductive layer of the laminated wiring film for the electronic component by a sputtering mode to form a metal covering layer for flat panel displays, thin film solar devices, semiconductor devices and the like.
Description
Technical Field
The application belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of a molybdenum alloy tube target, the molybdenum alloy tube target and application.
Background
With the technology of flat panel display devices such as liquid crystal displays and display panels, it is necessary to reduce the resistance of wiring films. Meanwhile, with the large screen, high definition, high speed response of flat panel displays, and the large size of flexible panels, lower film resistance levels are also required.
A Thin Film Transistor (TFT) uses Al or Cu as a main wiring material as a driving element of a display panel. However, if Al or Cu is in direct contact with Si, thermal diffusion is formed due to thermal processing during the manufacturing process, so that the thin film transistor performance is deteriorated. Therefore, a laminated wiring film needs to be provided between Al/Cu and Si.
Mo, mo-Nb, mo-Ti and other molybdenum alloys have good corrosion resistance and heat resistance, and good adhesion with a substrate, and can be used for preparing a laminated wiring film. However, in the production process, the laminated wiring film may be left in the atmosphere for a long time after the laminated wiring film is formed on the substrate. Meanwhile, when the signal cable is mounted on the display panel, it is sometimes necessary to heat in the atmosphere, and in the semiconductor thin film using an oxide, heat treatment under an aerobic atmosphere is required for the purpose of improving the performance and stabilization. Therefore, there is a strong demand for enhancing the oxidation resistance of the laminated wiring film. In addition, a resin film used for a lightweight and flexible display panel that is portable has moisture permeability as compared with a glass substrate, and a laminated wiring film is required to have high moisture resistance. However, the moisture resistance and oxidation resistance of pure Mo, mo—ti, and other materials are insufficient, and oxidation may occur, resulting in a problem that the resistance value of Al or Cu is significantly increased.
Patent CN2012102930608 discloses a molybdenum alloy target for laminated wiring films, in which a certain amount of Ni and Ti are added to molybdenum in order to improve the moisture resistance and oxidation resistance of a pure molybdenum plating film, which contributes to stable manufacture of electronic parts and improvement of reliability.
Patent CN2014100909230 discloses a molybdenum alloy target for electronic parts, which is improved in oxidation resistance by adding Ni and improved in moisture resistance by adding W.
Patent CN2017114460697 discloses a molybdenum alloy target material component containing Ni, nb, ti and other elements, which can better improve the moisture resistance and oxidation resistance of pure molybdenum and keep lower film resistance.
The above patent has the advantages that by adding a certain amount of Ni, ti or W and other elements into the molybdenum substrate, the moisture resistance and the oxidation resistance of the molybdenum target sputtering film are improved together, and the lower resistance value is kept. However, the preparation of the target material is mainly performed by Hot Isostatic Pressing (HIP), and as the length of the target material increases, the HIP forming size is severely limited by the size of HIP equipment, and the high-performance molybdenum alloy target material cannot be produced in batch. Moreover, due to the poor formability of molybdenum alloy targets, tubular target products of different lengths cannot be prepared by deformation means such as extrusion, forging and the like.
Disclosure of Invention
The application aims to provide a preparation method of a molybdenum alloy tube target material, the molybdenum alloy tube target material and application.
According to the molybdenum alloy tube target material provided by the application, after rhenium element is added, the plasticity and toughness of the target material are increased, and the deformation processing capacity of the target material is improved. The molybdenum alloy tube target material is extruded and molded in the subsequent preparation process, so that the grain size can be refined. In addition, considering that the price of rhenium is relatively high, the application effectively plays a role in improving the performance and processing capability of the target material by adding a small amount of rhenium to be matched with other components.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the first aspect of the application provides a preparation method of a molybdenum alloy tube target, which comprises the following steps:
mixing powder: respectively weighing raw materials according to the mass fraction of each element in the molybdenum alloy tube target material, and uniformly mixing to obtain molybdenum alloy powder; the molybdenum alloy tube target comprises the following components in percentage by mass: ni:10-30% (e.g. 12%, 15%, 20%, 25%), ti:5-25% (e.g., 6%, 8%, 10%, 15%, 20%), re:0.5 to 5% (e.g., 0.7%, 0.9%, 1.2%, 1.5%, 2%, 2.5%, 3%, 4%), M:0-15% (e.g., 1%, 3%, 5%, 8%, 10%, 13%), M being at least one of Cr, zr, ta, nb, said M being used to replace a portion of Ti, the balance being Mo and unavoidable impurities, and the mass percentage content of Mo in said molybdenum alloy tube target being not less than 50% (e.g., 52%, 60%, 70%);
cold isostatic pressing: placing the mixed powder into a die, and performing cold isostatic pressing to obtain a first blank;
hot isostatic pressing: performing hot isostatic pressing on the first blank to obtain a second blank;
extrusion molding: extruding and forming the second blank to obtain a third blank;
annealing: and annealing the third blank.
The Ni in the target material component of the molybdenum alloy tube can improve the oxidation resistance of the film layer formed by the target material, the Ti can improve the moisture resistance of the film layer, and proper addition of the Ni can ensure the oxidation resistance and the moisture resistance of the film layer, can also ensure the low resistance of the wiring film, and does not influence the etching speed of the etchant.
The molybdenum alloy tube target material is added with a small amount of Re element, and the addition of rhenium element with a specific proportion and other elements with a specific proportion in the molybdenum alloy are combined to act together, so that rhenium plays a role of rhenium in the molybdenum alloy, the room temperature plasticity of the molybdenum alloy is improved, the plastic-brittle transition temperature is reduced, grains are thinned and the like. By adding Re element into the molybdenum alloy tube target, the deformation performance of the target can be improved, cracks can not be generated during large deformation processing, and the grain size difference of the target obtained by the preferable molybdenum alloy component proportion is particularly small due to fine grains of the target structure, the grains are uniform, and the film layer prepared by the target provided by the application has more uniform thickness and higher sputtering speed. When the Re element is used in an amount exceeding 5%, on the one hand, the cost is increased, and on the other hand, when the Re element is excessively added, re can form an alloy phase with other elements, and the subsequent coating effect is affected. When the Re element consumption is less than 0.5%, the effect of effectively refining grains and enhancing the plasticity of the target material cannot be achieved.
The M element has the function of enhancing the moisture resistance of the target coating, can be used for partially replacing Ti with the same moisture resistance, and can also improve the oxidation resistance and the like of the target coating. However, from the standpoint of interaction of various components in the target, it is preferable that the element M may only partially replace Ti.
In some embodiments, the method for preparing a molybdenum alloy tube target further comprises:
shaping: shaping the first blank after cold isostatic pressing;
and (3) covering: before the hot isostatic pressing, placing the shaped first blank into a sheath, and vacuumizing and sealing;
removing the sheath: machining the sheath of the second billet after the hot isostatic pressing;
machining: the third blank is machined prior to the annealing process.
In some embodiments, the molybdenum alloy tube target comprises, in mass percent: ni:10 to 30% (e.g. 12%, 14%, 18%, 20%, 25%), ti:5-25% (e.g., 6%, 8%, 10%, 13%, 16%, 19%, 23%), re:1 to 5% (e.g., 1.2%, 1.5%, 2%, 3%, 4%), M:0-5% (e.g., 0.5%, 1%, 2%, 3%, 4%), the balance Mo and unavoidable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 60% (e.g., 61%, 65%, 70%, 80%).
In the preferred composition range, the molybdenum alloy tube target has better properties.
In some embodiments, in the powder mixing step, the raw materials include: the purity of the molybdenum powder is more than or equal to 3N5, and the Fisher size range of the molybdenum powder is preferably 2.5-4 mu m; the purity of the nickel powder is more than or equal to 3N, and the Fisher size range of the nickel powder is preferably 2-3 mu m; the titanium source is titanium powder or titanium hydride, the purity of the titanium powder is more than or equal to 3N, the Fisher size range of the titanium powder is preferably 2-4 mu m, the purity of the titanium hydride is more than or equal to 2N, and the Fisher size range of the titanium hydride is preferably 2-4 mu m; the purity of the rhenium powder is more than or equal to 4N, and the Fisher size of the rhenium powder is preferably 2-4 mu m.
In some embodiments, the titanium element in the molybdenum alloy tube target is added in the form of molybdenum titanium alloy powder; the molybdenum-titanium alloy powder is obtained by mixing part of molybdenum powder in raw materials with titanium hydride powder and then carrying out reduction treatment;
preferably, the molybdenum-titanium alloy powder has a molybdenum-titanium mass ratio of 90:10 to 70:30 (e.g., 85:15, 80:20, 75:25).
Preferably, in the process of preparing the molybdenum-titanium alloy powder, the reduction treatment is performed in a hydrogen atmosphere at a temperature of 500 to 900 ℃ (e.g., 600 ℃, 700 ℃, 800 ℃) for a time of 2 to 8 hours (3 hours, 4 hours, 5 hours, 6 hours).
In the hydrogen reduction treatment, the gas flow is determined according to the size of the reduction furnace chamber, and the pressure is micro-positive pressure. Titanium hydride is selected as a titanium source to make the prepared molybdenum-titanium alloy powder more uniform; titanium powder can also be directly used as a source for direct mixing, but the uniformity of the powder is inferior to that of the titanium hydride molybdenum-doped powder reduction process.
In some embodiments, the powder mixing is performed in a ball milling tank, the ball material ratio is 1:1-2:1, argon is filled after the air is pumped to negative pressure, preferably the argon pressure in the ball milling tank is one atmosphere, the mixing time is 10h-16h (for example, 12h and 14 h), and the rotating speed is 50-300r/min.
In some embodiments, the cold isostatic pressing has a pressing pressure of 150-200 MPa (e.g., 170MPa, 190 MPa) and a dwell time of 5-20 minutes (e.g., 8 minutes, 10 minutes, 15 minutes, 18 minutes). Preferably, the die is a tubular die made of stainless steel.
The cold isostatic pressing process of the present application may provide the first billet with a relative density of 55-65%.
In some embodiments, the hot isostatic pressing is maintained at a temperature of 900 ℃ -980 ℃ (e.g., 920 ℃, 940 ℃, 960 ℃), a pressure of 100-170MPa (e.g., 120MPa, 140MPa, 160 MPa), and a dwell time of 2-5h (e.g., 3h, 4 h).
The hot isostatic pressing process of the application may allow for a densification of the second billet of some molybdenum alloy components up to 100%.
For the condition that the density of the blank cannot reach 100% only through the hot isostatic pressing process, a high-temperature sintering step can be added between the hot isostatic pressing and cold isostatic pressing steps, so that the sintering effect of alloy components is improved, and the density of the blank is further improved.
In some embodiments, the extrusion is a reduced temperature extrusion, the start temperature of the extrusion is 1100-1400 ℃ (e.g., 1150 ℃, 1200 ℃, 1300 ℃) and the end temperature of the extrusion is 900-1100 ℃ (e.g., 950 ℃, 1000 ℃, 1050 ℃). Before each pass of extrusion, the second blank is placed into a muffle furnace, heated in air or argon atmosphere, kept at 1100-1400 ℃ for 30-120 minutes (for example, 40 minutes, 60 minutes, 80 minutes and 100 minutes), and extruded for each pass after being discharged.
The temperature-reducing extrusion is specifically that the heating and heat-preserving temperature before the extrusion of the next time is lower than that before the extrusion of the previous time;
preferably, the temperature of the heating and preserving heat before the extrusion of the next pass is reduced by more than or equal to 100 ℃ (for example, 10 ℃, 20 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃) based on the temperature of the heating and preserving heat before the extrusion of the previous pass;
preferably, the extrusion deformation rate of each pass of the extrusion is 15-25% (e.g. 17%, 19%, 21%, 23%), and the total deformation of the extrusion is 40-80% (e.g. 50%, 60%, 70%).
The extrusion starting temperature is controlled within the range of 1100-1400 ℃, and the extrusion forming effect is good. When the extrusion starting temperature is too high, nickel can melt, oxidation is serious, and when the extrusion starting temperature is low, a blank is easy to crack in the extrusion forming process. The extrusion molding end temperature is controlled to 900-1100 ℃ (for example 1050 ℃, 1100 ℃, 1150 ℃) to ensure the molding performance and avoid cracking.
The extrusion deformation rate of each pass is controlled to be 15-25%, the deformation performance of the material can be fully utilized, when the deformation rate is too large, the blank is cracked in the extrusion deformation process, and meanwhile, the pass cooling is controlled to be within 100 ℃ so as to maintain the good strength and plasticity of the material and avoid the cracking.
In some embodiments, the annealing treatment is performed under an argon atmosphere at an annealing temperature of 1000-1300 ℃ (e.g., 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃), and an annealing soak time of 60-120 minutes (e.g., 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes).
The annealing temperature is controlled in the range, so that the anisotropism of the extruded target material can be eliminated, and the molybdenum alloy tube target material with uniform structure and fine grains can be obtained. When the annealing temperature is lower than 1000 ℃, the structure of the target material is uneven, when the annealing temperature is higher than 1300 ℃, the crystal grains are abnormally grown, mixed crystals appear, and the effect of the subsequent sputtering coating of the target material is affected.
In some embodiments, after the annealing treatment, a uniform fine grain target with a grain size of 100 μm or less (e.g., 60 μm, 70 μm, 80 μm, 90 μm) and a grain size of 4-5 grades can be obtained.
The molybdenum alloy tube target prepared by the application has fine grains, and the sputtering rate is faster than that of a target with coarse grains. And the grain size of the target material has smaller difference (even distribution), and the thickness distribution of the thin film deposited by sputtering the target material is more even. The quality of the film obtained by sputtering the molybdenum alloy tube target material prepared by the application can be greatly improved.
The second aspect of the application provides a molybdenum alloy tube target prepared by the method.
In some embodiments, the molybdenum alloy tube target has a grain size of 100 μm or less (e.g., 60 μm, 70 μm, 80 μm, 90 μm), with a grain size of 4-5 grades.
The third aspect of the application provides application of the molybdenum alloy tube target material. The molybdenum alloy tube target is attached to a main conductive layer of a laminated wiring film for electronic components such as a flat panel display, a thin film solar device, or a semiconductor device by sputtering to form a metal coating layer.
Compared with the prior art, the application has the beneficial effects that:
1) After rhenium is added, the plasticity and toughness of the target material are increased, and the deformation processing capability of the target material is improved.
2) The molybdenum alloy tube target material can refine the grain size through extrusion molding in the subsequent preparation process, and the uniform fine-grain target material with the grain size less than or equal to 100 mu m and the grain size of 4-5 grades can be obtained.
3) The application effectively plays a role in improving the target performance and processing capacity by adding a small amount of rhenium to be matched with other components.
4) The molybdenum alloy tube target prepared by the application has fine grains, and the sputtering rate is faster than that of a target with coarse grains. Moreover, the grain size of the target material has smaller difference (even distribution), and the thickness distribution of the thin film deposited by sputtering the target material is more even. The quality of the film obtained by sputtering the molybdenum alloy target material prepared by the application can be greatly improved.
Drawings
FIG. 1 is a schematic diagram of microstructure morphology of a molybdenum alloy tube target material prepared by an embodiment of the application.
Detailed Description
The following examples further illustrate the present application in detail, but the scope of the present application is not limited to the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The drugs or instruments used were conventional products available commercially without the manufacturer's attention.
Re element can exert the rhenium effect in molybdenum, improve the room temperature plasticity of the material, reduce the plastic-brittle transition temperature, refine grains and the like, and can also improve the deformation performance of the target by adding Re element into the molybdenum alloy tube target, prepare a large-size plate-shaped target by deformation modes such as extrusion and the like, and obtain the target with uniform fine grains by annealing treatment.
The present application will be described in detail with reference to the following examples.
Unless otherwise specified, the powder particle sizes indicated in the examples below are all Fisher particle sizes, with the proportions being mass ratios.
The grain size grade test in the embodiment of the application is based on the standard GB/T6394 metal average grain size determination method.
The yield referred to in the examples below is 100% of the number of acceptable blanks obtained after extrusion deformation/the number of hot-pressed blanks subjected to extrusion deformation.
Example 1:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with purity of 3N5 and granularity of 3.5 mu m; ni powder with purity of 3N and granularity of 3.2 mu m; 3N TiH2 powder with the granularity of 3.4 mu m; rhenium powder with purity of 4N and granularity of 4 mu m, and according to the mass ratio of each element in the target material, mo: ni: ti: re=60:20:18:2, 140Kg of raw material was disposed. Wherein the adding of titanium is to add all titanium hydride powder into partial raw material molybdenum powder, then reduce the powder for 4 hours at 800 ℃ in hydrogen atmosphere to obtain reduced molybdenum-titanium alloy powder (the mass ratio of molybdenum element and titanium element in the molybdenum-titanium alloy powder is 1:1), and then add the molybdenum-titanium alloy powder into the rest powder to be mixed;
step 2: placing the powder obtained in the step 1 into a ball milling tank, pumping air to negative pressure according to a ball material ratio of 1:1, filling argon to atmospheric pressure, and mixing for 13h at a rotating speed of 200r/min;
step 3: placing the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, performing cold isostatic pressing, and maintaining the pressure for 10 minutes under 200 MPa;
step 4: shaping the CIP tubular pressed compact obtained in the step 3 to ensure that the geometry of the blank is complete;
step 5: putting the pressed compact after shaping in the step 4 into a sheath, and pumping air to 10 -1 Pa, maintaining air suction for 5 hours, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath in the step 5, wherein the heat preservation temperature is 920 ℃, the pressure is 120MPa, and the heat preservation and pressure maintaining time is 4 hours;
step 7: the sheath in the step 6 is machined and removed, so that the outer circular surface of the tube target is smooth, no bulge exists, the outer diameter of the tube blank is 180mm, and the inner diameter of the tube blank is 140mm;
step 8: placing the tube blank obtained in the step 7 into a muffle furnace, heating in air atmosphere, wherein the extrusion starting temperature is 1350 ℃, the heat preservation time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with the temperature before each pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 980 ℃, the tube blank size is 120mm in outer diameter and 100mm in inner diameter;
step 9: machining the inner surface and the outer surface of the tube blank obtained in the step 8 to obtain a tube blank with the outer diameter of 115mm and the inner diameter of 105 mm;
step 10: and (3) annealing the tube blank obtained in the step (9) in Ar gas atmosphere at 1100 ℃ for 90 minutes to obtain the uniform fine-grained tube with the grain size of 66-92 mu m and the grain size of 4 grades, wherein the specific reference can be seen in figure 1.
The tube target material obtained in the embodiment has no cracks and the yield is 100%.
Example 2:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with purity of 3N5 and granularity of 3.8 mu m; ni powder with purity of 3N and granularity of 2.4 mu m; tiH of purity 3N 2 Powder, particle size 3.0 μm; rhenium powder with purity of 4N and granularity of 3.5 mu m, according to the mass ratio of each element in the target material, mo: ni: ti: re=73:15:10:2, 200Kg of raw materials are prepared, wherein titanium is added into part of raw material molybdenum powder, the raw materials are added into all titanium hydride powder, the raw materials are reduced for 4 hours at 750 ℃ in hydrogen atmosphere, reduced molybdenum-titanium alloy powder (the mass ratio of molybdenum element to titanium element in the molybdenum-titanium alloy powder is 2:1) is obtained, and the molybdenum-titanium alloy powder is added into the rest of powder to be mixed;
step 2: placing the powder obtained in the step 1 into a ball milling tank, pumping air to negative pressure according to a ball material ratio of 1:2, filling argon to one atmosphere, and mixing for 15 hours at a rotating speed of 200r/min;
step 3: placing the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, performing cold isostatic pressing, and maintaining the pressure for 8 minutes under 200 MPa;
step 4: shaping the CIP tubular pressed compact obtained in the step 3 to ensure that the geometry of the blank is complete;
step 5: putting the pressed compact after shaping in the step 4 into a sheath, and pumping air to 10 -2 Pa, maintaining air suction for 4 hours, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath in the step 5, wherein the heat preservation temperature is 940 ℃, the pressure is 150MPa, and the heat preservation and pressure maintaining time is 3h;
step 7: the sheath in the step 6 is machined and removed to ensure that the outer circular surface of the tube target is smooth and free of bulges, the outer diameter of the tube blank is 200mm, and the inner diameter of the tube blank is 120mm;
step 8: placing the tube blank obtained in the step 7 into a muffle furnace, heating in air atmosphere, wherein the extrusion starting temperature is 1300 ℃, the heat preservation time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with the temperature before each pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is 1050 ℃, the tube blank size is 150mm in outer diameter and 130mm in inner diameter;
step 9: machining the inner surface and the outer surface of the tube blank obtained in the step 8 to obtain a tube blank with the outer diameter of 145mm and the inner diameter of 135mm;
step 10: and (3) annealing the tube blank obtained in the step (9) in Ar gas atmosphere, wherein the annealing temperature is 1250 ℃, and the heat preservation time is 90 minutes, so that the uniform fine-grained tube with the grain size of 60-85 mu m and the grain size of 5 grades is obtained.
The tubular target obtained in the embodiment has no cracks and the yield is 100%.
Example 3:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with purity of 3N5 and granularity of 3.2 mu m; ni powder with purity of 3N and granularity of 3.5 mu m; tiH of purity 3N 2 Powder, particle size 3.5 μm; rhenium powder with purity of 4N and granularity of 3.5 mu m, according to the mass ratio of each element in the target material, mo: ni: ti: re=70:15:10:5, 70Kg is configured, wherein titanium is added into part of molybdenum powder, titanium hydride with the mass ratio of 40% is added, the mixture is reduced for 3 hours at 800 ℃ in hydrogen atmosphere, reduced molybdenum-titanium alloy powder is obtained, and the molybdenum-titanium alloy powder is added into the rest of powder to be mixed;
step 2: placing the powder obtained in the step 1 into a ball milling tank, pumping air to negative pressure according to a ball material ratio of 1:1, filling argon to one atmosphere, and mixing for 16 hours at a rotating speed of 200r/min;
step 3: placing the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, performing cold isostatic pressing, and maintaining the pressure for 15 minutes at 150 MPa;
step 4: shaping the CIP tubular pressed compact obtained in the step 3 to ensure that the geometry of the blank is complete;
step 5: putting the pressed compact after shaping in the step 4 into a sheath, and pumping air to 10 -1 Pa, maintaining air suction for 6 hours, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath in the step 5, wherein the heat preservation temperature is 920 ℃, the pressure is 170MPa, and the heat preservation and pressure maintaining time is 3h;
step 7: the sheath in the step 6 is machined and removed, so that the outer circular surface of the tube target is smooth, no bulge exists, the outer diameter of the tube blank is 240mm, and the inner diameter of the tube blank is 100mm;
step 8: placing the tube blank obtained in the step 7 into a muffle furnace, heating in air atmosphere, wherein the extrusion starting temperature is 1350 ℃, the heat preservation time is 120 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with the temperature before each pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1080 ℃, and the tube blank size is 160mm in outer diameter and 130mm in inner diameter;
step 9: machining the inner surface and the outer surface of the tube blank obtained in the step 8 to obtain a tube blank with the outer diameter of 155mm and the inner diameter of 135mm;
step 10: and (3) annealing the tube blank obtained in the step (9) in Ar gas atmosphere, wherein the annealing temperature is 1250 ℃, and the heat preservation time is 60 minutes, so that the uniform fine-grained tube with the grain size of 55-80 mu m and the grain size of 5 grades is obtained.
The tubular target obtained in the embodiment has no cracks and the yield is 100%.
Example 4:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with purity of 3N5 and granularity of 3.8 mu m; ni powder with purity of 3N and granularity of 3.5 mu m; tiH of purity 3N 2 Powder, particle size 3.2 μm; rhenium powder with purity of 4N and granularity of 2.8 mu m, according to the mass ratio of each element in the target material, mo: ni: ti: re=74:15:10:1, configured 150Kg; adding titanium into part of raw material molybdenum powder, adding the whole titanium hydride powder, then reducing the mixture for 4 hours at 800 ℃ in hydrogen atmosphere to obtain reduced molybdenum-titanium alloy powder (the mass ratio of molybdenum element to titanium element in the molybdenum-titanium alloy powder is 2:1), and adding the molybdenum-titanium alloy powder into the rest of powder to be mixed;
step 2: placing the powder obtained in the step 1 into a ball milling tank, pumping air to negative pressure according to a ball material ratio of 1:2, filling argon to one atmosphere, and mixing for 16 hours at a rotating speed of 200r/min;
step 3: placing the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, performing cold isostatic pressing, and maintaining the pressure for 10 minutes under 200 MPa;
step 4: shaping the CIP tubular pressed compact obtained in the step 3 to ensure that the geometry of the blank is complete;
step 5: putting the pressed compact after shaping in the step 4 into a sheath, and pumping air to 10 -2 Pa, maintaining air suction for 4 hours, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath in the step 5, wherein the heat preservation system is 930 ℃, the pressure is 150MPa, and the heat preservation and pressure maintaining time is 4 hours;
step 7: the sheath in the step 6 is machined and removed, so that the outer circular surface of the tube target is smooth, no bulge exists, the outer diameter of the tube blank is 220mm, and the inner diameter of the tube blank is 100mm;
step 8: placing the tube blank obtained in the step 7 into a muffle furnace, heating in air atmosphere, wherein the extrusion starting temperature is 1350 ℃, the heat preservation time is 90 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with the temperature before each pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1080 ℃, and the tube blank size is 165mm in outer diameter and 135mm in inner diameter;
step 9: machining the inner surface and the outer surface of the tube blank obtained in the step 8 to obtain a tube blank with the outer diameter of 160mm and the inner diameter of 140mm;
step 10: and (3) annealing the tube blank in the step (9) in Ar atmosphere at 1200 ℃ for 100 minutes to obtain the uniform fine-grained tube with the grain size of 70-100 μm and the grain size of 4-level.
The tube target material obtained in the embodiment has no cracks and the yield is 100%.
Example 5
Step 1, pure Mo powder with purity of 3N5 and granularity of 3.8 mu m; ni powder with purity of 3N and granularity of 2.4 mu m; 3N TiH2 powder with the granularity of 3.4 mu m; rhenium powder with purity of 4N and granularity of 4 mu m; cr is prepared from chromium powder with granularity of 3.5 mu m according to the mass ratio of Mo in the target material: ni: ti: re: cr=60:20:16:2:2, 140Kg of raw material was configured; adding titanium into part of raw material molybdenum powder, adding the whole titanium hydride powder, then reducing the mixture for 4 hours at 800 ℃ in hydrogen atmosphere to obtain reduced molybdenum-titanium alloy powder (the mass ratio of molybdenum element to titanium element in the molybdenum-titanium alloy powder is 1:1), and adding the molybdenum-titanium alloy powder into the rest of powder to be mixed;
the subsequent procedure is as in example 1.
The grain size of the obtained target material is 55-85 mu m, and the grain size is grade 5.
The tubular target obtained in the embodiment has no cracks and the yield is 100%.
Comparative example 1
The preparation method was the same as in example 1 except that the extrusion process parameters were different from example 1. The pass deformation in the extrusion molding process of this comparative example was 30%.
In the first pass of extrusion, surface cracks appear on the blank, and in the second pass of extrusion, the blank cracks.
The molybdenum alloy tube prepared in comparative example 1 has more cracks, and the crack part is required to be removed by machining, so that the utilization rate of the material is affected.
Comparative example 2
The preparation was the same as in example 1, except that rhenium was not added.
The molybdenum alloy tube target material prepared in comparative example 2 is difficult to deform, and is severely cracked in the first extrusion pass, so that deformation treatment cannot be performed.
Comparative example 3
The comparative example comprises the following components in mass ratio Mo: ni: ti: re=69:15:10:6, 140Kg of raw material was configured; the remainder was the same as in example 3.
The molybdenum alloy tube target prepared in the comparative example 3 has the advantages that the cost is greatly improved, the rhenium content is too high, the difficulty degree of deformation is increased, and cracks appear on the surface of the blank in the deformation process.
Meanwhile, when the Re content is large, re can form alloy phases with other elements, and the subsequent coating effect is affected.
Part of the grains have a size exceeding 100 μm and poor uniformity of grains.
The tube target of this comparative example had cracks with a yield of 50%.
Comparative example 4
The same as in example 1, except that the extrusion start temperature was 1500 ℃.
The extrusion of comparative example 4 was excessively high in starting temperature, nickel in the billet was partially melted, and the surface oxidation was severe, the thermoplastic properties of the billet were deteriorated, and the billet was cracked during extrusion.
Comparative example 5
The same as in example 1, except that the heating and holding temperature of each pass was lowered by 120℃based on the previous heating and holding temperature in the extrusion process of this comparative example.
The grain size of the tubular target obtained in this comparative example is 90 μm to 160 μm, and the uniformity of the grains is poor.
The pipe target material obtained by the embodiment has cracks, and the yield is less than 50%.
Comparative example 6
The same as in example 1, except that the annealing temperature was 1350 ℃.
The molybdenum alloy tube target prepared in comparative example 6 has larger crystal grain size of 120-200 μm and 1-3 grade grain size, mixed crystal appears, and larger crystal grains are locally arranged.
The present application is described in detail above. It will be obvious to those skilled in the art that the present application may be practiced in a wide variety of equivalent parameters, proportions, and conditions without departing from the spirit and scope of the application, and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. The application of some of the basic features may be done in accordance with the scope of the claims that follow.
Claims (14)
1. The preparation method of the molybdenum alloy tube target is characterized by comprising the following steps of:
mixing powder: respectively weighing raw materials according to the mass fraction of each element in the molybdenum alloy tube target material, and uniformly mixing to obtain molybdenum alloy powder; wherein, the molybdenum alloy tube target comprises Ni by mass percent: 10-30%, ti:5-25%, re: 0.5-5%, M:0-15% of M is at least one of Cr, zr, ta, nb, wherein M is used for replacing part of Ti, the balance is Mo and unavoidable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 50%;
cold isostatic pressing: placing the mixed powder into a die, and performing cold isostatic pressing to obtain a first blank;
hot isostatic pressing: performing hot isostatic pressing on the first blank to obtain a second blank;
extrusion molding: extruding and forming the second blank to obtain a third blank;
annealing: annealing the third blank;
the extrusion molding is cooling extrusion, the starting temperature of the extrusion molding is 1100-1400 ℃, and the ending temperature of the extrusion molding is 900-1100 ℃;
the extrusion deformation rate of each pass of extrusion is 15-25%, and the total deformation of extrusion molding is 40-80%.
2. The method of preparing a molybdenum alloy tube target as defined in claim 1, further comprising:
shaping: shaping the first blank after cold isostatic pressing;
and (3) covering: before the hot isostatic pressing, placing the shaped first blank into a sheath, and vacuumizing and sealing;
removing the sheath: machining the sheath of the second billet after the hot isostatic pressing;
machining: the third blank is machined prior to the annealing process.
3. The method for producing a molybdenum alloy tube target as defined in claim 2, wherein the molybdenum alloy tube target comprises, in mass percent, ni:10-30%, ti:5-25%, re:1-5%, M:0-5%, M is at least one of Cr, zr, ta, nb, M is used for replacing part of Ti, the balance is Mo and unavoidable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 60%.
4. The method for preparing a molybdenum alloy tube target as defined in claim 1, wherein in the powder mixing step, the raw materials include: molybdenum powder with purity more than or equal to 3N5 and Fisher particle size range of 2.5-4 mu m; nickel powder with purity not less than 3N and Fisher size range of 2-3 μm; the titanium source is titanium powder or titanium hydride, the purity of the titanium powder is more than or equal to 3N, the Fisher size range of the titanium powder is 2-4 mu m, the purity of the titanium hydride is more than or equal to 2N, and the Fisher size range of the titanium hydride is 2-4 mu m; and the purity of the rhenium powder is more than or equal to 4N, and the Fisher particle size of the rhenium powder is 2-4 mu m.
5. The method for producing a molybdenum alloy tube target as defined in claim 4, wherein the titanium element in the molybdenum alloy tube target is added in the form of molybdenum titanium alloy powder; the molybdenum-titanium alloy powder is obtained by mixing partial molybdenum powder in raw materials with titanium hydride powder and then carrying out reduction treatment.
6. The method for preparing a molybdenum alloy tube target according to claim 5, wherein the molybdenum-titanium alloy powder has a mass ratio of molybdenum to titanium of 90:10-70:30.
7. The method for preparing a molybdenum alloy tube target material according to claim 5,
in the process of preparing the molybdenum-titanium alloy powder, the reduction treatment is carried out in a hydrogen atmosphere, the temperature of the reduction treatment is 500-900 ℃, and the time of the reduction treatment is 2-8 hours.
8. The method for producing a molybdenum alloy tube target according to any one of claim 1 to 7,
the powder mixing is carried out in a ball milling tank, the ball material ratio is 1:1-2:1, argon is filled after the air is pumped to negative pressure, the argon pressure in the ball milling tank is one atmosphere, the mixing time is 10-16 h, and the rotating speed is 50-300 r/min;
in the cold isostatic pressing, the pressing pressure of the cold isostatic pressing is 150-200 MPa, and the pressure maintaining time is 5-20 minutes; and/or the mould is a tubular mould made of stainless steel;
the heat preservation temperature of the hot isostatic pressing is 900-980 ℃, the pressure is 100-170MPa, and the pressure maintaining time is 2-5h.
9. The method for preparing a molybdenum alloy tube target according to claim 8, wherein before each pass of extrusion, the second blank is put into a muffle furnace, heated in air or argon atmosphere, at a temperature of 1100-1400 ℃ for 30-120 minutes, and extruded for each pass after being discharged;
the temperature-reducing extrusion is specifically that the heating and heat-preserving temperature before the extrusion of the next time is sequentially lower than the heating and heat-preserving temperature before the extrusion of the previous time.
10. The method for preparing a molybdenum alloy tube target material according to claim 9,
the heating and heat preservation temperature before the extrusion of the next pass is reduced by more than 0 and less than or equal to 100 ℃ based on the heating and heat preservation temperature of the previous pass.
11. The method for preparing a molybdenum alloy tube target according to claim 8, wherein the annealing treatment is performed in an argon atmosphere at a temperature of 1000-1300 ℃ for a time of 60-120 minutes.
12. A molybdenum alloy tube target prepared by the method of any one of claims 1-11.
13. The molybdenum alloy tube target according to claim 12, wherein the molybdenum alloy tube target has a grain size of 100 μm or less and a grain size of 4-5 grades.
14. Use of the molybdenum alloy tube target according to claim 12 or 13, attached by sputtering to a main conductive layer of a laminated wiring film for an electronic component, which is a flat panel display, a thin film solar or a semiconductor device, to form a metal cover layer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210565049.6A CN114939661B (en) | 2022-05-23 | 2022-05-23 | Preparation method of molybdenum alloy tube target, molybdenum alloy tube target and application |
| PCT/CN2023/095630 WO2023208249A1 (en) | 2022-05-23 | 2023-05-22 | Preparation method for molybdenum alloy tube target material, molybdenum alloy tube target material, and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210565049.6A CN114939661B (en) | 2022-05-23 | 2022-05-23 | Preparation method of molybdenum alloy tube target, molybdenum alloy tube target and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114939661A CN114939661A (en) | 2022-08-26 |
| CN114939661B true CN114939661B (en) | 2023-11-03 |
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| CN115502403A (en) * | 2022-09-29 | 2022-12-23 | 宁波江丰电子材料股份有限公司 | Preparation method of large-size and high-density molybdenum target |
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