CN117187610A

CN117187610A - Chromium-titanium target material and preparation method thereof

Info

Publication number: CN117187610A
Application number: CN202311164370.4A
Authority: CN
Inventors: 文崇斌; 朱刘; 童培云
Original assignee: Vital Thin Film Materials Guangdong Co Ltd
Current assignee: Vital Thin Film Materials Guangdong Co Ltd
Priority date: 2023-09-11
Filing date: 2023-09-11
Publication date: 2023-12-08

Abstract

The application belongs to the technical field of target production, and discloses a preparation method of a chromium-titanium target, which improves the relative density and the uniformity of component distribution of the chromium-titanium target through the preparation steps of primary mixing, sintering, ball milling and crushing, secondary mixing and hot isostatic pressing, and meanwhile, in the experimental process, the mass ratio of chromium powder to titanium powder is 85-95: 5-15, and the preparation method of the chromium-titanium target has low requirements on the grain size of the raw materials, so that the preparation method of the chromium-titanium target has a high application range, and in addition, the application also discloses the chromium-titanium target.

Description

Chromium-titanium target material and preparation method thereof

Technical Field

The application relates to the technical field of target preparation, in particular to a chromium-titanium target and a preparation method thereof.

Background

Metallic chromium (Cr) is a bluish-white metal. Chromium has strong passivation capability in the atmosphere, can keep luster for a long time, has good corrosion resistance to various acids and strong alkali, and has good chemical stability. Chromium also has the characteristics of high hardness, high resistivity and the like. Because of the various properties of chromium, chromium and its alloys or compound films prepared by various surface techniques are widely used in surface engineering, for example: mechanical functional films, microelectronic films, electromagnetic functional films, optical films, decorative functional films, and the like. With the development of high and new technologies, high-purity chromium alloy sputtering targets with different performances and different requirements are required in the technical fields of microelectronic semiconductor integrated circuits, large curtain wall glass, automobile rearview mirrors and the like. The sputtering film coating is to utilize sputtering phenomenon to prepare various films, namely, the surface of the target material is bombarded by charged ions in a vacuum chamber, so that the bombarded particles deposit on a substrate to form the film. The magnetron sputtering coating has the advantages of good adhesiveness, compact film quality, water and electricity saving, no three-waste treatment and the like, so that the magnetron sputtering coating has great application advantages.

The coating obtained after construction coating of the chromium-titanium target material prepared by doping titanium element in metal chromium has the characteristics of high hardness, smooth surface, good oxidation resistance and the like, the application proportion of the coating in the sputtering coating field is gradually increased, but in the actual production process, the purity and the particle size of chromium powder and titanium powder supplied by different suppliers are obviously different, and even the particle sizes of chromium powder and titanium powder produced by the same manufacturer are obviously different, meanwhile, the density and the flow degree of the chromium-titanium target material in a molten state are extremely difficult to control in the production process.

Chinese patent application 201210507051.4 discloses a method for producing a highly dense chromium alloy target, comprising sequentially performing the steps of vacuum degassing, stepwise heating and adding, pressure maintaining furnace cooling, hot forging, annealing, hot rolling, annealing and machining, wherein: chromium powder with the mesh of-200, the purity of more than 99.95 weight percent and the oxygen content of less than 1000ppm is adopted as a raw material; after the raw materials are subjected to the steps of vacuum degassing, staged heating and adding, pressure maintaining furnace cooling, hot forging, annealing, hot rolling and annealing in sequence, the chromium alloy target with higher purity is obtained, and meanwhile, the grain size of the chromium alloy is smaller than 100 microns, and meanwhile, the chromium alloy target with uniform components and density is obtained;

as can be seen from observing example 3 of the scheme, the chromium powder and the titanium powder are mixed according to the weight ratio of 9:1, and finally the chromium-titanium alloy target with high density and high purity is prepared, the crystal grains of the target are uniformly distributed, the size of the crystal grains is lower than 100 micrometers, and the chromium-titanium alloy target has good three-point bending strength, and the specific performances of the chromium-titanium alloy target are shown in table 1:

table 1: performance parameters of chromium-titanium alloy targets in comparative document 1

Name of product

Relative density of

Purity of

Grain size

Three point bending strength

Grain distribution

Oxygen content

Chromium-titanium alloy target material

99.5％

99.91％

Less than 100 μm

119MPa

Uniformity of

822ppm

From the above table, it is seen that the chromium-titanium alloy target material also has a lower oxygen content, which is thought to be caused in part by chromium powder and titanium powder with lower oxygen content in the raw materials;

meanwhile, we can find that although the solution greatly improves the uniformity of the distribution of crystal grains of the chromium-titanium alloy target, at the same time, the solution does not excessively design the uniformity of the distribution of chromium and titanium, and the good uniformity of the distribution of chromium and titanium has a critical influence on the performance of a film obtained by sputtering the target.

Chinese patent application 201680009216.1 discloses a chromium-titanium alloy sputtering target and a manufacturing method thereof, wherein the atomic ratio of the chromium-titanium alloy sputtering target in the method is expressed by Cr _100-X -Ti _X 、40≤X≤60

The remainder including unavoidable impurities including Mg, al, si, mn, ni, cu and Sn in a total amount of 1 to 50 mass ppm;

the method comprises mixing Ti powder containing Mg, al, si, mn, ni, cu and Sn in a total amount of 1 to 50 mass ppm as impurities with Cr powder containing Mg, al, si, mn, ni, cu and Sn in a total amount of 1 to 50 mass ppm as impurities, and pressure sintering to obtain a chromium-titanium alloy sputtering target;

meanwhile, as a result of various investigations on the cause of particle generation during sputtering, it was confirmed that magnesium (Mg), aluminum (Al), silicon (Si), manganese (Mn), nickel (Ni), copper (Cu) and tin (Sn), which are impurities contained, were starting points of nodule generation. Further, it has been found that by setting the chromium-titanium alloy sputtering target material to have a high purity in which these impurities are controlled within a specific range, the occurrence of nodules can be suppressed; therefore, the scheme is characterized in that the content of impurity components in chromium and titanium is substantially inhibited, so that the number of nodules generated after sintering of the chromium-titanium alloy sputtering target is inhibited, and the generation of fine particles of the target in the subsequent sputtering process is improved; and the subsequent performance test results of the scheme can also see that the scheme more discusses the relation between the impurity content and the nodule number in the target, but does not make excessive design for the uniformity degree of the distribution of the chromium and titanium components in the target.

The problem that this scheme needs to solve: how to provide a preparation method of a chromium-titanium target material with high component dispersion uniformity.

Disclosure of Invention

The application aims to provide a preparation method of a chromium-titanium target material, which can prepare the chromium-titanium target material with higher relative density, and can further improve the dispersion uniformity degree of chromium-titanium components in the target material, thereby further improving the performance of a chromium-titanium film or coating obtained in the subsequent sputtering process.

In order to achieve the above purpose, the application discloses a preparation method of a chromium-titanium target, which comprises the following steps:

step 1: mixing and stirring chromium powder and titanium powder to obtain chromium-titanium mixed powder;

step 2: sintering the chromium-titanium mixed powder prepared in the step 1 to obtain a sintered chromium-titanium alloy structure;

step 3: ball milling, crushing and sieving the chromium-titanium alloy tissue prepared in the step 2 to obtain first chromium-titanium alloy powder;

step 4: stirring the first chromium-titanium alloy powder prepared in the step 3 again to obtain second chromium-titanium alloy powder;

step 5: sequentially performing hot isostatic pressing treatment, cooling, depressurization and machining on the second chromium-titanium alloy powder to obtain a chromium-titanium target;

in the step 1, the mass ratio of the chromium powder to the titanium powder is 85-95: 5 to 15.

Further preferably, the mass ratio of chromium powder to titanium powder includes, but is not limited to: 85: 15. 90: 10. 95:15;

preferably, step 1 specifically includes:

under the protection of inert gas, placing chromium powder and titanium powder into a homogenizing mixer to be mixed for 4-6 hours to obtain chromium-titanium mixed powder; wherein the stirring speed of the homogenizing mixer is 30-50 r/min, and the rotating speed of the homogenizing mixer is 60-80 r/min.

Preferably, step 2 specifically includes:

and (3) placing the chromium-titanium mixed powder prepared in the step (1) into a vacuum heat treatment furnace, and sintering for 1-3 hours at the temperature of 500-650 ℃ to obtain a sintered chromium-titanium alloy structure.

Preferably, step 3 specifically includes:

and (3) putting the sintered chromium-titanium alloy tissue prepared in the step (2) into a ball mill for ball milling, and sieving with a 50-mesh sieve to obtain first chromium-titanium alloy powder.

Preferably, step 4 specifically includes:

placing the first chromium-titanium alloy powder prepared in the step 3 into a double-motion homogenizer for homogenizing for 4-6 hours to obtain second chromium-titanium alloy powder; the stirring speed of the double-motion homogenizer is 30-50 r/min, and the rotating speed of the double-motion homogenizer is 60-80 r/min.

Preferably, step 5 specifically includes:

and (3) loading the second chromium-titanium alloy powder prepared in the step (4) into a stainless steel sheath, vacuumizing, sealing and welding, putting into a hot isostatic pressing furnace, performing hot isostatic pressing for 1-1.5 h at 950-1100 ℃ and under 180-200 MPa, and then cooling, taking out and machining to obtain the chromium-titanium target.

Preferably, step 3 further specifically includes:

placing the sintered chromium-titanium alloy tissue prepared in the step 2 into a ball mill for ball milling, and sequentially sieving with a 50-mesh sieve, a 100-mesh sieve and a 150-mesh sieve to obtain large-particle-size first chromium-titanium alloy powder with the particle size of 50-100 meshes respectively;

medium-grain-diameter first chromium-titanium alloy powder with grain diameter of 100-150 meshes;

a small particle size first chromium titanium alloy powder having a particle size less than 150 mesh;

mixing the large-grain-size first chromium-titanium alloy powder, the medium-grain-size first chromium-titanium alloy powder and the small-grain-size first chromium-titanium alloy powder according to a ratio of 2-4: 3: 3-5 to obtain first chromium-titanium alloy powder;

further preferably, the mass ratio of the large-grain-size first chromium-titanium alloy powder, the medium-grain-size first chromium-titanium alloy powder, and the small-grain-size first chromium-titanium alloy powder includes, but is not limited to: 2:3:5. 3:3: 5. 4:3: 5. 2:3: 3. 3:3: 3. 4:3:3. 2:3: 4. 3:3: 4. 4:3:4, a step of;

in addition, the application also discloses a chromium-titanium target material, which is prepared by the preparation method of the chromium-titanium target material.

Preferably, the chromium titanium target has a relative density of greater than or equal to 99.0%.

Preferably, in the chromium-titanium target, the difference of the titanium content of each position is less than or equal to 0.5%.

The beneficial effects of the application are as follows: according to the application, through the preparation steps of mixing, sintering, crushing, secondary mixing and hot isostatic pressing, the relative density and the component distribution uniformity degree of the prepared chromium-titanium target material are further improved, meanwhile, in the preparation process, the reason for improving the relative density is considered to be that in the crushing and secondary mixing process, a large number of pores, defects and the like still exist in a chromium-titanium alloy tissue after sintering, the crushed secondary mixing not only causes the pores and defects to disappear, but also the contact between the first chromium-titanium alloy powder is more compact in the secondary mixing process, so that the density of the chromium-titanium target material is improved;

meanwhile, in the process of crushing and secondary mixing, as the fluidity of the chromium and titanium in a molten state is different during sintering, chromium or titanium elements at partial positions are gathered, so that uneven distribution of chromium and titanium in a chromium-titanium alloy structure is reduced, and after sintering, the chromium-titanium alloy structure is scattered again and mixed again, so that rearrangement of the chromium and titanium is realized, and the distribution uniformity degree of the chromium and titanium is greatly improved.

Detailed Description

The present application will be described more fully hereinafter with reference to the accompanying drawings, in which specific conditions, either conventional or manufacturer-suggested, are not explicitly stated. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

Example 1

Step 1: firstly, introducing inert gas to a double-motion homogenizer with a stirring device, and then adding chromium powder and titanium powder into the double-motion homogenizer for homogenization for 4 hours to prepare chromium-titanium mixed powder; wherein the mass ratio of the chromium powder to the titanium powder is 95:5, stirring at a speed of 30r/min by a homogenizer; the rotation speed of the homogenizer is 70r/min;

step 2: placing the chromium-titanium mixed powder prepared in the step 1 into a vacuum heat treatment furnace, and keeping the temperature at 650 ℃ for 2 hours to react chromium and titanium to obtain a sintered chromium-titanium alloy structure;

step 3: ball milling and crushing the sintered chromium-titanium alloy tissue, and sieving the crushed chromium-titanium alloy tissue with a 50-mesh sieve to obtain first chromium-titanium alloy powder;

step 4: homogenizing the first chromium-titanium alloy powder in the step 3 in a double-motion homogenizer for 4 hours to obtain second chromium-titanium alloy powder; wherein the stirring speed of the homogenizer is 30r/min; the rotation speed of the homogenizer is 70r/min.

Step 5: and (3) loading the second chromium-titanium alloy powder prepared in the step (4) into a stainless steel sheath, vacuumizing for sealing welding, putting into a hot isostatic pressing furnace for sintering for 1h, wherein the sintering pressure is 180Mpa, the sintering temperature is 1100 ℃, cooling and depressurizing, removing the sheath, and machining to obtain the chromium-titanium target.

Example 2

Step 1: firstly, introducing inert gas to a double-motion homogenizer with a stirring device, and then adding chromium powder and titanium powder into the double-motion homogenizer for homogenization for 6 hours to prepare chromium-titanium mixed powder; wherein the mass ratio of the chromium powder to the titanium powder is 90:10, the stirring speed of the homogenizer is 50r/min; the rotation speed of the homogenizer is 80r/min;

step 2: placing the chromium-titanium mixed powder prepared in the step 1 into a vacuum heat treatment furnace, and keeping the temperature at 500 ℃ for 3 hours to react chromium and titanium to obtain a sintered chromium-titanium alloy structure;

step 4: homogenizing the first chromium-titanium alloy powder in the step 3 in a double-motion homogenizer for 6 hours to obtain second chromium-titanium alloy powder; wherein the stirring speed of the homogenizer is 50r/min; the rotation speed of the homogenizer is 80r/min.

Step 5: and (3) loading the second chromium-titanium alloy powder prepared in the step (4) into a stainless steel sheath, vacuumizing for sealing welding, putting into a hot isostatic pressing furnace for sintering for 1.5h, wherein the sintering pressure is 200Mpa, the sintering temperature is 950 ℃, reducing the temperature and the pressure, removing the sheath, and machining to obtain the chromium-titanium target.

Example 3

Step 1: firstly, introducing inert gas to a double-motion homogenizer with a stirring device, and then adding chromium powder and titanium powder into the double-motion homogenizer for homogenization for 5 hours to prepare chromium-titanium mixed powder; wherein the mass ratio of the chromium powder to the titanium powder is 85:15; the stirring speed of the homogenizer is 40r/min, and the rotating speed of the homogenizer is 60r/min.

Step 2: placing the chromium-titanium mixed powder obtained in the step 1 into a vacuum heat treatment furnace, and keeping the temperature at 550 ℃ for 1h to react chromium and titanium to obtain a sintered chromium-titanium alloy structure;

step 3: ball milling and crushing the sintered chromium-titanium alloy tissue, and sieving with a 50-mesh sieve;

step 4: homogenizing the first chromium-titanium alloy powder in the step 3 in a double-motion homogenizer for 5 hours to obtain second chromium-titanium alloy powder; the stirring speed of the homogenizer is 40r/min, and the rotating speed of the homogenizer is 60r/min.

Step 5: and (3) loading the second chromium-titanium alloy powder prepared in the step (4) into a stainless steel sheath, vacuumizing for sealing welding, putting into a hot isostatic pressing furnace for sintering for 75min, wherein the sintering pressure is 190Mpa, the sintering temperature is 1000 ℃, cooling and depressurizing, removing the sheath, and machining to obtain the chromium-titanium target.

Example 4

The method is basically the same as that of the example 1, except that in the step 3, the sintered chromium-titanium alloy tissue is crushed by ball milling and sequentially passes through a 50-mesh sieve, a 100-mesh sieve and a 150-mesh sieve; taking first chromium-titanium alloy powder with the particle size of between 50 and 100 meshes as large-particle-size first chromium-titanium alloy powder;

taking first chromium-titanium alloy powder with the grain size of between 100 and 150 meshes as medium-grain-size first chromium-titanium alloy powder;

taking the first chromium-titanium alloy powder with the particle size of less than 150 meshes as small-particle-size first chromium-titanium alloy powder;

then mixing the large-grain-size first chromium-titanium alloy powder, the medium-grain-size first chromium-titanium alloy powder and the small-grain-size first chromium-titanium alloy powder according to a ratio of 3:3:4, putting the mixture into a double-motion homogenizer for homogenization.

Example 5

Substantially the same as in example 4, except that the mass ratio of the large particle size first chromium titanium alloy powder, the medium particle size first chromium titanium alloy powder, and the small particle size first chromium titanium alloy powder was 2:3:5.

example 6

Substantially the same as in example 4, except that the mass ratio of the large particle size first chromium titanium alloy powder, the medium particle size first chromium titanium alloy powder, and the small particle size first chromium titanium alloy powder was 4:3:3.

comparative example 1

Substantially the same as in example 1, except that in step 1, the mass ratio of chromium powder to titanium powder was 60:40.

comparative example 2

Substantially the same as in example 1, except that in step 1, the mass ratio of chromium powder to titanium powder was 98:2.

comparative example 3

step 2: and (3) loading the chromium-titanium mixed powder prepared in the step (1) into a stainless steel sheath, vacuumizing for sealing welding, putting into a hot isostatic pressing furnace for sintering for 1h, wherein the sintering pressure is 180Mpa, the sintering temperature is 1100 ℃, cooling and depressurizing, removing the sheath, and machining to obtain the chromium-titanium target.

Comparative example 4

step 4: and (3) filling the sieved chromium-titanium alloy tissue powder prepared in the step (3) into a stainless steel sheath, vacuumizing for sealing welding, putting into a hot isostatic pressing furnace for sintering for 1h, wherein the sintering pressure is 180Mpa, the sintering temperature is 1100 ℃, reducing the temperature and the pressure, removing the sheath, and machining to obtain the chromium-titanium target.

Comparative example 5

Step 1: firstly, introducing inert gas into a double-motion homogenizer with a stirring device, and then mixing chromium powder and titanium powder to prepare chromium-titanium mixed powder;

Performance test:

relative density: the water drainage method is used for measurement, the testing instrument is a solid density testing instrument, and the calculation method is as follows: relative density = actual density/theoretical density;

titanium content test: respectively testing the titanium content of 3 different points of the chromium-titanium target material;

the results of the relative density and titanium content tests are shown in table 2:

table 2: chromium-titanium target performance test results

Analysis of results:

1. as can be seen from examples 1-3, the mass ratio of the chromium powder to the titanium powder is 85-95: in the interval of 5-15, the method has relatively obvious effect on the improvement of the relative density of the final target material and the improvement of the uniformity degree of the component distribution;

meanwhile, in the experimental process, the particle sizes of the chromium powder and the titanium powder in the step 1 are not limited or screened in each embodiment, but the chromium-titanium target obtained in the embodiments 1-3 still has excellent relative density and uniform component distribution, and therefore, the preparation method of the chromium-titanium target has low requirements on the particle sizes of raw materials;

2. according to the embodiment 4-6, the first chromium-titanium alloy powder screened in the step 3 is mixed and matched with large, medium and small particle sizes, and the mass ratio of the first chromium-titanium alloy powder with the large, medium and small particle sizes is controlled, so that the relative density of the target material and the uniformity of distribution of components are further improved.

3. It can be seen from example 1 and comparative examples 1-2 that when the mass ratio of chromium powder to titanium powder exceeds or is smaller than that of chromium powder: titanium powder=85 to 95: 5-15, the preparation method of the chromium-titanium target obviously reduces the effect of improving the relative density and the component distribution uniformity degree of the chromium-titanium target, and reduces the improving capability of the component distribution uniformity degree more seriously;

4. as can be seen from example 1 and comparative examples 3 to 5, when comparative example 3 omits the steps of sintering, crushing and secondary mixing, the relative density and the component dispersion uniformity of the chromium-titanium target material all have a significant tendency to decrease;

when the step of secondary mixing is omitted in comparative example 4, the relative density and the uniform dispersion degree of the components of the chromium-titanium target material still generate different degrees of descending trend;

when the comparative example 5 omits the homogenization operation in the primary mixing process, the relative density and the component dispersion uniformity of the chromium-titanium target material are also reduced to a certain extent, so that in the preparation method of the chromium-titanium target material, the improvement of the relative density and the component dispersion uniformity of the chromium-titanium target material is the result of the synergism of a plurality of steps;

the above embodiments are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.

Claims

1. The preparation method of the chromium-titanium target is characterized by comprising the following steps of:

step 1: stirring and mixing chromium powder and titanium powder to obtain chromium-titanium mixed powder, wherein the mass ratio of the chromium powder to the titanium powder is 85-95: 5 to 15;

step 4: stirring the first chromium-titanium alloy powder prepared in the step 3 to obtain second chromium-titanium alloy powder;

step 5: and sequentially performing hot isostatic pressing treatment, cooling, depressurization and machining on the second chromium-titanium alloy powder to obtain the chromium-titanium target.

2. The method for preparing a chromium-titanium target according to claim 1, wherein the step 1 specifically comprises:

3. The method for preparing a chromium-titanium target according to claim 1, wherein the step 2 specifically comprises:

4. The method for preparing a chromium-titanium target according to claim 1, wherein the step 3 specifically comprises:

5. The method for preparing a chromium-titanium target according to claim 1, wherein the step 4 specifically comprises:

6. The method for preparing a chromium-titanium target according to claim 1, wherein the step 5 specifically comprises:

7. The method for preparing a chromium-titanium target according to claim 4, wherein the step 3 further specifically comprises:

mixing the large-grain-size first chromium-titanium alloy powder, the medium-grain-size first chromium-titanium alloy powder and the small-grain-size first chromium-titanium alloy powder according to a ratio of 2-4: 3:3 to 5 to obtain the first chromium-titanium alloy powder.

8. A chromium-titanium target, characterized by being produced by the production method of a chromium-titanium target according to any one of claims 1 to 7.

9. The chromium-titanium target according to claim 8, wherein the chromium-titanium target has a relative density of greater than or equal to 99.0%.

10. The chromium-titanium target according to claim 8, wherein the difference in titanium content at each position in the chromium-titanium target is less than or equal to 0.5%.