CN114892134A - Molybdenum alloy tube target material and preparation method and application thereof - Google Patents
Molybdenum alloy tube target material and preparation method and application thereof Download PDFInfo
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- CN114892134A CN114892134A CN202210567605.3A CN202210567605A CN114892134A CN 114892134 A CN114892134 A CN 114892134A CN 202210567605 A CN202210567605 A CN 202210567605A CN 114892134 A CN114892134 A CN 114892134A
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- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 70
- 239000013077 target material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 26
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 19
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 19
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 18
- 238000004544 sputter deposition Methods 0.000 claims abstract description 11
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 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
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 56
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 31
- 239000012298 atmosphere Substances 0.000 claims description 23
- 238000004321 preservation Methods 0.000 claims description 23
- DECCZIUVGMLHKQ-UHFFFAOYSA-N rhenium tungsten Chemical compound [W].[Re] DECCZIUVGMLHKQ-UHFFFAOYSA-N 0.000 claims description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 22
- 229910000691 Re alloy Inorganic materials 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 238000003754 machining Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 238000009924 canning Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000462 isostatic pressing Methods 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000005086 pumping Methods 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 241001377594 Rhene Species 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000280 densification 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
- 238000005530 etching Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011946 reduction process 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
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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
-
- 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
-
- 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
- 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
- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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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
- B22F3/20—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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Abstract
The application provides a molybdenum alloy tube target material and a preparation method and application thereof, belonging to the technical field of powder metallurgy. The target comprises the following components in percentage by mass: 10-30%, Ti: 5-25%, W: 1-20%, Re: 0.5-5%, M: 0-15 percent of Mo, wherein M is at least one of Cr, Zr, Ta and Nb, M is used for replacing partial Ti, the balance is Mo and inevitable impurities, the mass percent of Mo in the molybdenum alloy tube target material is not less than 50 percent, and the molybdenum alloy tube target material is prepared by the working procedures of cold isostatic pressing, sheathing, hot isostatic pressing, extrusion forming, annealing and the like. The target material provided by the application has the advantages of good plasticity and toughness, good deformability and fine and uniform crystal grains. The thickness distribution of the film sputtered and deposited by the target material prepared by the method is more uniform, and the film can be attached to the main conductive layer of the laminated wiring film for electronic components by a sputtering mode to form a metal covering layer and is used for flat panel displays, thin film solar energy, semiconductor devices and the like.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method of a molybdenum alloy tube target material, the molybdenum alloy tube target material and application.
Background
With the technological upgrading of flat display devices such as liquid crystal displays and display panels, it is necessary to reduce the resistance of wiring films. Meanwhile, with the increase in size of flat panel displays, large screens, high definition, and high-speed response, and flexible panels, a low level of film resistance is also required.
Thin Film Transistors (TFTs) are used as driving elements of display panels, and Al or Cu is used as a main wiring material. However, if Al or Cu is in direct contact with Si, thermal diffusion occurs during the manufacturing process due to thermal processing, so that the performance of the thin film transistor 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 is formed on the substrate and then sometimes left in the atmosphere for a long time. Meanwhile, when a signal cable is mounted on a display panel, heating in the atmosphere is sometimes required, and in a semiconductor film using an oxide, heating treatment in an aerobic atmosphere is required for performance improvement and stabilization. Therefore, there is a strong demand for enhancing the oxidation resistance of the laminated interconnection film. In addition, resin films used for portable, lightweight, flexible display panels have moisture permeability as compared with glass substrates, and therefore, laminated wiring films are required to have high moisture resistance. However, materials such as pure Mo and Mo-Ti have insufficient moisture resistance and oxidation resistance, and may be oxidized to significantly increase the resistance value of Al or Cu.
Patent CN2012102930608 discloses a molybdenum alloy target for a laminated wiring film, in which a certain amount of Ni and Ti is added to molybdenum in order to improve the moisture resistance and oxidation resistance of a pure molybdenum plating film, which contributes to stable production of electronic parts and improves reliability.
Patent CN2014100909230 discloses a molybdenum alloy target material for electronic components, wherein Ni is added to improve oxidation resistance, and W is added to improve moisture resistance.
Patent CN2017114460697 discloses a molybdenum alloy target material component containing elements such as Ni, Nb, Ti, etc., which can better improve the moisture resistance and oxidation resistance of pure molybdenum and keep low film resistance.
In the above patent, a certain amount of elements such as Ni, Ti, or W is added to the molybdenum substrate, thereby improving the moisture resistance and oxidation resistance of the molybdenum target sputtering film and maintaining a low resistance value. However, the preparation of the target material is mainly formed by Hot Isostatic Pressing (HIP), and as the length of the target material is increased, the size of the HIP forming is seriously limited by the size of HIP equipment, so that the high-performance molybdenum alloy target material cannot be produced in batch. Moreover, due to the poor formability of the molybdenum alloy target, tubular target products with different lengths cannot be prepared by deformation modes such as extrusion and forging.
Disclosure of Invention
In view of the above problems, an object of the present application is to provide a method for preparing a molybdenum alloy tube target, and uses thereof.
According to the molybdenum alloy tube target material, after the rhenium element is added, the plasticity and toughness of the target material are improved, and the deformation processing capacity of the target material is improved. The molybdenum alloy tube target material can be subjected to extrusion forming in the subsequent preparation process to refine the grain size. In addition, considering that the price of rhenium is expensive, the target material effectively improves the performance and the processing capacity of the target material by adding a small amount of rhenium to be matched with other components.
In order to achieve the purpose, the following technical scheme is adopted in the application:
the application provides a molybdenum alloy tube target material in a first aspect, which comprises the following components in percentage by mass: ni: 10-30% (e.g., 15%, 20%, 25%), Ti: 5-25% (e.g., 6%, 8%, 10%, 15%, 20%), W: 1-20% (e.g., 1.5%, 2%, 3%, 5%, 7%, 10%, 13%, 16%, 18%), Re: 0.5-5% (e.g., 0.7%, 1%, 2%, 3%, 4%), M: 0-15% (e.g., 0.5%, 1%, 3%, 5%, 8%, 10%, 13%), M is at least one of Cr, Zr, Ta, Nb, the M is used in place of a part of Ti, the balance is Mo and inevitable impurities, and the content of Mo in the molybdenum alloy tube target is not less than 50% by mass (e.g., 52%, 60%, 70%).
Ni can improve the oxidation resistance of the rete formed by this application target, and Ti can improve the moisture resistance of rete, and the oxidation resistance and the moisture resistance of rete not only can be guaranteed in the proper amount addition of the two, can also guarantee the low resistance of distribution membrane, do not influence the etching speed of etchant.
According to the molybdenum alloy tube target material, a small amount of Re element is added, and the addition of the rhenium element with a specific proportion and other elements with a specific proportion in the molybdenum alloy act together, so that rhenium plays a 'rhenium effect' in the molybdenum alloy, the room temperature plasticity of the molybdenum alloy is improved, the plastic-brittleness transition temperature is reduced, grains are refined, and the like. The Re element is added into the molybdenum alloy tube target, so that the deformation performance of the target can be improved, cracks can not be generated during large-deformation processing, the grain size difference of the target obtained by the optimized molybdenum alloy component proportion is very small due to the fine grain size of the target tissue, the grains are uniform, the thickness of a film layer prepared by the target provided by the application is more uniform, and the sputtering speed is higher. When the amount of Re exceeds 5%, on the one hand, the cost increases, and on the other hand, when the amount of Re is excessively added, Re may form an alloy phase with other elements, affecting the effect of subsequent plating. When the dosage of the Re element is less than 0.5 percent, the effects of effectively refining crystal 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 film, can be used for partially replacing Ti with the same moisture resistance, and can also improve the oxidation resistance of the target coating film. However, from the viewpoint of interaction of the various components in the target, it is preferable that the element M be only partially substituted for Ti.
In the molybdenum alloy tube target material, the W element not only has the effect of enhancing the moisture resistance, but also can strengthen the rhenium effect and further refine grains, and the Re element can play the rhenium effect in molybdenum and tungsten, thereby playing the roles of improving the room temperature plasticity of the material, reducing the plastic-brittle transition temperature, refining grains and the like and improving the deformation performance of the target material. In addition, the W element can improve the comprehensive properties of the film formed by the target material, such as heat resistance.
Preferably, the molybdenum alloy tube target material 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%, 13%, 16%, 19%, 22%), W: 1-10% (e.g., 2%, 4%, 6%, 8%), Re: 1-5% (e.g., 1.5%, 2.0%, 2.5%, 3%, 3.5%, 4%, 4.5%), M: 0-5% (e.g., 0.5%, 1%, 2%, 3%, 4%), and the balance of Mo and inevitable impurities, and the content of Mo in the molybdenum alloy tube target is not less than 60% by mass (e.g., 61%, 70%, 75%, 80%).
Under the preferable composition range, the various performances of the molybdenum alloy tube target are better.
The second aspect of the present application provides a method for preparing the molybdenum alloy tube target, which comprises the following steps:
mixing powder: respectively weighing the raw materials according to the mass fractions of the elements in the molybdenum alloy tube target material, and uniformly mixing to obtain molybdenum alloy powder;
cold isostatic pressing: putting the mixed powder into a die, and carrying out cold isostatic pressing to obtain a first blank;
shaping: shaping the first blank;
and (3) canning: placing the shaped first blank into a sheath, and vacuumizing and sealing;
hot isostatic pressing forming: carrying out hot isostatic pressing on the first billet with the sheath to obtain a second billet;
removing the sheath: machining away the wrapper of the second blank;
extrusion molding: carrying out extrusion forming on the second blank without the sheath to obtain a third blank;
annealing treatment: and annealing the third blank to obtain the finished molybdenum alloy target.
In some embodiments, the method for preparing a molybdenum alloy tube target further comprises:
machining: machining the third billet prior to the annealing treatment.
In some embodiments, in the step of mixing, the raw materials comprise: the purity of the molybdenum powder is more than or equal to 3N5, and the Fisher particle 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 purity of the titanium powder is more than or equal to 3N, and the Fisher size range of the titanium powder is preferably 2-4 mu m; the purity of the tungsten powder is 3N5, and the Fisher particle size of the tungsten powder is preferably 2.0-3.0 mu m; rhenium source, for rhene powder or ammonium rhenate, the purity of rhene powder is greater than or equal to 4N, the fisher's granularity of rhene powder is preferably 2 ~ 4 mu m, the purity of ammonium rhenate is greater than or equal to 4N, the fisher's granularity of ammonium rhenate is preferably 2.0 ~ 4.0 mu m.
In some embodiments, the rhenium element in the molybdenum alloy tube target is added in the form of a tungsten-rhenium alloy powder; the tungsten-rhenium alloy powder is obtained by mixing all tungsten powder in raw materials with ammonium rhenate and then carrying out reduction treatment;
preferably, the tungsten-rhenium mass ratio of the tungsten-rhenium alloy powder is 85: 15-50: 50 (such as 80: 20, 70:30 and 60: 40).
Preferably, in the process of preparing the tungsten-rhenium alloy powder, the reduction treatment is carried out in a hydrogen atmosphere, the temperature of the reduction treatment is 500-900 ℃ (for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃), and the time of the reduction treatment is 2-8 h (for example, 3h, 4h, 5h, 6h, 7 h).
In the hydrogen reduction treatment, the gas flow is determined according to the size of the reduction furnace, and the pressure is micro-positive pressure. Ammonium rhenate is selected as a rhenium source so as to enable the prepared tungsten-rhenium powder to be more uniform and consistent; the rhenium powder can also be directly used as a source for directly mixing materials, but the uniformity of the powder is not as good as that of the reduction process of the tungsten powder doped with the ammonium rhenate.
In some embodiments, the mixing is performed in a ball milling tank, the ball-to-material ratio is 1:1 to 2:1, the air is pumped to a negative pressure, then argon is filled, preferably, the argon pressure in the ball milling tank is one atmosphere, the mixing time is 10h to 16h (for example, 12h and 14h), and the rotating speed is 50 to 300 r/min.
In some embodiments, the cold isostatic pressing is performed at a pressing pressure of 150 to 200MPa and a dwell time of 5 to 20 minutes. Preferably, the mold is a tubular mold made of stainless steel.
The cold isostatic pressing process can enable the relative density of the first blank to be 55-65%.
In some embodiments, the holding temperature for hot isostatic pressing is 900 ℃ to 980 ℃ (e.g., 930 ℃, 960 ℃), the pressure is 100-.
The hot isostatic pressing process of the present application may provide 100% densification of the second billet formed of certain molybdenum alloy components.
For the situation that the density of the blank can not reach 100% only by the hot isostatic pressing process, a high-temperature sintering step can be added between the hot isostatic pressing forming step and the cold isostatic pressing forming step so as to improve the sintering effect of alloy components and further improve the density of the blank.
In some embodiments, the extrusion is a reduced temperature extrusion, the extrusion starting temperature being 1100-1400 ℃ (e.g., 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃) and the extrusion ending temperature being 900-. Before each-pass extrusion, the second blank is placed into a muffle furnace, heated in air or argon atmosphere, kept at the temperature of 1100-1400 ℃ (for example, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and 1350 ℃) for 30-120 minutes (for example, 40 minutes, 50 minutes, 70 minutes, 90 minutes and 110 minutes), and the extrusion of each pass is started after the second blank is taken out of the furnace.
The temperature-reducing extrusion is that the heating and heat-preserving temperature before the next extrusion is lower than the heating and heat-preserving temperature before the previous extrusion;
preferably, the heating and holding temperature before the next extrusion is decreased by more than 0 ℃ and less than or equal to 100 ℃ (e.g., 10 ℃, 20 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃) based on the heating and holding temperature before the previous extrusion;
preferably, the extrusion deformation rate per pass of the extrusion is 15-25% (e.g. 17%, 19%, 23%) and the total deformation of the extrusion is 40-80% (e.g. 45%, 50%, 60%, 70%, 75%).
The extrusion starting temperature is controlled within the range of 1100-1400 ℃, and the extrusion molding effect is better. When the extrusion starting temperature is too high, nickel is melted and causes severe oxidation, and when the extrusion starting temperature is low, a billet is prone to cracking in the extrusion forming process. The extrusion molding finishing temperature is controlled at 900-1100 ℃ 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 that the good strength and plasticity of the material are maintained, and the cracking is avoided.
In some embodiments, the annealing is performed under an argon atmosphere at an annealing temperature of 1000 to 1300 ℃ (e.g., 1050 ℃, 1100 ℃, 1200 ℃) and an annealing hold time of 60 to 120 minutes (e.g., 70 minutes, 80 minutes, 90 minutes, 110 minutes).
The annealing temperature is controlled within the range, so that the anisotropy of the extruded target material can be eliminated, and the molybdenum alloy tube target material with uniform structure and fine grains is obtained. When the annealing temperature is lower than 1000 ℃, the structure of the target material can not be fully recrystallized, partial crystal grains are still in a deformation state, the structure of the target material is uneven, and when the annealing temperature is higher than 1300 ℃, the crystal grains grow abnormally, mixed crystals occur, and the subsequent sputtering coating effect of the target material is influenced.
In some embodiments, after the annealing treatment, a uniform fine-grained target material 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 to 5 grades can be obtained.
The molybdenum alloy tube target material prepared by the method has fine crystal grains, and the sputtering rate is higher than that of a target with coarse crystal grains. And the grain size of the target material has smaller difference (even distribution), and the thickness distribution of the film sputtered and deposited by the target is more even. The quality of the film obtained by sputtering the molybdenum alloy tube target material prepared by the method can be greatly improved.
The third aspect of the application provides the 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 an electronic component by sputtering to form a metal coating layer, wherein the electronic component is a flat panel display, a thin film solar device or a semiconductor device.
Compared with the prior art, the beneficial effects of this application are:
1) after the 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.
2) The molybdenum alloy tube target material can be subjected to extrusion forming in the subsequent preparation process, so that the grain size can be refined, and a uniform fine-grain target material with the grain size of less than or equal to 100 mu m and the grain size of 4-5 grades can be obtained.
3) According to the method, a small amount of rhenium is added to be matched with other components, so that the effect of improving the performance and the processing capacity of the target material is effectively achieved.
4) The molybdenum alloy tube target material prepared by the method has fine crystal grains, and the sputtering rate is higher than that of a target with coarse crystal grains. Moreover, the grain size of the target material has smaller difference (even distribution), and the thickness distribution of the film deposited by target sputtering is more even. The quality of the film obtained by sputtering the molybdenum alloy tube target material prepared by the method can be greatly improved.
Drawings
Fig. 1 is a schematic microstructure and morphology of a molybdenum alloy tube target prepared in an embodiment of the present application.
Detailed Description
The following examples further illustrate the content of the present application in detail, and the scope of the present application includes but is not limited to the following examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The medicines or instruments used are not indicated by manufacturers, and are all conventional products which can be obtained commercially.
Re element can play a 'rhenium effect' in molybdenum and tungsten, improve the room temperature plasticity of materials, reduce the plastic-brittle transition temperature, refine grains and the like, the deformation performance of the target can be improved by adding the Re element and the W element in the molybdenum alloy tube target, large-size plate-shaped targets can be prepared by extrusion and other deformation modes, and the uniform and fine-grained targets can be obtained by annealing treatment.
The present application will be described in detail below with reference to specific examples.
Unless otherwise specified, the powder particle sizes indicated in the following examples are all the Fisher's particle sizes, and the proportions are mass ratios.
The standard for testing the grain size level in the embodiment of the application is GB/T6394 Metal average grain size determination method.
The following examples refer to the yield as the number of acceptable tube blanks after extrusion deformation/the number of hot-pressed blanks subjected to extrusion deformation 100%.
Example 1:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with the purity of 3N5 and the granularity of 3.5 mu m; ni powder with the purity of 3N and the granularity of 3.2 mu m; ti powder with the purity of 3N and the granularity of 3.7 mu m; tungsten powder with the purity of 3N5 and the granularity of 2.5 mu m; ammonium rhenate with purity of 4N and granularity of 4 mu m, wherein the ammonium rhenate is prepared from the following raw materials in percentage by mass: ni: ti: w: 140Kg of raw material was prepared with Re 60:20:18:1: 1. Adding rhenium into all tungsten powder, namely adding all ammonium rhenate (the mass ratio of the tungsten powder to the rhenium powder in the tungsten-rhenium alloy powder is 1: 1), reducing for 3 hours at 850 ℃ in a hydrogen atmosphere to obtain reduced tungsten-rhenium alloy powder, and adding the tungsten-rhenium alloy powder into the rest powder to be mixed;
step 2: putting the powder obtained in the step 1 into a ball milling tank, wherein the ball material ratio is 1:1, pumping to negative pressure, filling argon to one atmosphere, mixing for 10 hours, and rotating at the speed of 200 r/min;
and step 3: putting the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, and performing Cold Isostatic Pressing (CIP) under 150MPa for 15 minutes;
and 4, step 4: shaping the CIP tubular pressed blank obtained in the step 3 to ensure that the blank has regular and complete geometric dimension;
and 5: putting the pressed blank shaped in the step 4 into a sheath, and exhausting air to 10 DEG -1 Pa, keeping pumping for 6h, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath obtained in the step 5, wherein the heat preservation temperature is 930 ℃, the pressure is 130MPa, and the heat preservation and pressure maintaining time is 4 hours;
and 7: removing the sheath in the step 6 by machining to ensure that the outer circular surface of the tube target is flat and has no bulge, and the outer diameter of the tube blank is 240mm and the inner diameter is 200 mm;
and 8: putting the tube blank obtained in the step 7 into a muffle furnace, heating the tube blank in an 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 that of the previous pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1100 ℃, and the tube blank has the outer diameter of 165mm and the inner diameter of 130 mm;
and 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 135 mm;
step 10: and (4) annealing the tube blank obtained in the step (9) in Ar atmosphere at the annealing temperature of 1200 ℃ for 60 minutes to obtain the uniform fine-grained tube with the grain size of 70-100 mu m and the grain size of 4 grade.
The tube target obtained in this example had no cracks, and the yield was 100%.
Example 2:
a molybdenum alloy tube target and a preparation method thereof comprise the following steps:
step 1: pure Mo powder with the purity of 3N5 and the granularity of 3.8 mu m; ni powder with the purity of 3N and the granularity of 2.4 mu m; ti powder with the purity of 3N and the granularity of 3.0 mu m; tungsten powder with the purity of 3N5 and the granularity of 2.5 mu m; ammonium rhenate with purity of 4N, granularity of 3.5 mu m, Mo: ni: ti: w: preparing 140Kg of raw material, namely Re 68:15:10:5:2, wherein the rhenium is added by adding all ammonium rhenate into all tungsten powder (the mass ratio of the tungsten powder to the rhenium powder in the tungsten-rhenium alloy powder is 5: 2), reducing for 4 hours at 750 ℃ in hydrogen atmosphere to obtain reduced tungsten-rhenium alloy powder, and adding the tungsten-rhenium alloy powder into the rest of powder to be mixed;
step 2: putting the powder obtained in the step 1 into a ball milling tank, wherein the ball material ratio is 1:2, pumping to negative pressure, filling argon to one atmosphere, mixing for 12h, and rotating at the speed of 200 r/min;
and step 3: putting the mixed powder obtained in the step 2 into a tubular die made of stainless steel, and performing Cold Isostatic Pressing (CIP) under the pressure of 200MPa for 10 minutes;
and 4, step 4: shaping the CIP tubular pressed blank obtained in the step 3 to ensure that the blank has regular and complete geometric dimension;
and 5: putting the pressed blank shaped in the step 4 into a sheath, and exhausting air to 10 DEG -1 Pa, keeping pumping for 5 hours, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath obtained in the step 5, wherein the heat preservation temperature is 920 ℃, the pressure is 130MPa, and the heat preservation and pressure maintaining time is 3 h;
and 7: removing the sheath in the step 6 by machining to ensure that the outer circular surface of the tube target is flat and has no bulge, and the outer diameter of the tube blank is 240mm and the inner diameter is 140 mm;
and 8: putting the tube blank obtained in the step 7 into a muffle furnace, heating the tube blank in an air atmosphere, wherein the extrusion starting temperature is 1350 ℃, the heat preservation time is 100 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with that of the previous pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1080 ℃, and the size of the tube blank is 150mm in outer diameter and 120mm in inner diameter;
and 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 140mm and the inner diameter of 125 mm;
step 10: and (3) annealing the tube blank obtained in the step (9) under Ar atmosphere at the annealing temperature of 1150 ℃ for 120 minutes to obtain the uniform fine-grained tube with the grain size of 60-90 mu m and the grain size of 4-5 grades.
The tubular target obtained by the embodiment has no crack, 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 the purity of 3N5 and the granularity of 3.2 mu m; ni powder with the purity of 3N and the granularity of 3.5 mu m; ti powder with the purity of 3N and the granularity of 3.5 mu m; tungsten powder with the purity of 3N5 and the granularity of 3.2 mu m; ammonium rhenate with purity of 4N, granularity of 3.5 mu m, Mo: ni: ti: w: preparing 70Kg of raw material, wherein the Re is 65:15:10:5:5, adding rhenium into all tungsten powder, adding all ammonium rhenate (according to the mass ratio of the tungsten powder to the rhenium powder in the tungsten-rhenium alloy powder being 5: 5), reducing for 3h at 800 ℃ in hydrogen atmosphere to obtain reduced tungsten-rhenium alloy powder, and adding the tungsten-rhenium alloy powder into the rest powder to be mixed;
step 2: putting the powder obtained in the step 1 into a ball milling tank, wherein the ball material ratio is 1:1, pumping to negative pressure, filling argon to one atmosphere, mixing for 13h, and rotating at the speed of 200 r/min;
and step 3: putting the mixed powder obtained in the step 2 into a tubular mold made of stainless steel, and performing Cold Isostatic Pressing (CIP) under 150MPa for 10 minutes;
and 4, step 4: shaping the CIP tubular pressed blank obtained in the step 3 to ensure that the blank has regular and complete geometric dimension;
and 5: putting the pressed blank shaped in the step 4 into a sheath, and exhausting air to 10 DEG -2 Pa, keeping pumping for 4h, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath obtained in the step 5, wherein the heat preservation temperature is 940 ℃, the pressure is 150MPa, and the heat preservation and pressure maintaining time is 4 h;
and 7: removing the sheath machine in the step 6 to ensure that the outer circular surface of the tube target is flat and has no bulge, and the outer diameter of the tube blank is 230mm, and the inner diameter of the tube blank is 150 mm;
and 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 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 that of the previous pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1050 ℃, and the outer diameter of the obtained tube blank is 160mm, and the inner diameter is 120 mm;
and 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 125 mm;
step 10: and (3) annealing the tube blank obtained in the step (9) under Ar atmosphere at the annealing temperature of 1200 ℃ for 90 minutes to obtain the uniform fine-grained tube with the grain size of 65-90 mu m and the grain size of 4 grade.
The tubular target obtained by the embodiment has no crack, 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 the purity of 3N5 and the granularity of 3.8 mu m; ni powder with the purity of 3N and the granularity of 3.5 mu m; ti powder with the purity of 3N and the granularity of 3.2 mu m; tungsten powder with the purity of 3N5 and the granularity of 2.5 mu m; rhenium powder with the purity of 4N and the granularity of 2.8 mu m is prepared from the following raw materials in percentage by mass: ni: ti: w: preparing 200Kg of raw material with Re being 62:15:10:10: 3;
step 2: putting the powder obtained in the step 1 into a ball milling tank, wherein the ball material ratio is 1:1, pumping to negative pressure, filling argon to one atmosphere, mixing for 14h, and rotating at the speed of 200 r/min;
and step 3: putting the mixed powder obtained in the step 2 into a tubular die made of stainless steel, and performing Cold Isostatic Pressing (CIP) under the pressure of 200MPa for 10 minutes;
and 4, step 4: shaping the CIP tubular pressed blank obtained in the step 3 to ensure that the blank has regular and complete geometric dimension;
and 5: putting the pressed blank shaped in the step 4 into a sheath, and exhausting air to 10 DEG -1 Pa, keeping pumping for 6h, and sealing;
step 6: performing Hot Isostatic Pressing (HIP) on the sheath obtained in the step 5, wherein the heat preservation temperature is 960 ℃, the pressure is 140MPa, and the heat preservation and pressure maintaining time is 3 h;
and 7: removing the sheath in the step 6 by machining to ensure that the outer circular surface of the tube target is flat and has no bulge, and the outer diameter of the tube blank is 240mm and the inner diameter is 160 mm;
and 8: putting 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 110 minutes, the extrusion deformation rate of each pass is 15-25%, the heat preservation temperature before each pass is reduced by 50 ℃ compared with that of the previous pass, the heat preservation time before each pass is 90 minutes, the extrusion deformation finishing temperature is about 1100 ℃, and the size of the tube blank is 170mm in outer diameter and 130mm in inner diameter;
and 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 165mm and the inner diameter of 135 mm;
step 10: and (4) annealing the tube blank obtained in the step (9) in Ar atmosphere at 1250 ℃ for 60 minutes to obtain a uniform fine-grain tube with the grain size of 65-95 mu m and the grain size of 4 grade.
The tubular target obtained by the embodiment has no crack, and the yield is 100%.
Example 5
Step 1, pure Mo powder with the purity of 3N5 is subjected to granularity of 3.8 mu m; ni powder with the purity of 3N and the granularity of 2.4 mu m; ti powder with the purity of 3N and the granularity of 3.0 mu m; tungsten powder with the purity of 3N5 and the granularity of 2.5 mu m; ammonium rhenate with purity of 4N and granularity of 3.5 microns; cr powder with the purity of 3N and the granularity of 3.5 mu m is prepared according to the mass ratio of Mo: ni: ti: w: re: preparing 140Kg of raw material with Cr being 60:20:16:1:1: 2; the rhenium is added by adding all ammonium rhenate into all tungsten powder (the mass ratio of the tungsten powder to the rhenium powder in the tungsten-rhenium alloy powder is 1: 1), reducing for 3 hours at 850 ℃ in a hydrogen atmosphere to obtain reduced tungsten-rhenium alloy powder, and adding the tungsten-rhenium alloy powder into the rest of powder to be mixed.
The subsequent steps were the same as in example 1.
The grain size of the obtained target material is 60-90 mu m, and the grain size is 4-5 grade.
The tubular target obtained by the embodiment has no crack, and the yield is 100%.
Comparative example 1
The preparation method was the same as example 1 except that the extrusion molding 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 forming, the blank has surface cracks, and in the second pass of extrusion forming, the blank cracks.
The molybdenum alloy tube target prepared in the comparative example 1 has more cracks, and the cracked part needs to be machined and removed, so that the utilization rate of the material is influenced.
Comparative example 2
The preparation method was the same as in example 1 except that no rhenium element was added.
The molybdenum alloy target material prepared in the comparative example 2 is difficult to deform, and can be seriously cracked in the first extrusion process, so that deformation treatment cannot be carried out.
Comparative example 3
The comparative example is that Mo: ni: ti: w: re 55:20:18: 1: 6, preparing 140Kg of raw material; the rest is the same as in example 1.
The molybdenum alloy target material prepared in the comparative example 3 has the advantages that the cost is greatly improved, the rhenium content is too high, the deformation difficulty is increased, and cracks are easy to appear on the surface of the blank material in the deformation process. The grain size of part of the grains exceeds 100 μm, and the uniformity of the grains is poor.
Meanwhile, when the Re content is high, the Re can form an alloy phase with other components to influence the subsequent film coating effect.
The tube target of this comparative example had cracks, and the yield was 50%.
Comparative example 4
The same as in example 1 except for the extrusion initiation temperature of 1500 ℃.
The extrusion start temperature of comparative example 4 was too high, nickel in the billet was locally melted, and surface oxidation was severe, the thermoplasticity of the billet was deteriorated, and the billet was cracked during extrusion.
Comparative example 5
The same as example 1, except that in the extrusion process of the present comparative example, the temperature of the heating and holding temperature in each pass was decreased by 120 ℃ based on the temperature of the previous heating and holding temperature.
The grain size of the tubular target obtained by the comparative example is 100-160 mu m, and the grain uniformity is poor.
The tube target obtained in this example had cracks, and the yield was less than 50%.
Comparative example 6
The only difference is that the annealing temperature is 1350 deg.c, as in example 1.
The molybdenum alloy tube target prepared by the comparative example 6 has larger grain size of 120-200 mu m, grain size of 2-3 grade, mixed crystal and larger grains locally.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, proportions, and conditions without departing from the spirit and scope of the application and without undue experimentation. While this application has been given specific examples, it will be appreciated that further modifications may be made. In general, this application is intended to cover any variations, uses, or adaptations of the invention 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 invention pertains. The use of some of the essential features is possible within the scope of the claims attached below.
Claims (10)
1. The molybdenum alloy tube target is characterized by comprising the following components in percentage by mass: 10-30%, Ti: 5-25%, W: 1-20%, Re: 0.5-5%, M: 0-15%, wherein M is at least one of Cr, Zr, Ta and Nb, the M is used for replacing part of Ti, the balance is Mo and inevitable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 50%.
2. The molybdenum alloy tube target according to claim 1, which comprises, in mass percent, Ni: 10-30%, Ti: 5-25%, W: 1-10%, Re: 1-5%, M: 0-5%, wherein M is at least one of Cr, Zr, Ta and Nb, M is used for replacing part of Ti, and the balance is Mo and inevitable impurities, and the mass percentage content of Mo in the molybdenum alloy tube target is not less than 60%.
3. A method for preparing a molybdenum alloy tube target according to any one of claims 1 to 2, comprising the steps of:
mixing powder: weighing the raw materials according to the mass fractions of the elements in the molybdenum alloy tube target material of claim 1 or 2, and uniformly mixing to obtain molybdenum alloy powder;
cold isostatic pressing: putting the mixed powder into a die, and carrying out cold isostatic pressing to obtain a first blank;
hot isostatic pressing forming: carrying out hot isostatic pressing on the first billet to obtain a second billet;
extrusion molding: carrying out extrusion forming on the second blank to obtain a third blank;
annealing treatment: and annealing the third blank.
4. The method for preparing a molybdenum alloy target according to claim 3, further comprising:
shaping: shaping the first blank after the cold isostatic pressing;
and (3) canning: before the hot isostatic pressing forming, placing the shaped first blank into a sheath, and vacuumizing and sealing;
removing the sheath: machining the envelope of the second billet after the hot isostatic pressing;
machining: machining the third billet prior to the annealing treatment.
5. The method for preparing a molybdenum alloy target according to claim 3,
in the powder mixing step, the raw materials comprise: the purity of the molybdenum powder is more than or equal to 3N5, and the Fisher particle 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 purity of the titanium powder is more than or equal to 3N, and the Fisher size range of the titanium powder is preferably 2-4 mu m; the purity of the tungsten powder is 3N5, and the Fisher particle size of the tungsten powder is preferably 2.0-3.0 mu m; the rhenium source is rhenium powder or ammonium rhenate, the purity of the rhenium powder is more than or equal to 4N, the Fisher particle size of the rhenium powder is preferably 2-4 mu m, the purity of the ammonium rhenate is more than or equal to 4N, and the Fisher particle size of the ammonium rhenate is preferably 2.0-4.0 mu m;
preferably, the rhenium element in the molybdenum alloy tube target is added in the form of tungsten-rhenium alloy powder; the tungsten-rhenium alloy powder is obtained by mixing all the tungsten powder in raw materials with the ammonium rhenate and then carrying out reduction treatment;
preferably, the tungsten-rhenium mass ratio of the tungsten-rhenium alloy powder is 85: 15-50: 50;
preferably, in the process of preparing the tungsten-rhenium 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.
6. The method for preparing a molybdenum alloy target according to any one of claims 3 to 5,
the powder mixing is carried out in a ball milling tank, the ball material ratio is 1: 1-2: 1, the argon is filled after the air is pumped to the negative pressure, the argon pressure in the ball milling tank is preferably 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; preferably, the mold is a tubular mold made of stainless steel;
the heat preservation temperature of the heat isostatic pressing molding is 900-980 ℃, the pressure is 100-.
7. The method for preparing the molybdenum alloy target material as claimed in claim 6, wherein the extrusion molding is cooling extrusion, the extrusion molding starting temperature is 1100-1400 ℃, and the extrusion molding finishing temperature is 900-1100 ℃; and
before each-pass extrusion, the second blank is placed into a muffle furnace, heated in air or argon atmosphere at the temperature of 1100-1400 ℃, and subjected to heat preservation for 30-120 minutes, and the extrusion of each pass is started after the second blank is discharged;
the cooling extrusion is that the heating and heat-preserving temperature before the next extrusion is sequentially lower than the heating and heat-preserving temperature before the previous extrusion;
preferably, the heating and heat-preserving temperature before the next extrusion is reduced by more than 0 to less than or equal to 100 ℃ on the basis of the heating and heat-preserving temperature of the previous extrusion;
preferably, the extrusion deformation rate of each pass of the extrusion is 15-25%, and the total deformation amount of the extrusion forming is 40-80%.
8. The method for preparing the molybdenum alloy target according to claim 7, wherein the annealing treatment is performed in an argon atmosphere, the annealing temperature is 1000-1300 ℃, and the annealing heat preservation time is 60-120 minutes.
9. The method for preparing a molybdenum alloy target according to claim 8, wherein a uniform fine-grained target having a grain size of 100 μm or less and a grain size of 4-5 levels can be obtained.
10. Use of a molybdenum alloy tube target prepared by the method for preparing a molybdenum alloy tube target according to any one of claims 3 to 9, wherein the molybdenum alloy tube target is attached by sputtering to a main conductive layer of a laminated wiring film for electronic components to form a metal coating layer, preferably the electronic components are flat panel displays, thin film solar devices or semiconductor devices.
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