CN113652656A - Preparation method of tantalum-silicon dioxide sputtering target material - Google Patents
Preparation method of tantalum-silicon dioxide sputtering target material Download PDFInfo
- Publication number
- CN113652656A CN113652656A CN202110944849.4A CN202110944849A CN113652656A CN 113652656 A CN113652656 A CN 113652656A CN 202110944849 A CN202110944849 A CN 202110944849A CN 113652656 A CN113652656 A CN 113652656A
- Authority
- CN
- China
- Prior art keywords
- tantalum
- silicon dioxide
- powder
- sputtering target
- mixed powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
Abstract
The invention relates to a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the following steps: (1) uniformly mixing tantalum powder and silicon dioxide powder; (2) carrying out hot-pressing sintering treatment on the obtained mixed powder at 1530-1570 ℃ to obtain a tantalum-silicon dioxide sputtering target crude product; (3) and machining to obtain the tantalum-silicon dioxide sputtering target material. The preparation method comprises powder mixing, hot-pressing sintering and machining, particularly the temperature of the hot-pressing sintering is controlled to 1530-1570 ℃, the tantalum-silicon dioxide sputtering target with the purity of more than or equal to 99.9% and the density of more than or equal to 98% can be prepared, the internal organization structure is uniform, the performance requirement of vacuum sputtering is met, the energy consumption and the cost can be reduced, the preparation method has the advantages of short flow and simplicity in operation, and is suitable for large-scale popularization.
Description
Technical Field
The invention relates to the field of target preparation, in particular to a preparation method of a tantalum-silicon dioxide sputtering target.
Background
Physical Vapor Deposition (PVD) refers to a process of evaporating a material source by using a low-voltage and large-current arc discharge technique under a vacuum condition, ionizing both evaporated substances and gas by using gas discharge, and then depositing the evaporated substances and reaction products thereof on a workpiece by an acceleration action of an electric field to form a film with a special function. The PVD technology is a core technology of various industries such as semiconductor chip manufacturing industry, solar energy industry, LCD manufacturing industry and the like, and the main methods comprise vacuum evaporation, arc plasma plating, ion coating, molecular beam epitaxy, sputtering coating and the like.
Sputtering is one of the main techniques for preparing thin film materials, and is characterized in that ions generated by an ion source are accelerated and gathered in vacuum to form ion beam flow with high speed energy, the ion beam flows bombard the surface of a solid, kinetic energy exchange is carried out between the ions and atoms on the surface of the solid, the atoms on the surface of the solid leave the solid and are deposited on the surface of a substrate, and the bombarded solid is a raw material for preparing a thin film deposited by a sputtering method and is generally called as a sputtering target material.
Sputtering targets are generally obtained by powder metallurgy sintering molding processes because the sputtering targets prepared by the processes have unique chemical compositions and mechanical and physical properties that cannot be obtained by conventional fusion casting methods. The powder metallurgy sintering forming process is divided into a hot pressing sintering method and a hot isostatic pressing method, and although the sputtering target material prepared by the hot isostatic pressing method can realize higher densification and has more uniform internal organization structure, the hot isostatic pressing method has the defects of high energy consumption and high cost. In contrast, hot press sintering presses powder or pressed compact uniaxially at high temperature, which generates activation diffusion and creep phenomena, and is widely applied in the fields of sintering of solid materials, large-area welding of dissimilar metals and the like. The main principle of hot-pressing sintering is that crystal lattice and crystal boundary diffusion and plastic flow are carried out at high temperature, and the microstructure of the hot-pressing sintered material, such as grain size, grain distribution and the like, is generally ideal, so that the hot-pressing sintered material has the advantages of low energy consumption and low cost.
In recent years, the physical vapor deposition technology in China is greatly promoted, the PVD industry is vigorously developed, the demand and the variety of high-purity sputtering targets are greatly increased, the composite oxide film is often prepared by respectively utilizing tantalum targets and silicon dioxide targets in the prior art, for example, CN112342506A discloses a preparation method of a low-stress low-absorption oxide film, the Ta with the stress of-120 MPa and the absorption loss of 8ppm can be realized by adopting a dual-ion-beam sputtering deposition technology, taking a tantalum target and a silicon dioxide target as the sputtering targets and selecting proper dual-ion-beam sputtering preparation process parameters2O5Film and SiO with stress of-80 MPa and absorption loss of 4ppm2And (3) preparing a film. However, the high purity tantalum target and the carbon dioxide target produced in China at present have the defects of low purity, low density and the like, cannot meet the requirements of high-end electronic industry on the target quality, are only partially used in low-end products, and cannot meet the latest requirements of the industry by respectively utilizing the tantalum target and the silicon dioxide target, so that the development of the tantalum-silicon dioxide sputtering target is urgently needed.
The tantalum-silicon dioxide sputtering target is a novel sputtering target, is used as a good conductor for vacuum sputtering and can be used for preparing a contact type sensing device. The contact image sensor is used in a scanner, the photosensitive units are closely arranged, light ray information reflected by a scanned manuscript is directly collected, and the contact image sensor can help to manufacture the scanner with lower cost due to low manufacturing cost. At present, only a few enterprises such as Japan three-well chemistry and the like can produce high-purity and high-density tantalum-silicon dioxide target materials worldwide, and the research and development of a production technology of tantalum-silicon dioxide sputtering target materials is a powerful means for breaking through foreign monopolies and reducing the industry cost.
In summary, there is a need to develop a method for preparing a tantalum-silicon dioxide sputtering target, so that the purity of the prepared tantalum-silicon dioxide sputtering target is not less than 99.9%, the density is not less than 98%, the internal organization structure is uniform, and the performance requirement of vacuum sputtering is met.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the steps of powder mixing, hot-pressing sintering and machining, particularly, the temperature of the hot-pressing sintering is controlled to be 1530-1570 ℃, so that the tantalum-silicon dioxide sputtering target material with the purity of more than or equal to 99.9% and the density of more than or equal to 98% can be prepared, the internal organization structure is uniform, the performance requirements of vacuum sputtering are met, the energy consumption and the cost can be reduced, the preparation method has the advantages of shorter flow and simplicity in operation, and is suitable for large-scale popularization.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the following steps:
(1) uniformly mixing tantalum powder and silicon dioxide powder to obtain mixed powder;
(2) carrying out hot-pressing sintering treatment on the mixed powder in the step (1) at the temperature of 1530-1570 ℃ to obtain a tantalum-silicon dioxide sputtering target crude product;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
The preparation method adopts hot-pressing sintering treatment, strictly controls the temperature of the hot-pressing sintering to be 1530-1570 ℃, can greatly improve the density of the tantalum-silicon dioxide sputtering target material, meets the high requirements of more than 98% of density and uniform internal organization structure, can reduce energy consumption and cost, has the advantages of short flow and simple operation, and is suitable for large-scale popularization.
It is worth to say that the tantalum-silicon dioxide sputtering target material comprises silicon dioxide components as oxides, different from common alloy sputtering target materials, chemical reaction can occur in the preparation process, covalent bonds are generated, and then a new alloy phase is generated, and the compactness of tantalum and silicon dioxide is improved mainly by means of hot-pressing sintering in the preparation process. In addition, on the basis of no tantalum-silicon dioxide phase diagram, through a large number of experiments, the inventor finds that the compactness of the tantalum-silicon dioxide sputtering target can be effectively ensured only by strictly controlling the hot-pressing sintering temperature to be 1530-1570 ℃.
The temperature of the hot press sintering treatment of the present invention is 1530 to 1570 ℃, for example 1530 ℃, 1535 ℃, 1540 ℃, 1545 ℃, 1550 ℃, 1555 ℃, 1560 ℃, 1565 ℃ or 1570 ℃, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
It is worth noting that the temperature of the hot-pressing sintering treatment is strictly limited within the range of 1530-1570 ℃ by the preparation method, so that the problems of abnormal growth of crystal grains and the like caused by overhigh temperature can be prevented, and the problem of substandard density caused by overlow temperature can be prevented.
In a preferred embodiment of the present invention, the mixed powder in the step (1) contains 30 to 40 mass% of silicon dioxide, and the balance of tantalum and inevitable impurities.
The mass percentage of silica in the mixed powder of the present invention is 30 to 40%, for example, 30%, 32%, 34%, 35%, 37%, 39%, or 40%, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
It is worth to be noted that the tantalum-silicon dioxide sputtering target material is used for preparing a composite oxide film, a certain conductive performance needs to be prepared, the mass percent of silicon dioxide in the powder mixing process is controlled to be 30-40%, the resistivity of the tantalum-silicon dioxide sputtering target material can be ensured to be 1.5-5 k omega cm, and the conductive performance requirement of the composite oxide film is further ensured; furthermore, the total content of unavoidable impurities in the mixed powder according to the invention is < 0.01%.
As a preferable technical scheme of the invention, the average grain size of the tantalum powder in the step (1) is less than 45 μm, and the average grain size of the tantalum powder is ensured to be less than 45 μm by screening.
Preferably, the average particle size of the silicon dioxide powder in the step (1) is less than 10 μm, and the silicon dioxide powder is screened to ensure that the average particle size of the silicon dioxide powder is less than 10 μm.
It should be noted that the average particle size in the present invention refers to D50, i.e., the particle size corresponding to the cumulative percentage of particle size distribution of a sample reaching 50%.
As a preferred embodiment of the present invention, the mixing in step (1) is carried out in a powder mixer.
Preferably, the mixing in step (1) is performed by dry mixing with zirconia balls.
It is worth mentioning that the zirconium oxide ball is added for dry mixing, so that the tantalum powder and the silicon dioxide powder can be uniformly mixed, and after the mixing is finished, the zirconium oxide ball is taken out, so that the uniformly mixed powder can be obtained.
Preferably, the mass ratio of the zirconia balls to the ball material is 1 (6-8), such as 1:6, 1:6.2, 1:6.5, 1:6.8, 1:7, 1:7.2, 1:7.5, 1:7.8 or 1:8, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
It should be noted that the ball mass ratio of the present invention refers to the ratio of the mass of the zirconia balls to the sum of the masses of the tantalum powder and the silica powder.
Preferably, the mixing time in step (1) is 20-24 h, such as 20h, 21h, 22h, 23h or 24h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, before the hot pressing sintering treatment in the step (2), the method further comprises the steps of filling the mixed powder in the step (1) into a die, compacting, and sealing.
Preferably, the mold is a graphite mold.
Preferably, the compaction process comprises: firstly, the mixed powder in the die is subjected to leveling treatment to ensure that the planeness is less than 5mm, and then the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5 mm.
It is worth mentioning that the degree of flatness of the compaction treatment needs to be less than 5mm before the manual column pressing, so that the situation of local looseness in the manual column pressing process can be effectively prevented, then the compaction treatment is carried out through the manual column pressing, the degree of flatness is less than 0.5mm, the initial density requirement required by the hot-pressing sintering treatment can be met, and the tantalum-silicon dioxide sputtering target material with the density of more than or equal to 98% can be obtained through the subsequent hot-pressing sintering treatment.
As a preferable technical solution of the present invention, the hot press sintering process in the step (2) includes the following steps:
putting the mixed powder in the step (1) into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, firstly heating to 900-1000 ℃, preserving heat for 1-1.5 h, then heating to 1250-1300 ℃, preserving heat for 1-1.5 h, then heating to 1530-1570 ℃, preserving heat for 1-1.5 h, and finally pressurizing to 30-40 MPa, preserving heat and preserving pressure for 2-2.5 h.
The hot-pressing sintering treatment adopts a staged heating operation, wherein the primary heating is performed to 900-1000 ℃, the secondary heating is performed to 1250-1300 ℃, the third heating is performed to 1530-1570 ℃, and the target pressure is performed by pressurizing to 30-40 MPa, so that the internal and external temperatures of the tantalum-silicon dioxide mixed powder are uniform, the integral densification degree of the product in the heat preservation and pressure maintaining processes is uniform, and the cracking problem caused by insufficient local shrinkage degree is avoided; and the temperature of the secondary heating is 1250-1300 ℃, so that the critical initial densification requirement can be met, and a density basis is provided for the subsequent overall densification at the target temperature.
The temperature of the first-stage heating in the hot press sintering treatment of the present invention is 900 to 1000 ℃, for example, 900 ℃, 930 ℃, 950 ℃, 980 ℃ or 1000 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The temperature of the second temperature rise of the hot pressing sintering treatment of the present invention is 1250 to 1300 ℃, for example, 1250 ℃, 1260 ℃, 1270 ℃, 1280 ℃, 1290 ℃ or 1300 ℃, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The heat preservation time corresponding to the first-stage heating, the second-stage heating and the third-stage heating of the hot pressing sintering treatment is 1-1.5 h, such as 1h, 1.1h, 1.2h, 1.3h, 1.4h or 1.5h, etc., but the heat preservation time is not limited to the recited values, and other values not recited in the numerical value range are also applicable.
The pressure of the hot press sintering treatment of the present invention is 30 to 40MPa, for example, 30MPa, 32MPa, 34MPa, 35MPa, 37MPa, 39MPa or 40MPa, but the pressure is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The heat-preserving and pressure-maintaining time of the hot-pressing sintering treatment of the present invention is 2 to 2.5 hours, for example, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, or 2.5 hours, but the present invention is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable embodiment of the present invention, the rate of temperature rise to 900 to 1000 ℃ is 8 to 12 ℃/min, for example, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min, 10.5 ℃/min, 11 ℃/min, 11.5 ℃/min, or 12 ℃/min, but is not limited to the above-mentioned values, and other values not mentioned within the above-mentioned range are also applicable.
Preferably, the rate of temperature increase to 1250 to 1300 ℃ is 3 to 7 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, or 7 ℃/min, but not limited to the recited values, and other values not recited within this range are also applicable.
Preferably, the rate of heating to 1530-1570 ℃ is 3-7 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, or 7 ℃/min, but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, after the heat preservation at 1530-1570 ℃ is finished, pressurizing to 30-40 MPa within 90 min.
As the preferable technical scheme of the invention, in the heating processes of heating to 900-1000 ℃, 1250-1300 ℃ and 1530-1570 ℃, the internal pressure of the sealed die needs to be controlled to be less than 6MPa, because: on one hand, in the temperature rise process, the pressure in the die is increased due to the fact that the tantalum-silicon dioxide mixed powder expands when heated, the internal pressure needs to be controlled to be less than 6MPa to guarantee that the die cannot deform, and on the other hand, the powder can be fully heated and expanded and can move freely due to the control of the internal pressure.
Preferably, after the heat preservation and pressure maintenance are finished, the hot-pressing sintering furnace is closed and cooled, and then argon is filled until the vacuum representation number is between-0.06 and-0.08 MPa, such as-0.06 MPa, -0.065MPa, -0.07MPa, -0.075MPa or-0.08 MPa, but the invention is not limited to the values listed, and other values in the value range are also applicable.
Preferably, when the temperature in the hot-pressing sintering furnace is lower than 200 ℃, the blank in the die is taken out, and the tantalum-silicon dioxide sputtering target crude product can be obtained.
As a preferred technical scheme of the invention, the machining in the step (3) comprises grinding and/or wire cutting.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing tantalum powder with the average particle size of less than 45 mu m and silicon dioxide powder with the average particle size of less than 10 mu m in a powder mixer according to the mass ratio, wherein the mixing adopts a mode of adding zirconia balls for dry mixing, the mass ratio of the ball materials is controlled to be 1 (6-8), and the tantalum powder and the silicon dioxide powder are uniformly mixed for 20-24 hours to obtain mixed powder;
wherein the mass percent of silicon dioxide in the mixed powder is 30-40%, and the balance is tantalum and inevitable impurities;
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 900-1000 ℃ at a heating rate of 8-12 ℃/min, preserving heat for 1-1.5 h, heating to 1250-1300 ℃ at a heating rate of 3-7 ℃/min, preserving heat for 1-1.5 h, heating to 1530-1570 ℃ at a heating rate of 3-7 ℃/min, preserving heat for 1-1.5 h, and finally pressurizing to 30-40 MPa within 90min, preserving heat and maintaining pressure for 2-2.5 h; wherein, in the temperature rising process of rising the temperature to 900-1000 ℃, rising the temperature to 1250-1300 ℃ and rising the temperature to 1530-1570 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
after the heat preservation and pressure maintenance are finished, closing the hot-pressing sintering furnace and cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target material;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the preparation method comprises powder mixing, hot-pressing sintering and machining, particularly the temperature of the hot-pressing sintering is controlled to 1530-1570 ℃, the tantalum-silicon dioxide sputtering target with the purity of more than or equal to 99.9 percent and the density of more than or equal to 98 percent can be prepared, the internal organization structure is uniform, the performance requirement of vacuum sputtering is met,
(2) the preparation method disclosed by the invention can reduce energy consumption and cost, has the advantages of short process and simplicity in operation, and is suitable for large-scale popularization.
Drawings
FIG. 1 is a flow chart of a method for preparing a tantalum-silicon dioxide sputtering target material provided by the invention.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Fig. 1 shows a flow chart of a method for preparing a tantalum-silicon dioxide sputtering target material provided by the invention, which specifically comprises the following steps:
(1) uniformly mixing tantalum powder and silicon dioxide powder to obtain mixed powder;
(2) filling the mixed powder obtained in the step (1) into a die, sealing the die, and performing hot-pressing sintering treatment on the mixed powder at the temperature of 1530-1570 ℃ to obtain a tantalum-silicon dioxide sputtering target crude product;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
To facilitate understanding of the invention, the following examples are set forth:
example 1
The embodiment provides a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the following steps:
(1) mixing tantalum powder with the average grain size of less than 45 mu m and silicon dioxide powder with the average grain size of less than 10 mu m in a powder mixer according to the mass ratio, wherein the mixing adopts a mode of adding zirconia balls for dry mixing, the mass ratio of the ball materials is controlled to be 1:7, and the tantalum powder and the silicon dioxide powder are uniformly mixed for 24 hours to obtain mixed powder;
wherein the mass percent of silicon dioxide in the mixed powder is 34.58%, and the balance is tantalum and inevitable impurities;
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 1000 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, heating to 1550 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, and finally pressurizing to 35MPa within 90min, preserving heat and maintaining pressure for 2 h; wherein, in the temperature rising processes of rising to 1000 ℃, rising to 1300 ℃ and rising to 1550 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
after the heat preservation and pressure maintenance are finished, closing the hot-pressing sintering furnace and cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target material;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
Example 2
The embodiment provides a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the following steps:
(1) mixing tantalum powder with the average grain size of less than 45 mu m and silicon dioxide powder with the average grain size of less than 10 mu m in a powder mixer according to the mass ratio, wherein the mixing adopts a mode of adding zirconia balls for dry mixing, the mass ratio of the ball materials is controlled to be 1:6, and the tantalum powder and the silicon dioxide powder are uniformly mixed after 20 hours to obtain mixed powder;
wherein the mass percent of silicon dioxide in the mixed powder is 40%, and the balance is tantalum and inevitable impurities;
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 900 ℃ at the heating rate of 8 ℃/min, preserving heat for 1.5h, heating to 1250 ℃ at the heating rate of 3 ℃/min, preserving heat for 1.5h, heating to 1530 ℃ at the heating rate of 3 ℃/min, preserving heat for 1.5h, and finally pressurizing to 30MPa within 90min, preserving heat and maintaining pressure for 2.5 h; wherein, in the temperature rising processes of rising to 900 ℃, rising to 1250 ℃ and rising to 1530 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
after the heat preservation and pressure maintenance are finished, closing the hot-pressing sintering furnace and cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target material;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
Example 3
The embodiment provides a preparation method of a tantalum-silicon dioxide sputtering target material, which comprises the following steps:
(1) mixing tantalum powder with the average grain size of less than 45 mu m and silicon dioxide powder with the average grain size of less than 10 mu m in a powder mixer according to the mass ratio, wherein the mixing adopts a mode of adding zirconia balls for dry mixing, the mass ratio of the ball materials is controlled to be 1:8, and the tantalum powder and the silicon dioxide powder are uniformly mixed for 22 hours to obtain mixed powder;
wherein the mass percent of silicon dioxide in the mixed powder is 30%, and the balance is tantalum and inevitable impurities;
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 1000 ℃ at the heating rate of 12 ℃/min, preserving heat for 1.5h, heating to 1300 ℃ at the heating rate of 7 ℃/min, preserving heat for 1.5h, heating to 1570 ℃ at the heating rate of 7 ℃/min, preserving heat for 1.5h, and finally pressurizing to 40MPa within 90min, preserving heat and maintaining pressure for 2.3 h; wherein, in the temperature rising processes of rising to 1000 ℃, rising to 1300 ℃ and rising to 1570 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
after the heat preservation and pressure maintenance are finished, closing the hot-pressing sintering furnace and cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target material;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
Example 4
The embodiment provides a method for preparing a tantalum-silicon dioxide sputtering target, except that the three-stage heating manner in the step (2) is replaced by a two-stage heating manner, and other conditions are completely the same as those in the embodiment 1, and the specific contents are as follows:
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 1000 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, heating to 1550 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, and finally pressurizing to 35MPa within 90min, preserving heat and maintaining pressure for 2 h; wherein, in the temperature rising processes of rising to 1000 ℃, rising to 1300 ℃ and rising to 1550 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
and after the heat preservation and pressure preservation are finished, closing the hot-pressing sintering furnace, cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target.
Example 5
The embodiment provides a method for preparing a tantalum-silicon dioxide sputtering target, except that the three-stage heating manner in the step (3) is replaced by a two-stage heating manner, and other conditions are completely the same as those in the embodiment 1, and the specific contents are as follows:
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 1300 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, heating to 1550 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, and finally pressurizing to 35MPa within 90min, preserving heat and maintaining pressure for 2 h; wherein, in the temperature rising processes of rising to 1000 ℃, rising to 1300 ℃ and rising to 1550 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
and after the heat preservation and pressure preservation are finished, closing the hot-pressing sintering furnace, cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target.
Comparative example 1
The present comparative example provides a method for producing a tantalum-silica sputtering target, in which the conditions were exactly the same as in example 1, except that the temperature of the three-stage temperature increase (i.e., the target temperature of hot press sintering) in the hot press sintering process described in step (3) was changed from "1550℃" to "1450℃".
Comparative example 2
This comparative example provides a method for producing a tantalum-silica sputtering target, in which the conditions were exactly the same as in example 1 except that the temperature of the three-stage temperature increase (i.e., the target temperature of hot-press sintering) in the hot-press sintering process described in step (3) was changed from "1550" to "1650".
The preparation methods of the tantalum-silicon dioxide sputtering target materials prepared in the above embodiments and comparative examples are used for carrying out relevant tests on density, purity, resistivity and internal structure uniformity, and the specific contents are as follows:
(i) density: the measurement is carried out according to the basket hanging method disclosed in the national standard GB/T3850-2015 Density measurement method for dense sintered metal materials and hard alloys;
(ii) purity: measuring by Glow Discharge Mass Spectrometry (GDMS);
(iii) resistivity: measuring by adopting a four-probe resistance tester according to the four-point probe film resistance tester operating specification;
(iv) internal structure uniformity: firstly, a visual standard sample is taken as a standard, and then the surface is clean and uniform in color and luster after precision processing, and no bunch-shaped or dot-shaped specks appear, so that the segregation phenomenon does not appear when the internal structure is uniform;
the specific test results are shown in table 1.
TABLE 1
In conclusion, the preparation method comprises powder mixing, hot-pressing sintering and machining, particularly the temperature of the hot-pressing sintering is controlled to be 1530-1570 ℃, the tantalum-silicon dioxide sputtering target with the purity of more than or equal to 99.9% and the density of more than or equal to 98% can be prepared, the internal organization structure is uniform, the performance requirement of vacuum sputtering is met, the energy consumption and the cost can be reduced, the preparation method has the advantages of short process and simplicity in operation, and is suitable for large-scale popularization.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The preparation method of the tantalum-silicon dioxide sputtering target material is characterized by comprising the following steps:
(1) uniformly mixing tantalum powder and silicon dioxide powder to obtain mixed powder;
(2) carrying out hot-pressing sintering treatment on the mixed powder in the step (1) at the temperature of 1530-1570 ℃ to obtain a tantalum-silicon dioxide sputtering target crude product;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
2. The method according to claim 1, wherein the mixed powder of step (1) contains 30 to 40 mass% of silica, and the balance of tantalum and inevitable impurities.
3. The method according to claim 1 or 2, wherein the average particle size of the tantalum powder of step (1) is less than 45 μm;
preferably, the average particle size of the silica powder in step (1) is less than 10 μm.
4. The method according to any one of claims 1 to 3, wherein the mixing in step (1) is carried out in a powder mixer;
preferably, the mixing in the step (1) adopts a mode of dry mixing by adding zirconia balls;
preferably, the mass ratio of the ball materials corresponding to the zirconia balls is 1 (6-8);
preferably, the mixing time in the step (1) is 20-24 h.
5. The preparation method according to any one of claims 1 to 4, further comprising, before the hot press sintering process in step (2), loading the mixed powder in step (1) into a mold, compacting the mixed powder, and sealing the mold;
preferably, the mold is a graphite mold;
preferably, the compaction process comprises: firstly, the mixed powder in the die is subjected to leveling treatment to ensure that the planeness is less than 5mm, and then the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5 mm.
6. The production method according to any one of claims 1 to 5, wherein the hot press sintering treatment in the step (2) comprises the following steps:
putting the mixed powder in the step (1) into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, firstly heating to 900-1000 ℃, preserving heat for 1-1.5 h, then heating to 1250-1300 ℃, preserving heat for 1-1.5 h, then heating to 1530-1570 ℃, preserving heat for 1-1.5 h, and finally pressurizing to 30-40 MPa, preserving heat and preserving pressure for 2-2.5 h.
7. The method according to claim 6, wherein the rate of temperature rise to 900 to 1000 ℃ is 8 to 12 ℃/min;
preferably, the heating rate of heating to 1250-1300 ℃ is 3-7 ℃/min;
preferably, the heating rate of heating to 1530-1570 ℃ is 3-7 ℃/min;
preferably, after the heat preservation at 1530-1570 ℃ is finished, pressurizing to 30-40 MPa within 90 min.
8. The preparation method according to claim 6 or 7, characterized in that after the heat preservation and pressure maintenance are finished, the hot-pressing sintering furnace is closed and cooled, and then argon is filled until the vacuum representation number is between-0.06 MPa and-0.08 MPa;
preferably, when the temperature in the hot-pressing sintering furnace is lower than 200 ℃, the blank in the die is taken out, and the tantalum-silicon dioxide sputtering target crude product can be obtained.
9. The production method according to any one of claims 1 to 8, wherein the machining in step (3) includes grinding and/or wire cutting.
10. The method according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) mixing tantalum powder with the average particle size of less than 45 mu m and silicon dioxide powder with the average particle size of less than 10 mu m in a powder mixer according to the mass ratio, wherein the mixing adopts a mode of adding zirconia balls for dry mixing, the mass ratio of the ball materials is controlled to be 1 (6-8), and the tantalum powder and the silicon dioxide powder are uniformly mixed for 20-24 hours to obtain mixed powder;
wherein the mass percent of silicon dioxide in the mixed powder is 30-40%, and the balance is tantalum and inevitable impurities;
(2) after the mixed powder in the step (1) is filled into a graphite die, firstly, the mixed powder in the die is subjected to flattening treatment to ensure that the planeness is less than 5mm, then, the mixed powder is subjected to compaction treatment in a manual compression column mode to ensure that the planeness is less than 0.5mm, and the mixed powder is sealed after the compaction treatment;
placing the sealed die into a hot-pressing sintering furnace, vacuumizing to be below 100Pa, heating to 900-1000 ℃ at a heating rate of 8-12 ℃/min, preserving heat for 1-1.5 h, heating to 1250-1300 ℃ at a heating rate of 3-7 ℃/min, preserving heat for 1-1.5 h, heating to 1530-1570 ℃ at a heating rate of 3-7 ℃/min, preserving heat for 1-1.5 h, and finally pressurizing to 30-40 MPa within 90min, preserving heat and maintaining pressure for 2-2.5 h; wherein, in the temperature rising process of rising the temperature to 900-1000 ℃, rising the temperature to 1250-1300 ℃ and rising the temperature to 1530-1570 ℃, the internal pressure of the sealed die is required to be controlled to be less than 6 MPa;
after the heat preservation and pressure maintenance are finished, closing the hot-pressing sintering furnace and cooling, then introducing argon until the vacuum representation number is between-0.06 and-0.08 MPa, and taking out the blank in the die when the temperature in the hot-pressing sintering furnace is less than 200 ℃ to obtain the crude product of the tantalum-silicon dioxide sputtering target material;
(3) and (3) machining the tantalum-silicon dioxide sputtering target crude product obtained in the step (2) to obtain the tantalum-silicon dioxide sputtering target.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110944849.4A CN113652656A (en) | 2021-08-17 | 2021-08-17 | Preparation method of tantalum-silicon dioxide sputtering target material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110944849.4A CN113652656A (en) | 2021-08-17 | 2021-08-17 | Preparation method of tantalum-silicon dioxide sputtering target material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113652656A true CN113652656A (en) | 2021-11-16 |
Family
ID=78491809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110944849.4A Pending CN113652656A (en) | 2021-08-17 | 2021-08-17 | Preparation method of tantalum-silicon dioxide sputtering target material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113652656A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951657A (en) * | 2022-05-31 | 2022-08-30 | 宁波江丰电子材料股份有限公司 | Preparation method of tantalum foil |
| CN115124330A (en) * | 2022-07-04 | 2022-09-30 | 宁波江丰电子材料股份有限公司 | Preparation method of silicon oxide ceramic target blank |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108655403A (en) * | 2018-06-25 | 2018-10-16 | 河南科技大学 | A kind of preparation method of electronic material high-purity tantalum target |
| CN112030120A (en) * | 2020-08-31 | 2020-12-04 | 宁波江丰电子材料股份有限公司 | Preparation method of tantalum-silicon alloy sputtering target material |
-
2021
- 2021-08-17 CN CN202110944849.4A patent/CN113652656A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108655403A (en) * | 2018-06-25 | 2018-10-16 | 河南科技大学 | A kind of preparation method of electronic material high-purity tantalum target |
| CN112030120A (en) * | 2020-08-31 | 2020-12-04 | 宁波江丰电子材料股份有限公司 | Preparation method of tantalum-silicon alloy sputtering target material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114951657A (en) * | 2022-05-31 | 2022-08-30 | 宁波江丰电子材料股份有限公司 | Preparation method of tantalum foil |
| CN114951657B (en) * | 2022-05-31 | 2024-04-12 | 宁波江丰电子材料股份有限公司 | Preparation method of tantalum foil |
| CN115124330A (en) * | 2022-07-04 | 2022-09-30 | 宁波江丰电子材料股份有限公司 | Preparation method of silicon oxide ceramic target blank |
| CN115124330B (en) * | 2022-07-04 | 2023-09-08 | 宁波江丰电子材料股份有限公司 | Preparation method of silicon oxide ceramic target blank |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2125270B1 (en) | Process for producing high density refractory metals&alloys sputtering targets | |
| KR102359630B1 (en) | W-ni sputter target | |
| CN112030120A (en) | Preparation method of tantalum-silicon alloy sputtering target material | |
| CN113579233B (en) | Tungsten-titanium alloy target material and preparation method and application thereof | |
| CN113652656A (en) | Preparation method of tantalum-silicon dioxide sputtering target material | |
| CN111057905B (en) | Method for preparing niobium-titanium alloy through powder metallurgy | |
| CN102069189A (en) | Powder metallurgy method for preparing high-purity materials | |
| TW202024000A (en) | Cr-Si sintered body | |
| KR20210025710A (en) | Tungsten silicide target and method of manufacturing same | |
| WO1995004167A1 (en) | High melting point metallic silicide target and method for producing the same, high melting point metallic silicide film and semiconductor device | |
| CN112111719B (en) | Tungsten titanium silicon alloy sputtering target material and preparation method thereof | |
| CN108103464A (en) | A kind of preparation method of Fe, Al, Co, Cu, Cr, Mn alloy target material | |
| CN112111714B (en) | Preparation method of tantalum-aluminum alloy sputtering target material | |
| TWI551706B (en) | Cu-Ga target and a method for producing the same, and a light absorbing layer composed of a Cu-Ga based alloy film and a CIGS solar cell using the light absorbing layer | |
| CN115255367B (en) | Nickel-aluminum alloy sputtering target material and hot pressing preparation method thereof | |
| CN112011717B (en) | High-strength low-expansion composite material and preparation method thereof | |
| CN111455329B (en) | Aluminum-titanium-boron target material and powder solid-phase alloying sintering method thereof | |
| US20170175252A1 (en) | Sputtering Target Comprising Al-Te-Cu-Zr Alloy, and Method for Producing Same | |
| CN115261806B (en) | Nickel-aluminum alloy sputtering target material and hot isostatic pressing preparation method thereof | |
| CN113088909B (en) | Nickel-chromium alloy sputtering target material and hot-pressing preparation method thereof | |
| CN113549806A (en) | High-entropy alloy-based composite material and preparation method thereof | |
| CN114990499A (en) | Preparation method of molybdenum alloy target | |
| JP2004169064A (en) | Copper-tungsten alloy, and method of producing the same | |
| CN115298149B (en) | Cr-Si sintered compact, sputtering target, and method for producing thin film | |
| CN117024147B (en) | (Ta, nb, hf) x ) 2 C medium entropy alloyed carbide ceramic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |