CN116377403B - Preparation method of molybdenum-titanium target - Google Patents
Preparation method of molybdenum-titanium target Download PDFInfo
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- CN116377403B CN116377403B CN202310469917.5A CN202310469917A CN116377403B CN 116377403 B CN116377403 B CN 116377403B CN 202310469917 A CN202310469917 A CN 202310469917A CN 116377403 B CN116377403 B CN 116377403B
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- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 62
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000013077 target material Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003754 machining Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000004544 sputter deposition Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 230000002159 abnormal effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F3/10—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
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a preparation method of a molybdenum-titanium target, which comprises the following steps: s1, mixing molybdenum powder and titanium powder, and then performing high-energy ball milling, wherein molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and used as a ball material in the ball mill; s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and carrying out a reaction of molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials; s3, mixing the powder in the step S1 and the powder in the step S2, and performing cold isostatic pressing; s4, presintering and sintering are carried out in a protective gas atmosphere; s5, performing hot isostatic pressing treatment; s6, machining to obtain the molybdenum-titanium target. The density of the molybdenum-titanium target material is more than 99.9%; meanwhile, the internal tissue of the target material has no defects such as air holes, cracks and the like; the crystal grains are uniform, the molybdenum and the titanium in the target material are uniformly distributed, the impurity content of the molybdenum-titanium target is less than 10ppm, and the method is suitable for preparing the flat panel display.
Description
Technical Field
The invention belongs to the technical field of metal materials, and relates to a preparation method of a molybdenum-titanium target.
Background
The molybdenum-titanium alloy has low resistivity, good processability, good repeatability and small batch-to-batch performance difference, and is therefore commonly used as a wiring material for liquid crystal display devices. Molybdenum-titanium alloy targets are typically used for sputtering to produce molybdenum-titanium alloy wiring materials, and the molybdenum-titanium alloy targets are typically produced by a process comprising the steps of: ball milling, cold isostatic pressing, sintering, hot isostatic pressing/hot working of raw material powder.
However, the target material prepared by the process has uneven distribution of molybdenum and titanium, and different inter-grain molybdenum and titanium components have deviation, and the uneven grains can become the cause of abnormal discharge in the subsequent sputtering process, and the abnormal discharge of the target material can generate particle splashing or dropping, thereby influencing the performance of the molybdenum-titanium film. If the density of the molybdenum-titanium target is insufficient, when the target has pores, ar ions bombard the edges of the pores in the sputtering process, protrusions are generated, abnormal discharge is caused along with the accumulation of the protrusions, and then the caused particles splash or drop. Along with the increase of the grain size of the molybdenum-titanium target, the sputtering rate can change along with the grain orientation, the surface of the target can generate non-uniformity of the sputtering rate during sputtering, along with the increase of the grain size, the sputtering surface presents irregular stepped steps, abnormal discharge can be generated when the irregular stepped steps are accumulated to a certain extent, and particles are dropped. In addition, the residual processing strain can influence the sputtering rate of the surface of the molybdenum-titanium target, if the residual processing strain in the molybdenum-titanium target is large, the difference of the surface sputtering rate can be caused, a plurality of stepped parts can be generated due to the difference of the surface sputtering rate of the target, abnormal discharge can be generated when the residual processing strain is accumulated to a certain degree, and particles are dropped.
In order to improve the uniformity of components and the compactness of the target, a mode of increasing the sintering temperature and the hot pressing temperature is generally adopted to ensure that the structure is more uniform, but the increase of the temperature can cause the increase of the grain size, and the excessive grain size can also cause the splashing or dropping of particles caused by abnormal discharge. For example, patent 2023101124585 adopts three-stage heating in the sintering stage, sintering is carried out at 1600-1700 ℃, and the grain size is about 60 μm. The density can be improved and the grain size can be reduced by adopting a hot working mode, but residual working stress can be introduced, so that the difference of surface sputtering rates is caused. In addition, impurity elements are introduced during the ball milling process, which also becomes a cause of abnormal discharge.
Disclosure of Invention
The first object of the invention is to provide a preparation method of a molybdenum-titanium target, wherein the prepared target can reduce splashing or dropping of particles caused by abnormal discharge in a sputtering process.
The second object of the invention is to provide a molybdenum-titanium target.
The third object of the invention is to provide an application method of the molybdenum-titanium target. The first technical scheme adopted by the invention is that the preparation method of the molybdenum-titanium target comprises the following steps:
s1, mixing molybdenum powder and titanium powder, performing high-energy ball milling, wherein molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through the high-energy ball milling;
s2, placing part of the molybdenum-titanium alloy powder in the step S1 into a vacuum heat treatment furnace, and keeping the temperature at 800-1000 ℃ for 1-3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, uniformly mixing the molybdenum-titanium powder in the step S1 and the molybdenum-titanium powder in the step S2 in a mass ratio of 1:1-1:3, and forming a pressed compact through cold isostatic pressing;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas: presintering: heating the furnace temperature from room temperature to 900-950 ℃, and preserving heat for 3-8 h; sintering: heating the furnace temperature from 900-950 ℃ to 1200-1250 ℃, and preserving heat for 3-6 h;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 100-160MPa and 1000-1200 ℃;
s6, removing the oxidized and modified layer on the surface layer through mechanical processing to obtain the molybdenum-titanium target.
In the step S1, the high-energy ball milling time is 40-60h.
The average particle size of the molybdenum powder in step S1 is 5 μm to 20.0. Mu.m.
The purity of the molybdenum powder in the step S1 is more than 99.95 percent.
The average particle size of the titanium powder in step S1 is 5 μm to 20.0. Mu.m.
The purity of the titanium powder in the step S1 is more than 99.9 percent.
In the step S3, the pressure of the cold isostatic pressing is 160MPa-220MPa in the cold isostatic pressing process.
The second technical scheme adopted by the invention is that the molybdenum-titanium target material is prepared by the preparation method, the density of the molybdenum-titanium target material is more than 99.9 percent, the average grain size of the molybdenum-titanium target material is less than 30 mu m, and the impurity content of the molybdenum-titanium target material is less than 10ppm.
The third technical scheme adopted by the invention is an application method of the molybdenum-titanium target material in the preparation of a flat panel display.
The invention has the beneficial effects that:
firstly, mixing molybdenum powder and titanium powder, putting the mixed powder into a ball mill, and performing high-energy ball milling to ensure that the mixed powder completely reacts and is converted into molybdenum-titanium alloy powder. In the process, the molybdenum-titanium alloy is used as an inner wall material of the ball mill, and the molybdenum-titanium alloy is used as a ball material in the ball mill, so that the prepared target can reduce splashing or dropping of particles caused by abnormal discharge in the sputtering process.
According to the invention, the molybdenum-titanium alloy powder is used as a part of raw materials to prepare the target, so that more uniform element distribution and tissue morphology can be obtained at a lower sintering temperature and hot isostatic pressing temperature, the density of the target is more than or equal to 99.9%, and the grain size cannot be increased due to the lower hot isostatic pressing temperature, so that the splashing or falling of particles caused by abnormal discharge is reduced. The traditional process adopts 3-4 sections of procedures for sintering, the sintering temperature is generally between 1400 ℃ and 1700 ℃, and the sintering process can achieve the same technical effect by only two sections of sintering at 1200 ℃ to 1250 ℃, thereby simplifying the sintering process. The hot isostatic pressing temperature is too low, and the density of the target is insufficient; the hot isostatic pressing temperature is too high, the density can meet the requirement, but the grain size is obviously increased, molybdenum and titanium can also react with a carbon die, impurities are introduced, and the residual stress is higher; the process reduces the temperature of hot isostatic pressing and can realize better technical effect at high temperature and high pressure. The target material has high compactness, small residual processing stress and low impurity content.
The molybdenum-titanium target has high density which is more than 99.9 percent; meanwhile, the internal tissue of the target material has no defects such as air holes, cracks and the like; the grains are uniform, and the molybdenum and titanium in the target material are uniformly distributed; the average grain size is below 30 μm; the impurity content of the molybdenum-titanium target is less than 10ppm; is suitable for preparing the flat panel display.
The specific embodiment is as follows:
example 1:
s1, mixing molybdenum powder and titanium powder with average particle sizes of 15 mu m, performing high-energy ball milling for 60 hours, wherein molybdenum-titanium alloy is used as an inner wall material of a ball mill in the ball milling process, and used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and keeping the temperature at 1000 ℃ for 3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, mixing the powder in the step S1 and the powder in the step S2, and forming a pressed compact by cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200MPa, and the mass ratio of the powder in the step S1 to the powder in the step S2 is 1:2;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas;
presintering: heating the furnace temperature from room temperature to 950 ℃ and keeping the temperature for 6 hours;
sintering: heating the furnace temperature from 950 ℃ to 1200-1250 ℃ and keeping the temperature for 6h;
s5, carrying out hot isostatic pressing treatment on the sintered blank at the temperature of between 1000 and 1200 ℃ under the pressure of 150 MPa;
s6, removing the oxidized and modified layers on the surface layer through mechanical processing to obtain the molybdenum-titanium target material with the impurity content of less than 10ppm and the density of more than 99.9%.
The molybdenum titanium content, sintering temperature and hot isostatic pressing temperature of example 1 are shown in table 1.
Comparative example 1:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, performing high-energy ball milling for 60 hours, wherein the titanium content is 30% (at%), the Mo content is 70% (at%), a common ball mill is used in the ball milling process, and steel balls are used as materials of balls in the ball mill, so that molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and keeping the temperature at 1000 ℃ for 3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, mixing the powder in the step S1 and the powder in the step S2, and forming a pressed compact by cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200MPa, and the ratio of the powder in the step S1 to the powder in the step S2 is 1:2;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas;
presintering: heating the room temperature to 950 ℃ and keeping the temperature for 6 hours;
sintering: heating to 1200 ℃ at 950 ℃ and keeping the temperature for 6 hours;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 150MPa and 1000 ℃;
s6, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
Comparative example 2:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, performing high-energy ball milling for 60 hours, wherein the titanium content is 30% (at%), the Mo content is 70% (at%), a molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and is used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and keeping the temperature at 1000 ℃ for 3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, mixing the powder in the step S1 and the powder in the step S2, and forming a pressed compact by cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200MPa, and the ratio of the powder in the step S1 to the powder in the step S2 is 1:5;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas;
presintering: heating the room temperature to 950 ℃ and keeping the temperature for 6 hours;
sintering: heating to 1200 ℃ at 950 ℃ and keeping the temperature for 6 hours;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 150MPa and 1000 ℃;
s6, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
Comparative example 3:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, performing high-energy ball milling for 60 hours, wherein the titanium content is 30% (at%), the Mo content is 70% (at%), a molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and is used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, forming a pressed compact by cold isostatic pressing of the powder in the step S1, wherein the pressure of the cold isostatic pressing is 200MPa;
s3, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas;
presintering: heating the room temperature to 950 ℃ and keeping the temperature for 6 hours;
sintering: heating to 1200 ℃ at 950 ℃ and keeping the temperature for 6 hours;
s4, carrying out hot isostatic pressing treatment on the sintered blank at the temperature of 150MPa and 1000 ℃;
s5, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
Comparative example 4:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, and then performing high-energy ball milling for 60 hours by adopting a common ball mill, wherein steel balls are used as materials of balls in the ball mill, the content of titanium is 30% (at%), and the content of Mo is 70% (at%);
s2, forming a pressed compact by cold isostatic pressing of the powder in the step S1, wherein the pressure of the cold isostatic pressing is 200MPa;
s3, placing the pressed compact in an atmosphere protection furnace, and performing three-stage sintering under the atmosphere of protection gas, wherein the steps are as follows:
heating in the first section: the room temperature is raised to 950 ℃, and the first-stage heat preservation time is 6h;
and (3) heating in the second stage: heating to 1200 ℃ at 950 ℃ and keeping the temperature for 6 hours in the second stage;
and (3) heating in the third stage: then heating from 1250 ℃ to 1680 ℃ and keeping the temperature for 8 hours in the second section;
s4, carrying out hot isostatic pressing treatment on the sintered blank at 150MPa and 1350 ℃;
s5, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
Comparative example 5:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, performing high-energy ball milling for 60 hours, wherein the titanium content is 30% (at%), the Mo content is 70% (at%), a molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and is used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and keeping the temperature at 1000 ℃ for 3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, mixing the powder in the step S1 and the powder in the step S2, and forming a pressed compact by cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200MPa, and the ratio of the powder in the step S1 to the powder in the step S2 is 1:2;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering under the atmosphere of protection gas;
the sintering step is as follows: heating to 1200 ℃ at room temperature, and keeping the temperature for 6h;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 150MPa and 1000 ℃;
s6, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
Comparative example 6:
s1, mixing 15 mu m molybdenum powder and 15 mu m titanium powder, performing high-energy ball milling for 60 hours, wherein the titanium content is 30% (at%), the Mo content is 70% (at%), a molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, and is used as a ball material in the ball mill, and the molybdenum-titanium alloy powder is formed through high-energy ball milling;
s2, placing the partial molybdenum-titanium alloy powder into a vacuum heat treatment furnace, and keeping the temperature at 1000 ℃ for 3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder, wherein the molybdenum-titanium alloy powder is used as a part of raw materials;
s3, mixing the powder in the step S1 and the powder in the step S2, and forming a pressed compact by cold isostatic pressing, wherein the pressure of the cold isostatic pressing is 200MPa, and the ratio of the powder in the step S1 to the powder in the step S2 is 1:2;
s4, placing the pressed compact in an atmosphere protection furnace, and performing three-stage sintering under the atmosphere of protection gas, wherein the steps are as follows: heating in the first section: the room temperature is raised to 950 ℃, and the first-stage heat preservation time is 6h;
and (3) heating in the second stage: heating to 1200 ℃ at 950 ℃ and keeping the temperature for 6 hours in the second stage;
and (3) heating in the third stage: then heating from 1250 ℃ to 1680 ℃ and keeping the temperature for 8 hours in the second section;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 150MPa and 1000 ℃;
s6, removing the oxidized and modified layer on the surface layer through machining to obtain the molybdenum-titanium target.
TABLE 1 Process conditions for example 1
Table 2 properties of example 1 and comparative examples 1-7
The molybdenum-titanium target material prepared by the method is subjected to magnetron sputtering on the surface of a 6-inch substrate, a molybdenum-titanium alloy film is observed, the number of particles larger than 0.3 mu m is calculated, and as can be seen from Table 2, the number of thin film particles obtained by sputtering the molybdenum-titanium target material prepared by the method is less than 30. Comparative examples 1-6 did not employ the process of the present invention and the number of particles increased significantly.
The lower hot pressing temperature does not cause an increase in grain size, thereby reducing splashing or dropping of particles caused by abnormal discharge. As can be seen from the comparison of the example 1 and the comparative example 4, the conventional process adopts 3-4 sections of procedures for sintering, the sintering temperature is generally 1400-1700 ℃, the invention only needs two sections of sintering, and the sintering can achieve the same technical effect at 1200-1250 ℃, thereby simplifying the sintering process. The process reduces the temperature of hot isostatic pressing and can realize better technical effect at high temperature and high pressure. As can be seen from Table 2, the average grain size of the molybdenum-titanium target material prepared by the process of the invention is below 30 μm (13-22 μm). Comparative examples 1-6 did not employ the process of the present invention and the grain size increased significantly. In comparative example 5, the temperature was raised for one stage, the number of particles, the average grain size and the vickers hardness were not satisfied, and the density was also lowered. The comparative example 6 adopts three-stage heating, the grain size is obviously increased, and the number of grains is also increased.
The residual processing strain can influence the sputtering rate of the surface of the molybdenum-titanium target, if the residual processing strain in the molybdenum-titanium target is large, the difference of the surface sputtering rate can be caused, a plurality of stepped parts can be generated due to the difference of the surface sputtering rate of the target, abnormal discharge can be generated when the residual processing strain is accumulated to a certain degree, and particles are dropped. The hardness can reflect the situation of residual strain, so the situation of residual stress is compared by measuring the Vickers hardness value, and as can be seen from the table 2, the Vickers hardness of the molybdenum-titanium target material prepared by the process is below 216, which indicates that the residual stress is small. Comparative examples 1-6 did not employ the process of the present invention and had greater residual stresses. As can be seen from Table 2, the impurity content of the molybdenum-titanium target material prepared by the process of the invention is below 10ppm.
Claims (9)
1. The preparation method of the molybdenum-titanium target is characterized by comprising the following steps:
s1, mixing molybdenum powder and titanium powder, performing high-energy ball milling, wherein molybdenum-titanium alloy is used as an inner wall material of the ball mill in the ball milling process, is used as a ball material in the ball mill, and is formed into molybdenum-titanium alloy powder through high-energy ball milling;
s2, placing part of the molybdenum-titanium alloy powder in the step S1 into a vacuum heat treatment furnace, and keeping the temperature at 800-1000 ℃ for 1-3 hours to react molybdenum and titanium to generate molybdenum-titanium alloy powder;
s3, uniformly mixing the molybdenum-titanium alloy powder in the step S1 and the molybdenum-titanium alloy powder in the step S2 according to the mass ratio of 1:1-1:3, and forming a pressed compact through cold isostatic pressing;
s4, placing the pressed compact in an atmosphere protection furnace, and pre-sintering and sintering under the atmosphere of protection gas: presintering: heating the furnace temperature from room temperature to 900-950 ℃, and preserving heat for 3-8 h; sintering: heating the furnace temperature from 900-950 ℃ to 1200-1250 ℃, and preserving heat for 3-6 h;
s5, carrying out hot isostatic pressing treatment on the sintered blank at 100-160MPa and 1000-1200 ℃;
s6, removing the oxidized and modified layer on the surface layer through mechanical processing to obtain the molybdenum-titanium target.
2. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: in the step S1, the high-energy ball milling time is 40-60h.
3. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: the average particle size of the molybdenum powder in the step S1 is 5 mu m to 20.0 mu m.
4. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: the purity of the molybdenum powder in the step S1 is more than 99.95 percent.
5. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: the average particle size of the titanium powder in the step S1 is 5 mu m to 20.0 mu m.
6. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: the purity of the titanium powder in the step S1 is more than 99.9 percent.
7. The method for preparing a molybdenum-titanium target according to claim 1, characterized in that: in the step S3, the pressure of the cold isostatic pressing is 160MPa-220MPa in the cold isostatic pressing forming process.
8. Molybdenum-titanium target prepared by the preparation method of any one of the molybdenum-titanium targets according to claims 1-7, characterized in that the density of the molybdenum-titanium target is above 99.9%, the average grain size of the molybdenum-titanium target is below 30 μm, and the impurity content of the molybdenum-titanium target is less than 10ppm.
9. The method of claim 8, wherein the method is used in the manufacture of flat panel displays.
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| JP2011089188A (en) * | 2009-10-26 | 2011-05-06 | Ulvac Japan Ltd | Method for producing titanium-containing sputtering target |
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