CN116752105A - Titanium-niobium alloy target material and preparation method and application thereof - Google Patents
Titanium-niobium alloy target material and preparation method and application thereof Download PDFInfo
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- CN116752105A CN116752105A CN202310951307.9A CN202310951307A CN116752105A CN 116752105 A CN116752105 A CN 116752105A CN 202310951307 A CN202310951307 A CN 202310951307A CN 116752105 A CN116752105 A CN 116752105A
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- 229910001257 Nb alloy Inorganic materials 0.000 title claims abstract description 79
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000013077 target material Substances 0.000 title abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011812 mixed powder Substances 0.000 claims abstract description 23
- 238000007731 hot pressing Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000004321 preservation Methods 0.000 claims abstract description 20
- 238000005056 compaction Methods 0.000 claims abstract description 9
- 238000003754 machining Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000010955 niobium Substances 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000005477 sputtering target Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- -1 titanium aluminum niobium Chemical compound 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- 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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- 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
-
- 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
- C23C14/54—Controlling or regulating the coating process
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a titanium-niobium alloy target material, a preparation method and application thereof, wherein the preparation method of the titanium-niobium alloy target material comprises the following steps: (1) mixing titanium powder and niobium powder to obtain mixed powder; (2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and machining treatment in sequence to obtain the titanium-niobium alloy target; the vacuum hot-pressed sintering treatment in the step (2) comprises a first pressurizing treatment, a first heating treatment, a first keeping Wen Baoya treatment, a second heating treatment, a second heat-preserving pressure-maintaining treatment and a second pressurizing treatment which are sequentially carried out. According to the invention, the vacuum hot-pressing sintering treatment process is divided into the stages of multistage pressurization, temperature rise, heat preservation and pressure maintaining, so that the prepared titanium-niobium alloy target material is high in density and purity, and excellent in internal tissue structure, and can meet the high-performance requirement of being used as a sputtering target material.
Description
Technical Field
The invention relates to the technical field of sputtering target preparation, in particular to a titanium-niobium alloy target, and a preparation method and application thereof.
Background
The titanium-niobium alloy target has extremely high requirements on the purity, internal tissue structure, mechanical strength and appearance size of the target in the process of being used for semiconductor magnetron sputtering, and meanwhile, the components and the preparation process of the target play a decisive influence on each performance of the film.
The titanium-niobium alloy in the prior art is generally produced by smelting, continuous casting and rolling, but the melting point of niobium in the titanium-niobium alloy target is 2469 ℃ and the density is 8.57g/cm 3 While the active metallic titanium has a melting point of 1670 ℃ and a density of 4.50g/cm 3 The melting points and the densities of the two are greatly different, and the components are easy to be uneven when the titanium-niobium alloy is produced by adopting vacuum melting, so that the problem can be effectively solved by preparing a target blank by adopting a powder metallurgy sintering method.
CN 104557021a discloses a high-compactness titanium dioxide target and a preparation method thereof, wherein the target is prepared from the following raw materials in percentage by mass: 97.5 to 99.5 percent of titanium dioxide powder; 0.5 to 2.5 percent of activating agent niobium powder. The titanium dioxide target material is prepared through the working procedures of mixing, normal pressure sintering pretreatment, vacuum hot-pressing sintering. Due to the arrangement of the sintering process, the target material is easier to have the temperature and other requirements in the manufacturing process, the densification effect cannot be achieved, and the micro defects of air holes, uneven components and the like are generated in the target blank, so that the density of the alloy target material is still to be further improved.
CN 103614590a discloses a low-temperature high-strength fatigue-resistant titanium aluminum niobium alloy, which comprises the following components in percentage by mass: al 2.0-3.5 wt%, nb 12-16 wt% and Ti and inevitable impurity for the rest. CN 103692109a discloses a low-temperature high-strength titanium aluminum niobium alloy special welding wire, which comprises the following components in percentage by mass: 1.5 to 1.8 percent of Al, 10 to 11.5 percent of Nb, less than or equal to 0.10 percent of Fe, less than or equal to 0.05 percent of Si, less than or equal to 0.08 percent of C, less than or equal to 0.04 percent of N, less than or equal to 0.006 percent of H, less than or equal to 0.12 percent of O, and the balance of Ti. The alloy is produced by adopting a vacuum smelting technology, the requirement of an aluminum titanium niobium target material on the control of the microstructure grain size cannot be met, the internal components are easily uneven, and the titanium niobium alloy target material cannot be prepared by adopting the process.
Aiming at the defects of the prior art, the titanium-niobium alloy target material with high density, uniform internal components and high purity needs to be provided.
Disclosure of Invention
The invention aims to provide a titanium-niobium alloy target material, a preparation method and application thereof, wherein the mixed powder obtained by ball milling and mixing titanium powder and niobium powder is subjected to vacuum hot-pressing sintering, and various technological parameters in the vacuum hot-pressing sintering are controlled at the same time, so that the titanium-niobium alloy target material with high density, high purity and excellent internal tissue structure is prepared.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a titanium-niobium alloy target, which comprises the following steps:
(1) Mixing titanium powder and niobium powder to obtain mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and machining treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressed sintering treatment in the step (2) comprises a first pressurizing treatment, a first heating treatment, a first keeping Wen Baoya treatment, a second heating treatment, a second heat-preserving pressure-maintaining treatment and a second pressurizing treatment which are sequentially carried out.
According to the preparation method of the titanium-niobium alloy target, provided by the invention, the fact that the melting point and the density of titanium-niobium are greatly different is considered, the mixed powder obtained after the titanium powder and the niobium powder are subjected to ball milling is subjected to vacuum hot-pressing sintering, meanwhile, the vacuum hot-pressing sintering treatment process is divided into the stages of multistage pressurization, temperature rise, heat preservation and pressure maintaining, and the control of various technological parameters is combined, so that the prepared titanium-niobium alloy target is higher in density and purity, excellent in internal tissue structure and capable of meeting the high-performance requirement of being used as a sputtering target.
Preferably, the purity of the titanium powder in step (1) is > 99.98%, for example 99.985%, 99.99% or 99.995%, but not limited to the values recited, and other non-recited values within the range of values are equally applicable.
Preferably, the average particle size of the titanium powder in step (1) is less than 45. Mu.m, for example 40. Mu.m, 35. Mu.m, 30. Mu.m, 25. Mu.m, or 20. Mu.m, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the purity of the niobium powder in step (1) is > 99.95%, for example 99.96%, 99.97% or 99.98%, but not limited to the values recited, and other non-recited values within the range of values are equally applicable.
Preferably, the niobium powder in step (1) has an average particle size of < 60. Mu.m, for example 55. Mu.m, 50. Mu.m, 45. Mu.m, 40. Mu.m, or 35. Mu.m, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the mixing of step (1) is performed in an argon atmosphere.
The mixing is performed in an argon atmosphere to prevent air from affecting the purity of the powder, so that the purity of the prepared titanium-niobium alloy target is reduced.
Preferably, the mixed ball ratio in step (1) is 10 (1-3), and may be, for example, 10:1, 10:1.5, 10:2, 10:2.5 or 10:3, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the mixed powder balls of step (1) comprise hard zirconium balls and/or zirconium oxide balls.
Preferably, the mixing time of step (1) is not less than 48 hours, for example 48 hours, 49 hours, 50 hours, 51 hours or 52 hours, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The mixing time is controlled to be more than or equal to 48 hours, so that the mixed powder can be uniformly mixed without large particle agglomeration, and the mixing uniformity and the dispersibility can be reduced due to the short mixing time.
Preferably, the compacting treatment of step (2) is performed in a graphite mould.
The compaction treatment is as follows: and (3) filling the mixed powder into a graphite mold for compaction, then putting the graphite mold into a vacuum sintering furnace, and ensuring that the graphite mold is in a horizontal position after the vacuum sintering furnace is placed.
Preferably, the pressure of the first pressurization treatment in the step (2) is 5-20t, and the time is 2-10min.
The pressure of the first pressurizing treatment is 5-20t, for example, 5t, 8t, 10t, 15t or 20t, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The first pressure treatment time is 2-10min, for example, 2min, 4min, 6min, 8min or 10min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the step (2) further includes a step of vacuumizing to a vacuum degree of less than 100Pa after the first pressurizing treatment and before the first heating treatment, for example, 99Pa, 98Pa, 97Pa, 96Pa or 95Pa, but the method is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the first temperature increasing process of step (2) includes: heating to 1000-1100 deg.c at the heating rate of 5-10 deg.c/min.
The heating rate is 5-10deg.C/min, and may be, for example, 5deg.C/min, 6deg.C/min, 7deg.C/min, 8deg.C/min, or 10deg.C/min, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The temperature end point of the temperature rise is 1000 to 1100 ℃, for example, 1000 ℃, 1020 ℃, 1050 ℃, 1080 ℃, or 1100 ℃, but the temperature end point is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, in the step (2), the pressure in the first temperature raising treatment is greater than 50t, and the pressure relief treatment is performed.
In the first temperature raising process, the pressure in the die increases due to thermal expansion of the mixed powder, and therefore, in order to maintain the pressure stable, a pressure relief process is required when the pressure exceeds 50t.
The pressure > 50t in the first temperature increasing treatment may be, for example, 51t, 52t, 53t, 54t or 55t, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the temperature of the first protection Wen Baoya treatment in step (2) is 1000-1100 ℃, for example, 1000 ℃, 1020 ℃, 1050 ℃, 1080 ℃, or 1100 ℃, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the first protection Wen Baoya in step (2) is performed for a period of 60-90min, for example, 60min, 65min, 70min, 80min or 90min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the pressure of the first treatment Wen Baoya in step (2) is 48-50t, which may be 48t, 48.5t, 49t, 49.5t or 50t, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The first protection Wen Baoya is used for fully heating the titanium-niobium alloy green body, so that expansion still occurs in the process, pressure maintaining treatment is needed, the temperature, pressure and time are controlled within a reasonable range, the density of the prepared titanium-niobium alloy target material can be improved to some extent, and the density of the green body can be reduced beyond a limited range, so that performance is reduced.
Preferably, the second temperature increasing process of step (2) includes: raising the temperature to 1300-1500 ℃ at a heating rate of 1-5 ℃/min.
The heating rate is 1-5 deg.C/min, and may be, for example, 1 deg.C/min, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min or 5 deg.C/min, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The temperature end point of the temperature rise is 1300 to 1500 ℃, for example, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, or 1500 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the temperature of the second heat-preserving and pressure-maintaining treatment in the step (2) is 1300-1500 ℃, for example, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, or 1500 ℃, but the method is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the time of the second heat-preserving and pressure-maintaining treatment in the step (2) is more than or equal to 1h, for example, 1h, 1.5h, 2h, 2.5h or 3h, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable, preferably 1-2h.
Preferably, the pressure of the second heat-preserving and pressure-maintaining treatment in the step (2) is 48-50t, for example, 48t, 48.5t, 49t, 49.5t or 50t, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the second pressurizing treatment of step (2) includes: pressurizing to 290-310t in 2.9-3.1 h.
The pressurizing time is 2.9-3.1h, for example, 2.9h, 2.95h, 3h, 3.05h or 3.1h, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The pressure end point of the pressurization is 290-310t, for example, 290t, 295t, 300t, 305t or 310t, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the second pressurizing treatment in step (2) further comprises a step of removing the pressure.
Preferably, the pressure relief treatment includes: argon is introduced to the furnace pressure of-0.06 to-0.08 MPa, for example, -0.06MPa, -0.07MPa or-0.08 MPa, but the argon is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the pressure-removing treatment further comprises a step of cooling.
Preferably, the cooling comprises: cooling to the temperature of less than 200 ℃ along with the furnace, and then naturally cooling to the room temperature.
The furnace cooling to a temperature of < 200 ℃, for example, 195 ℃, 190 ℃, 185 ℃, 180 ℃ or 175 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the machining process of step (2) comprises grinding and/or wire cutting.
As a preferred technical scheme of the preparation method according to the first aspect of the present invention, the preparation method comprises the following steps:
(1) Mixing titanium powder with the purity of more than 99.98 percent, the average grain diameter of less than 45 mu m and niobium powder with the purity of more than 99.95 percent and the average grain diameter of less than 60 mu m for more than or equal to 48 hours in an argon atmosphere, wherein the ball ratio is 10 (1-3), and obtaining mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and machining treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressing sintering treatment in the step (2) comprises the steps of sequentially carrying out first pressurizing treatment for 2-10min at 5-20t, vacuumizing to a vacuum degree less than 100Pa, then heating to 1000-1100 ℃ at a heating rate of 5-10 ℃/min, wherein the pressure in the first heating treatment is more than 50t, and carrying out pressure relief treatment; treating the first heat preservation Wen Baoya at 1000-1100 ℃ and 48-50t for 60-90min, then heating to 1300-1500 ℃ at a heating rate of 1-5 ℃/min, and performing second heat preservation and pressure maintaining treatment at 1300-1500 ℃ and 48-50t for more than or equal to 1h; and (3) carrying out second pressurizing treatment for 290-310t within 2.9-3.1h, then introducing argon gas until the pressure in the furnace is-0.06-0.08 MPa, cooling to the temperature of less than 200 ℃ along with the furnace, and naturally cooling to the room temperature.
In a second aspect, the invention provides a titanium-niobium alloy target, which is prepared by the preparation method in the first aspect;
the mass percentage of niobium in the titanium-niobium alloy target is 1-20wt% and the balance is titanium.
The mass percentage of niobium in the titanium-niobium alloy target material is 1-20wt%, for example, 1wt%, 5wt%, 10wt%, 15wt% or 20wt%, but the titanium-niobium alloy target material is not limited to the listed values, and other non-listed values in the numerical range are applicable.
The density of the titanium-niobium alloy target material is more than or equal to 99%, the purity of the titanium-niobium alloy target material is more than or equal to 99.9%, and the internal structure of the titanium-niobium alloy target material is uniform by controlling the mass percentage ratio of niobium to titanium in the titanium-niobium alloy target material and combining the technological parameters of vacuum hot-pressing sintering treatment.
In a third aspect, the present invention provides the use of a titanium niobium alloy target as described in the second aspect for use in semiconductor magnetron sputtering.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method provided by the invention, the mixed powder obtained after ball milling and mixing of the titanium powder and the niobium powder is subjected to vacuum hot-pressing sintering, the vacuum hot-pressing sintering treatment process is divided into the stages of multistage pressurization, temperature rise, heat preservation and pressure maintaining, and the control of various technological parameters is combined, so that the prepared titanium-niobium alloy target material is higher in density, higher than or equal to 99.9% in purity, excellent in internal tissue structure and capable of meeting the high-performance requirement of being used as a sputtering target material.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a titanium-niobium alloy target, wherein the mass percentage of niobium in the titanium-niobium alloy target is 10wt%, and the balance is titanium.
The preparation method of the titanium-niobium alloy target comprises the following steps:
(1) Mixing titanium powder with the purity of 99.995 percent, the average grain diameter of 30 mu m and niobium powder with the purity of 99.98 percent and the average grain diameter of 45 mu m for 50 hours according to the formula amount in argon atmosphere, wherein the ball ratio is 10:2, and obtaining mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and grinding treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressing sintering treatment in the step (2) comprises the steps of sequentially carrying out first pressurizing treatment for 6min at 10t, vacuumizing to 97Pa, then heating to 1050 ℃ at the heating rate of 7 ℃/min, wherein the pressure in the first heating treatment is more than 50t, and carrying out pressure relief treatment; treating the first heat preservation Wen Baoya at 1050 ℃ and 49t for 70min, then heating to 1400 ℃ at a heating rate of 3 ℃/min, and performing second heat preservation and pressure maintaining treatment at 1400 ℃ and 49t for 2h; and (3) carrying out second pressurizing treatment to 300t within 3h, then introducing argon to the pressure of-0.07 MPa in the furnace, cooling to 185 ℃ along with the furnace, and naturally cooling to room temperature.
Example 2
The embodiment provides a titanium-niobium alloy target, wherein the mass percentage of niobium in the titanium-niobium alloy target is 1wt%, and the balance is titanium.
The preparation method of the titanium-niobium alloy target comprises the following steps:
(1) Mixing titanium powder with the purity of 99.99 percent, the average grain diameter of 20 mu m and niobium powder with the purity of 99.97 percent and the average grain diameter of 35 mu m for 52 hours according to the formula amount in argon atmosphere, wherein the ball ratio is 10:3, and obtaining mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and grinding treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressing sintering treatment in the step (2) comprises the steps of sequentially carrying out first pressurizing treatment for 10min at 5t, vacuumizing to the vacuum degree of 95Pa, then heating to 1000 ℃ at the heating rate of 5 ℃/min, wherein the pressure in the first heating treatment is more than 50t, and carrying out pressure relief treatment; treating at 1000 ℃ and 48t for 90min with a first heat preservation Wen Baoya, then heating to 1300 ℃ at a heating rate of 1 ℃/min, and treating at 1300 ℃ and 48t for 3h with a second heat preservation pressure maintaining; and (3) carrying out second pressurizing treatment to 290t within 2.9h, then introducing argon to the pressure of-0.06 MPa in the furnace, cooling to 175 ℃ along with the furnace, and naturally cooling to room temperature.
Example 3
The embodiment provides a titanium-niobium alloy target, wherein the mass percentage of niobium in the titanium-niobium alloy target is 20wt%, and the balance is titanium.
The preparation method of the titanium-niobium alloy target comprises the following steps:
(1) Mixing titanium powder with the purity of 99.985 percent, the average grain diameter of 40 mu m and niobium powder with the purity of 99.96 percent and the average grain diameter of 55 mu m for 48 hours according to the formula amount in argon atmosphere, wherein the ball ratio is 10:1, and obtaining mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and grinding treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressing sintering treatment in the step (2) comprises the steps of sequentially carrying out first pressurizing treatment for 2min at 20t, vacuumizing to the vacuum degree of 99Pa, then heating to 1100 ℃ at the heating rate of 10 ℃/min, wherein the pressure in the first heating treatment is more than 50t, and carrying out pressure relief treatment; treating at 1100 ℃ and 50t for 60min with a first heat preservation Wen Baoya, then heating to 1500 ℃ at a heating rate of 5 ℃/min, and treating at 1500 ℃ and 50t for 1h with a second heat preservation pressure maintaining; and (3) carrying out second pressurizing treatment to 310t within 3.1h, then introducing argon to the pressure of-0.08 MPa in the furnace, cooling to the temperature of 195 ℃ along with the furnace, and naturally cooling to the room temperature.
Example 4
The present embodiment provides a titanium-niobium alloy target, and the preparation method of the titanium-niobium alloy target is different from that of embodiment 1 in that the mixing time in step (1) is adjusted to 45h, and the rest is the same as that of embodiment 1.
Example 5
The present embodiment provides a titanium-niobium alloy target, and the preparation method of the titanium-niobium alloy target is different from that of embodiment 1 in that the temperature of the first protection Wen Baoya treatment in step (2) is adjusted to 950 ℃, and the rest is the same as that of embodiment 1.
Example 6
The present embodiment provides a titanium-niobium alloy target, and the preparation method of the titanium-niobium alloy target is different from that of embodiment 1 in that the temperature of the first protection Wen Baoya treatment in step (2) is adjusted to 1150 ℃, and the rest is the same as that of embodiment 1.
Example 7
The present embodiment provides a titanium-niobium alloy target, and the preparation method of the titanium-niobium alloy target is different from that of embodiment 1 in that the pressure of the second pressurizing treatment in step (2) is adjusted to 250t, and the rest is the same as embodiment 1.
Example 8
The present embodiment provides a titanium-niobium alloy target, and the preparation method of the titanium-niobium alloy target is different from that of embodiment 1 in that the pressure of the second pressurizing treatment in step (2) is adjusted to 320t, and the rest is the same as embodiment 1.
Comparative example 1
This comparative example provides a titanium-niobium alloy target, which is different from example 1 in that the first temperature raising treatment of step (2) and the first holding Wen Baoya treatment are not provided, and the rest is the same as example 1.
Comparative example 2
This comparative example provides a titanium-niobium alloy target, which is different from example 1 in that the second pressing treatment of step (2) is not provided, and the remainder is the same as example 1.
Comparative example 3
The comparative example provides a titanium-niobium alloy target, which is different from example 1 in that the mass percentage of niobium in the titanium-niobium alloy target is adjusted to 0.5wt% and the balance is titanium, and the preparation method of the titanium-niobium alloy target is the same as that of example 1.
Comparative example 4
The comparative example provides a titanium-niobium alloy target, which is different from example 1 in that the mass percentage of niobium in the titanium-niobium alloy target is adjusted to 23wt% and the balance is titanium, and the preparation method of the titanium-niobium alloy target is the same as that of example 1.
The titanium-niobium alloy targets provided in examples 1 to 8 and comparative examples 1 to 4 were subjected to density testing according to archimedes' displacement method and purity testing according to glow discharge mass spectrometry, and the results are shown in table 1; the internal structure uniformity of the titanium-niobium alloy target was observed by a scanning electron microscope, and the results were classified into three classes, namely "uniform", "relatively uniform" and "non-uniform", and the obtained results are shown in table 1.
TABLE 1
| Density (%) | Purity (%) | Internal tissue homogeneity | |
| Example 1 | 101.99 | 99.95 | Uniformity of |
| Example 2 | 101.23 | 99.95 | Uniformity of |
| Example 3 | 101.16 | 99.95 | Uniformity of |
| Example 4 | 98.81 | 99.95 | More uniform |
| Example 5 | 98.84 | 99.95 | More uniform |
| Example 6 | 97.86 | 99.95 | More uniform |
| Example 7 | 96.78 | 99.95 | More uniform |
| Example 8 | 95.95 | 99.95 | More uniform |
| Comparative example 1 | 95.74 | 99.95 | Non-uniformity of |
| Comparative example 2 | 95.34 | 99.95 | Non-uniformity of |
| Comparative example 3 | 96.62 | 99.95 | Non-uniformity of |
| Comparative example 4 | 97.54 | 99.95 | Non-uniformity of |
As can be seen from Table 1, comparing examples 1-3, the invention combines the control of various technological parameters by arranging multistage pressurization, temperature rise, heat preservation and pressure maintaining stages, and the purity and the compactness of the prepared titanium-niobium alloy target material are higher, and the internal structure is uniform;
as can be seen from comparison of example 1 and example 4, the mixing time is too short, the powder is unevenly mixed and large particle agglomeration exists, and the density is reduced; as can be seen from comparison of examples 1 and 5 and 6, the temperature of the first heat preservation Wen Baoya treatment and the second heat preservation pressure maintaining treatment has a great influence on the density and internal structure uniformity of the prepared titanium-niobium alloy target, the density is reduced when the temperature is too low or too high, and the structure uniformity is also reduced; as is clear from comparison of examples 1 and examples 7 and 8, the second pressurizing treatment was too low or too high in pressure, the density was slightly lowered, and the uniformity of the structure was also lowered;
as can be seen from the comparison between the example 1 and the comparative example 1, the density and the tissue uniformity are remarkably reduced due to the gradient design that the second heat and pressure preservation treatment is directly performed, but the heat and pressure preservation treatment is not performed; as is clear from the comparison of example 1 and comparative example 2, the copper salt resulted in a significant decrease in density and tissue uniformity without the second pressurization treatment; as can be seen from the comparison of the example 1 with the comparative examples 3 and 4, the niobium content and the titanium content in the titanium-niobium alloy target material need to be controlled within a reasonable range, and the excessively low niobium content or the excessively low titanium content can reduce the uniformity of the internal structure of the titanium-niobium alloy target material and affect the quality of the product.
In summary, according to the preparation method provided by the invention, the mixed powder obtained after ball grinding and mixing of the titanium powder and the niobium powder is subjected to vacuum hot-pressing sintering, the vacuum hot-pressing sintering treatment process is divided into the stages of multistage pressurization, temperature rise, heat preservation and pressure maintaining, and the control of various technological parameters is combined, so that the prepared titanium-niobium alloy target material is higher in compactness, higher than or equal to 99.9% in purity and excellent in internal tissue structure, and can meet the high-performance requirement of the sputtering target material.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The preparation method of the titanium-niobium alloy target is characterized by comprising the following steps of:
(1) Mixing titanium powder and niobium powder to obtain mixed powder;
(2) The mixed powder obtained in the step (1) is subjected to compaction treatment, vacuum hot-pressing sintering treatment and machining treatment in sequence to obtain the titanium-niobium alloy target;
the vacuum hot-pressed sintering treatment in the step (2) comprises a first pressurizing treatment, a first heating treatment, a first keeping Wen Baoya treatment, a second heating treatment, a second heat-preserving pressure-maintaining treatment and a second pressurizing treatment which are sequentially carried out.
2. The method of claim 1, wherein the purity of the titanium powder of step (1) is > 99.98%;
preferably, the titanium powder of step (1) has an average particle size of < 45 μm;
preferably, the purity of the niobium powder of step (1) is > 99.95%;
preferably, the niobium powder of step (1) has an average particle size of < 60. Mu.m.
3. The method of claim 1 or 2, wherein the mixing of step (1) is performed in an argon atmosphere;
preferably, the mixed ball ratio of the step (1) is 10 (1-3);
preferably, the mixed powder blend balls of step (1) comprise hard zirconium balls and/or zirconium oxide balls;
preferably, the mixing time of step (1) is not less than 48 hours.
4. A method according to any one of claims 1 to 3, wherein the first pressure treatment in step (2) is carried out at a pressure of 5 to 20t for a period of 2 to 10min;
preferably, the step (2) further comprises a step of vacuumizing to a vacuum degree of less than 100Pa after the first pressurizing treatment and before the first heating treatment;
preferably, the first temperature increasing process of step (2) includes: heating to 1000-1100 ℃ at a heating rate of 5-10 ℃/min;
preferably, in the step (2), the pressure in the first temperature raising treatment is greater than 50t, and the pressure relief treatment is performed.
5. The method according to any one of claims 1 to 4, wherein the first holding temperature Wen Baoya in step (2) is 1000 to 1100 ℃;
preferably, the first protection Wen Baoya of step (2) is processed for 60-90min;
preferably, the pressure of the first protection Wen Baoya treatment in step (2) is 48-50t.
6. The production method according to any one of claims 1 to 5, wherein the second temperature-increasing treatment of step (2) comprises: heating to 1300-1500 ℃ at a heating rate of 1-5 ℃/min;
preferably, the temperature of the second heat preservation and pressure maintaining treatment in the step (2) is 1300-1500 ℃;
preferably, the time of the second heat preservation and pressure maintaining treatment in the step (2) is more than or equal to 1h, preferably 1-2h;
preferably, the pressure of the second heat preservation and pressure maintaining treatment in the step (2) is 48-50t.
7. The production method according to any one of claims 1 to 6, wherein the second pressure treatment of step (2) comprises: pressurizing to 290-310t in 2.9-3.1 h;
preferably, the second pressurizing treatment in the step (2) further comprises a step of removing the pressurizing treatment;
preferably, the pressure relief treatment includes: argon is introduced until the pressure in the furnace is between-0.06 and-0.08 MPa;
preferably, the pressure-removing treatment further comprises a step of cooling;
preferably, the cooling comprises: cooling to the temperature of less than 200 ℃ along with the furnace, and then naturally cooling to the room temperature.
8. The method of any one of claims 1-7, wherein the machining process of step (2) comprises milling and/or wire cutting.
9. A titanium-niobium alloy target, characterized in that the titanium-niobium alloy target is prepared by the preparation method of any one of claims 1 to 8;
the mass percentage of niobium in the titanium-niobium alloy target is 1-20wt% and the balance is titanium.
10. Use of the titanium-niobium alloy target according to claim 9, wherein the titanium-niobium alloy target is used in semiconductor magnetron sputtering.
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| CN113073299A (en) * | 2021-03-24 | 2021-07-06 | 宁波江丰电子材料股份有限公司 | Preparation method of chromium-silicon alloy sputtering target material |
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| CN113073299A (en) * | 2021-03-24 | 2021-07-06 | 宁波江丰电子材料股份有限公司 | Preparation method of chromium-silicon alloy sputtering target material |
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