CN108642464B - Preparation method of high-purity ruthenium sputtering target material - Google Patents

Preparation method of high-purity ruthenium sputtering target material Download PDF

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CN108642464B
CN108642464B CN201810661515.4A CN201810661515A CN108642464B CN 108642464 B CN108642464 B CN 108642464B CN 201810661515 A CN201810661515 A CN 201810661515A CN 108642464 B CN108642464 B CN 108642464B
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powder
purity
ball
ruthenium
milling
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CN108642464A (en
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逯峙
游龙
郭帅东
王广欣
韩超
张鹏飞
杨斌
闫焉服
孙浩亮
李海涛
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Guangzhou Haipu Electronic Material Technology Co ltd
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Henan University of Science and Technology
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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
    • 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
    • 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
    • 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
    • B22F2003/145—Both compacting and sintering simultaneously by warm compacting, below debindering temperature
    • 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 relates to the technical field of powder metallurgy, in particular to a preparation method of a high-purity ruthenium sputtering target material, which mainly comprises the steps of crushing, ball milling, die filling, unidirectional hot press forming and the like, wherein in the die filling process, 3 powder materials with different granularity levels are mutually filled, and finally, sintering forming is carried out. The invention adopts a powder metallurgy method, can prepare the target material at the temperature lower than the melting point of the material, not only greatly reduces the operation difficulty of equipment, but also can effectively control the introduction of impurities in the preparation process, and can realize the controllable preparation of the tissue fineness of the target material by controlling the granularity of the raw material high-purity ruthenium powder and the sintering process system, thereby greatly reducing the production cost while improving the quality stability of the ruthenium target material product, and being capable of obtaining the high-performance low-cost high-purity ruthenium target material with uniform and controllable microstructure.

Description

Preparation method of high-purity ruthenium sputtering target material
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a preparation method of a high-purity ruthenium sputtering target material.
Background
As a key technology for manufacturing integrated circuits and chips, magnetron sputtering coating has the advantages of simple equipment, easiness in control, high film uniformity and the like. The quality of the sputtering target material has a decisive influence on the film coating effect of magnetron sputtering and the performance of semiconductor devices, so that the high-quality sputtering target material becomes an indispensable key material for the electronic information technology industry. The quality of the thin film formed after sputtering the target (such as the thickness and uniformity of the thin film) can significantly affect the performance of electronic products such as integrated circuits and chips, and the quality of the thin film greatly depends on the structural characteristics of the sputtering target, such as the grain size and the distribution thereof. Therefore, in order to improve the quality of the ruthenium target, it is very critical to control the grain size and grain orientation of the target.
At present, electron beam melting technology is mainly adopted at home and abroad to prepare high-purity target materials, then the high-purity target materials are subjected to organization regulation and control through shaping processing and heat treatment technology to obtain ideal grain size, and then later-stage processing is carried out to finish finished products.
The electron beam smelting process is complex, the smelting process has extremely high requirements on equipment conditions, and the electric power system has large load, so the preparation cost is very high. In addition, ruthenium belongs to high-temperature refractory metal, the melting point is as high as 2310 ℃, the preparation environment belongs to a high-temperature environment, and impurities in the environments such as a crucible, a heating body, a heat-insulating part and the like easily enter the melt, so that the impurities are mixed in the preparation of the high-purity target material, and the later-stage product performance is very unfavorable. The subsequent processing of the cast ingot needs to be repeatedly subjected to plastic processing and heat treatment, and the processes also reduce the purity of the target material and bury hidden troubles.
Disclosure of Invention
The invention aims to provide a preparation method of a high-purity ruthenium sputtering target, which can prepare the target at the temperature lower than the melting point of a material by adopting a powder metallurgy method, not only greatly reduces the operation difficulty of equipment, but also can effectively control the introduction of impurities in the preparation process, and can realize the controllable preparation of the tissue fineness of the target by controlling the granularity and the sintering process system of raw material high-purity ruthenium powder, thereby greatly reducing the production cost while improving the quality stability of ruthenium target products, and being capable of obtaining the high-performance low-cost high-purity ruthenium target with uniform and controllable microscopic structures.
In order to solve the technical problems, the technical scheme and the conception adopted by the invention are as follows: a preparation method of a high-purity ruthenium sputtering target comprises the following steps:
step one, crushing: crushing a high-purity ruthenium block raw material with the purity of more than 99.95% by using a crusher, and performing vibration screening to obtain powder with the particle size of less than 500 mu m; the inner liner of the crusher is provided with a pure ruthenium coating with the purity of more than 99.95 percent;
step two, ball milling: ball-milling the powder with the granularity of below 500 mu m obtained after crushing in a nitrogen atmosphere, mixing 3 high-purity ruthenium balls with different diameters for use, wherein the diameters of the ball-milling balls are all in the range of 5-15 mm, the purity of the ball-milling balls is over 99.95 percent, the ball-milling balls are ball-milled until the granularity is below 200 mu m, and performing multi-stage screening (multi-layer screens with different apertures are adopted for stage-by-stage screening) after ball-milling to obtain powder with multiple granularity levels (represented by the apertures of two adjacent layers of screens);
step three, die filling: taking 3 screened powder with granularity grades, namely powder I, powder II and powder III, wherein the granularity grade of the powder I is less than 10 mu m (the granularity grade is less than 10 mu m and refers to a particle set which can pass through a screen with the aperture of 10 mu m), and the granularity grade of the powder II is D1~D2μ m (meaning the diameter of the passing pore is D)2And can not pass through the screen with the aperture D1Aggregate of particles of (2), 50 μm. ltoreq.D1＜D2≤120μm，D2-D1= 20-30 μm, and the particle size of the powder material III is D3~D4μm，150μm≤D3＜D4≤200μm，D4-D3The powder I is 1/3-1/2 of the powder II, the powder III is 1/5-1/3 of the powder II, the three powders are uniformly mixed (if the powder II is not screened and directly filled into a mold, the particle size distribution range is wider, the mutual filling effect among all the particle sizes is not good, the product density is influenced, if the powder with smaller particle size is used alone, the cost is higher, the powder with moderate particle size is used as a main body, a small amount of large particle size is mixed into the powder, the gaps among the particles are hardly influenced, then a proper amount of small particle size powder is filled into the gaps, the filling effect is greatly improved, the production cost is reduced on the premise of ensuring the product density), the powder is filled into a graphite mold after drying, the graphite mold is vibrated and compacted, the pressure resistance limit of the graphite mold is above 40MPa, and the heat resistance limit is above 2100 ℃;
step four, unidirectional hot pressing molding: placing the graphite mold filled with the powder into a vacuum hot pressing furnace for unidirectional hot pressing sintering, wherein the sintering process is carried out in a protective gas atmosphere, the sintering temperature is 1600-1800 ℃, and the sintering pressure is 5-20 MP; heating at room temperature to 1000 ℃ at a heating rate of 5-10 ℃/min; heating at 1000-1500 deg.c at a rate of 5-8 deg.c/min; at the temperature of 1500 ℃ to the sintering temperature, the heating rate is 2-5 ℃/min; preserving heat for 30-120 min at the sintering temperature, and cooling and demolding after sintering to obtain a billet;
step five, machining: and (4) grinding and polishing the surface of the obtained compact, and processing the compact according to the size of a magnetron sputtering device to obtain the high-purity ruthenium sputtering target.
In the first step, the thickness of the pure material coating is 50-80 μm.
And in the second step, powder with the particle size of below 500 mu m is subjected to ball milling in a ball milling tank, wherein the volume fraction of nitrogen in the ball milling tank is 99%.
And in the second step, ball milling is carried out until the granularity is below 200 mu m and the volume average particle size is 60-70 mu m, and then multi-stage screening is carried out.
Step three, the size of the graphite mould is as follows: the outer dimension (120-180 mm) × (100-130 mm), and the inner cavity is 20-100 mm.
In the fourth step, the protective gas is argon, and the purity of the argon filled into the vacuum hot-pressing furnace is more than 99.999 percent.
Compared with the existing ruthenium target preparation technology, the invention has the advantages that:
1. the preparation process is relatively simple, the controllability of process parameters is strong, the equipment and energy cost is low, and the large-scale industrialization is easy to realize;
2. the preparation cost is low, the temperature of the preparation process is greatly reduced, the possibility of mixing impurities in the preparation process can be greatly reduced, and the purity is easier to ensure;
3. the later processing and deformation processes of the target are less, the microstructure of the product is stable, and the stability of the sputtering performance of the product is facilitated;
4. the adopted powder metallurgy process can realize the regulation and control of the structure fineness of the ruthenium target by methods such as adjusting the granularity of raw material powder, controlling a sintering process system, regulating and controlling a processing process and the like, and the controllability of the performance of the target is stronger.
Drawings
FIG. 1 is an X-ray diffraction pattern of a high purity Ru powder after ball milling and before sieving according to example 1 of the invention;
FIG. 2 is a photomicrograph of the morphology of the high purity Ru powder after ball milling and before sieving in example 1 of the invention;
FIG. 3 is the spectral data of the high purity Ru powder after ball milling and before sieving in example 1 of the invention;
FIG. 4 is an X-ray diffraction pattern of a high-purity Ru target prepared by the method of example 1 according to the invention;
FIG. 5 is a photomicrograph of the surface topography of a high purity Ru target prepared by the method of example 1 of the invention;
fig. 6 is the spectral data of the high purity Ru target material prepared by the method of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, and the details which are not described below are prior art or can be implemented by the prior art.
A preparation method of a high-purity ruthenium sputtering target comprises the following steps:
step one, crushing: crushing a high-purity ruthenium block raw material with the purity of more than 99.95% by using a crusher, and performing vibration screening to obtain powder with the particle size of less than 500 mu m; the inner liner of the crusher is provided with a pure ruthenium coating with the purity of more than 99.95 percent;
step two, ball milling: ball-milling the powder with the granularity of below 500 mu m obtained after crushing in a nitrogen atmosphere, mixing 3 high-purity ruthenium balls with different diameters for use, wherein the diameters of the ball-milling balls are all in the range of 5-15 mm, the purity of the ball-milling balls is over 99.95 percent, the ball-milling balls are ball-milled until the granularity is below 200 mu m, and performing multi-stage screening (multi-layer screens with different apertures are adopted for stage-by-stage screening) after ball-milling to obtain powder with multiple granularity levels (represented by the apertures of two adjacent layers of screens);
step three, die filling: taking the sieved powder with 3 granularity levels, namely powder I and powder IIAnd a powder III, wherein the powder I has a particle size of 10 μm or less (the particle size of 10 μm or less means a collection of particles capable of passing through a sieve having a pore size of 10 μm), and the powder II has a particle size of D1~D2μ m (meaning the diameter of the passing pore is D)2And can not pass through the screen with the aperture D1Aggregate of particles of (2), 50 μm. ltoreq.D1＜D2≤120μm，D2-D1= 20-30 μm, and the particle size of the powder material III is D3~D4μm，150μm≤D3＜D4≤200μm，D4-D3The powder I is 1/3-1/2 of the powder II, the powder III is 1/5-1/3 of the powder II, the three powders are uniformly mixed (if the powder II is not screened and directly filled into a mold, the particle size distribution range is wider, the mutual filling effect among all the particle sizes is not good, the product density is influenced, if the powder with smaller particle size is used alone, the cost is higher, the powder with moderate particle size is used as a main body, a small amount of large particle size is mixed into the powder, the gaps among the particles are hardly influenced, then a proper amount of small particle size powder is filled into the gaps, the filling effect is greatly improved, the production cost is reduced on the premise of ensuring the product density), the powder is filled into a graphite mold after drying, the graphite mold is vibrated and compacted, the pressure resistance limit of the graphite mold is above 40MPa, and the heat resistance limit is above 2100 ℃;
step four, unidirectional hot pressing molding: placing the graphite mold filled with the powder into a vacuum hot pressing furnace for unidirectional hot pressing sintering, wherein the sintering process is carried out in a protective gas atmosphere, the sintering temperature is 1600-1800 ℃, and the sintering pressure is 5-20 MP; heating at room temperature to 1000 ℃ at a heating rate of 5-10 ℃/min; heating at 1000-1500 deg.c at a rate of 5-8 deg.c/min; at the temperature of 1500 ℃ to the sintering temperature, the heating rate is 2-5 ℃/min; preserving heat for 30-120 min at the sintering temperature, and cooling and demolding after sintering to obtain a billet;
step five, machining: and (4) grinding and polishing the surface of the obtained compact, and processing the compact according to the size of a magnetron sputtering device to obtain the high-purity ruthenium sputtering target.
In the first step, the thickness of the pure material coating is 50-80 μm.
And in the second step, powder with the particle size of below 500 mu m is subjected to ball milling in a ball milling tank, wherein the volume fraction of nitrogen in the ball milling tank is 99%.
And in the second step, ball milling is carried out until the granularity is below 200 mu m and the volume average particle size is 60-70 mu m, and then multi-stage screening is carried out.
Step three, the size of the graphite mould is as follows: the outer dimension (120-180 mm) × (100-130 mm), and the inner cavity is 20-100 mm.
In the fourth step, the protective gas is argon, and the purity of the argon filled into the vacuum hot-pressing furnace is more than 99.999 percent.
Example 1
Crushing an industrially purified high-purity ruthenium block with the purity of more than 99.95 percent into small particles with the particle size of less than 500 mu m by a crusher, and carrying out ball milling under the nitrogen protective atmosphere, wherein the ball milling ball diameter is respectively as follows: 5mm, 10mm and 15mm, wherein the number ratio of the three balls is 9:4:1, the mass ratio of the total mass of the balls to the mass of the materials is 3:1, and the balls are ball-milled until the granularity is below 200 mu m and the volume average particle size is 60 mu m; the X-ray diffraction pattern of the high-purity Ru powder before screening after ball milling is shown in figure 1, the diffraction peak shows that only a pure ruthenium phase exists, and other phases do not exist in the powder, so that the cleanliness is high; according to the basic principle of phase analysis, the intensity of an XRD diffraction peak shows the crystallization degree of the material, and the higher the intensity of the diffraction peak is, the more perfect the crystallization is; therefore, the high-purity Ru powder has higher crystallinity; the microscopic morphology of the high-purity Ru powder after ball milling before sieving is shown in FIG. 2, and it can be seen that the Ru powder is formed by agglomeration of ultrafine Ru powder (the smallest Ru powder is less than 5 um) with very small particle size and is dozens of microns to hundreds of microns; this is a characteristic of ball-milled powder; the granularity of the ball-milled powder reaches the superfine grade, and the superfine structure is beneficial to improving the performance of the target material in the later period; the energy spectrum data of the high-purity Ru powder before screening after ball milling is shown in figure 3, and the powder only has a peak value of Ru element and basically has no peak values of other elements, and the fact that the powder does not contain other impurities and has reliable purity can be shown by combining figure 1; after ball milling and screening (multi-stage screening), uniformly mixing powder with three granularity levels of below 10 mu m, 80-100 mu m and 180-200 mu m according to the mass ratio of 1:3:1, drying, putting into a high-strength graphite die, separating ruthenium powder from a die punch by using a gasket to prevent bonding, and then putting into an upper die punch and a lower die punch; then compacting and putting the powder into a lower pressure head of a high-temperature hot-pressing furnace, adjusting the position and ensuring that the die is positioned at the center of the lower pressure head so as to ensure that the material is uniformly pressed during pressurization; starting a cooling water circulation system, vacuumizing the vacuum hot-pressing furnace until the vacuum degree is less than or equal to 20Pa, and filling Ar with the purity of more than or equal to 99.999 percent; when the air pressure in the hot pressing furnace is balanced, the temperature is increased and pressurized, and when the temperature is 1000 ℃, the temperature increasing speed is 10 ℃/min; when the temperature is 1000-1500 ℃, the heating speed is 8 ℃/min, and when the temperature is 1500-1600 ℃, the heating speed is 5 ℃/min; pressurizing while raising the temperature, wherein the applied pressure is 5 MPa; after the final temperature is 1600 ℃ and the temperature is kept for 30min, the heating system is closed to carry out natural cooling, so that the temperature in the hot pressing furnace is reduced to the room temperature; removing the pressure of the pressure head, breaking vacuum (communicating the gas in the furnace body and the gas outside the furnace body), taking the graphite mold out of the vacuum hot-pressing furnace, demolding and taking out a sample billet with the density of 10.1g/cm 3; polishing the surface of the high-purity ruthenium compact, and processing the high-purity ruthenium compact according to the size of magnetron sputtering equipment to obtain a high-purity ruthenium target; the X-ray diffraction pattern of the high-purity Ru target is shown in FIG. 4, only pure ruthenium phase still exists, the diffraction peak intensity is also high, and the crystallinity is good; the microscopic morphology of the surface of the high-purity Ru target is shown in FIG. 5, and the density is not high due to the adoption of smaller hot-pressing pressure, and pores appear on the surface of the material; the energy spectrum data of the high-purity Ru target material is shown in FIG. 6, and it can be seen that the prepared target material still only has a peak of ruthenium element, which indicates that the preparation environment maintains good cleanliness, and no other impurities are mixed in the formed material.
Example 2
The difference from example 1 is that: in the ball milling step, the ball milling ball diameters are respectively as follows: 5mm, 8mm and 13mm, wherein the number ratio of the three balls is 9:3:2, the mass ratio of the total mass of the balls to the mass of the materials is 2:1, and the balls are ball-milled until the granularity is below 200 mu m and the volume average particle size is 63 mu m; in the step of die filling, three kinds of powder with the granularity of less than 10 microns, 60-80 microns and 140-160 microns are uniformly mixed according to the mass ratio of 2:4: 1; in the step of single-direction hot-press molding, when the temperature is between room temperature and 1000 ℃, the heating speed is 10 ℃/min;when the temperature is 1000-1500 ℃, the heating speed is 7 ℃/min, and when the temperature is 1500-1600 ℃, the heating speed is 4 ℃/min; pressurizing while raising the temperature, wherein the applied pressure is 10 MPa; keeping the temperature at 1600 ℃ for 60 min; the density of the sample blank taken out after demoulding is 10.3g/cm3。
Example 3
The difference from example 1 is that: in the ball milling step, the ball milling ball diameters are respectively as follows: 5mm, 7mm and 14mm, wherein the number ratio of the three balls is 8:3:1, the mass ratio of the total mass of the balls to the mass of the materials is 2:1, and the balls are ball-milled until the granularity is below 200 mu m and the volume average particle size is 65 mu m; in the step of die filling, three kinds of powder with the particle size of less than 10 microns, 50-70 microns and 150-170 microns are uniformly mixed according to the mass ratio of 2:5: 1; in the step of single-direction hot-press molding, when the temperature is between room temperature and 1000 ℃, the heating speed is 10 ℃/min; when the temperature is 1000-1500 ℃, the heating rate is 6 ℃/min, and when the temperature is 1500-1700 ℃, the heating rate is 3 ℃/min; pressurizing while raising the temperature, wherein the applied pressure is 15 MPa; preserving the heat for 60min at the final temperature of 1700 ℃; the density of the sample blank taken out after demoulding is 10.5g/cm3。
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (1)

1. A preparation method of a high-purity ruthenium sputtering target material for integrated circuit coating is characterized by comprising the following steps:
step one, crushing: crushing a high-purity ruthenium block raw material with the purity of more than 99.95% by using a crusher, and performing vibration screening to obtain powder with the particle size of less than 500 mu m; the inner liner of the crusher is provided with a pure ruthenium coating with the purity of more than 99.95%, and the thickness of the pure ruthenium coating is 50-80 microns;
step two, ball milling: ball-milling the powder with the granularity of below 500 mu m obtained after crushing in a nitrogen atmosphere, wherein the ball-milling balls are mixed by 3 high-purity ruthenium balls with different diameters, the diameters of the ball-milling balls are respectively 5mm, 7mm and 14mm, the number ratio of the three ball balls is 8:3:1, the mass ratio of the total mass of the balls to the mass of the materials is 2:1, the purity of the ball-milling balls is more than 99.95%, the volume fraction of nitrogen in a ball-milling tank is 99%, the ball-milling balls are ball-milled until the granularity is below 200 mu m and the volume average particle size is 65 mu m, and the powder with multiple granularity levels is obtained by multi-stage screening after ball-milling;
step three, die filling: taking the sieved powder with 3 granularity levels, namely powder I, powder II and powder III, wherein the granularity level of the powder I is less than 10 mu m, and the granularity level of the powder II is D1~D2μm，D1=50μm，D2=70 μm, powder III having a particle size D3~D4μm，D3=150μm，D4And 5, uniformly mixing powder I, powder II and powder III according to the mass ratio of 2:5:1, drying, filling into a graphite mold, and compacting by using a tap, wherein the size of the graphite mold is as follows: the outer dimension (120-180 mm) × (100-130 mm), the inner cavity is 20-100 mm, the pressure resistance limit of the graphite mold is more than 40MPa, and the heat resistance limit is more than 2100 ℃;
step four, unidirectional hot pressing molding: placing the graphite mold filled with the powder into a vacuum hot-pressing furnace for unidirectional hot-pressing sintering, wherein the sintering process is carried out in an argon atmosphere with the purity of more than 99.999 percent, the sintering temperature is 1700 ℃, and the sintering pressure is 15 MP; heating at room temperature to 1000 deg.C at a rate of 10 deg.C/min; heating at 1000-1500 deg.c at a rate of 6 deg.c/min; at 1500 ℃ to the sintering temperature, the heating rate is 3 ℃/min; preserving heat for 60min at the sintering temperature, naturally cooling and demolding after sintering is finished to obtain a billet;
step five, machining: and (4) grinding and polishing the surface of the obtained compact, and processing the compact according to the size of a magnetron sputtering device to obtain the high-purity ruthenium sputtering target.
CN201810661515.4A 2018-06-25 2018-06-25 Preparation method of high-purity ruthenium sputtering target material Active CN108642464B (en)

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CN109158163A (en) * 2018-10-23 2019-01-08 广东迪奥应用材料科技有限公司 The crusher and its manufacturing method of high-purity material is deposited
CN110983265B (en) * 2019-12-24 2022-03-11 湖南欧泰稀有金属有限公司 Preparation method of special-shaped ruthenium product
CN110893467A (en) * 2019-12-24 2020-03-20 湖南欧泰稀有金属有限公司 Grinding tank and preparation method of high-purity superfine ruthenium powder
CN111270210B (en) * 2020-03-17 2021-11-12 贵研铂业股份有限公司 Ruthenium sputtering target with high oriented crystal grains and preparation method thereof
CN114378294A (en) * 2021-12-29 2022-04-22 盐城金美新材料有限公司 High-purity tantalum plate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005153127A (en) * 2003-11-28 2005-06-16 Olympus Corp Optical element molding die and its manufacturing method
CN102485378A (en) * 2010-12-06 2012-06-06 北京有色金属研究总院 Preparation method of ruthenium metal sputtering target material
CN102605332A (en) * 2012-03-25 2012-07-25 昆明贵金属研究所 Ru sputtering target with high purity and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005153127A (en) * 2003-11-28 2005-06-16 Olympus Corp Optical element molding die and its manufacturing method
CN102485378A (en) * 2010-12-06 2012-06-06 北京有色金属研究总院 Preparation method of ruthenium metal sputtering target material
CN102605332A (en) * 2012-03-25 2012-07-25 昆明贵金属研究所 Ru sputtering target with high purity and preparation method thereof

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