CN113004040B

CN113004040B - Carbon silicon carbide target material and preparation method and application thereof

Info

Publication number: CN113004040B
Application number: CN202110199569.5A
Authority: CN
Inventors: 姚力军; 边逸军; 潘杰; 王学泽; 杨慧珍
Original assignee: Ningbo Jiangfeng Electronic Material Co Ltd
Current assignee: Ningbo Jiangfeng Electronic Material Co Ltd
Priority date: 2021-02-22
Filing date: 2021-02-22
Publication date: 2022-05-06
Anticipated expiration: 2041-02-22
Also published as: KR102641901B1; KR20220120447A; WO2022174506A1; CN113004040A

Abstract

The invention provides a carbon silicon carbide target material and a preparation method and application thereof. The preparation method is simple in preparation process, and the silicon carbide target material with the density of more than or equal to 99.0% can be prepared by combining the secondary ball milling and the sintering process. The obtained silicon carbide carbon target has uniform and compact microstructure and excellent sputtering performance, can effectively improve the working efficiency and prolong the service life of printing equipment when being applied to the fields of 3D printing or thermal printing and the like, and has wide application prospect.

Description

Carbon silicon carbide target material and preparation method and application thereof

Technical Field

The invention relates to the technical field of targets, in particular to the technical field of silicon carbide carbon targets, and particularly relates to a silicon carbide carbon target and a preparation method and application thereof.

Background

The thermal print head comprises a substrate made of insulating material, a base layer formed on the substrate, lead electrodes formed on the base layer, a heating resistor strip formed above the lead electrodes and the base layer along a main printing direction, and a protective layer arranged above the lead electrodes and the heating resistor strip. The protective layer is usually an insulating layer or a combination of an insulating layer and a wear-resistant layer, and usually, both the insulating layer and the wear-resistant layer are made of low thermal conductivity materials. In the process of heating of the heating resistor body, heat generated by the heating resistor body is transferred to the printing medium through the protective layer, and the printing medium generates corresponding change according to the transferred heat. After the heating resistor body heats, the amount of heat transferred to the printing medium is directly related to the thickness and the heat conductivity of the protective layer.

In the process of temperature reduction of the thermal printing head, the working voltage stops printing and adding, the heating resistor stops heating, the ideal state is that in the moment that the working voltage stops printing and adding, the temperature on the surface of the protective layer is rapidly reduced to the required low-temperature state, the temperature reduction is realized only in a heat conduction mode in the process, so that the protective layer is required to have the characteristic of high heat conductivity at the moment, the residual heat in the protective layer is ensured to be conducted away in the moment, the actual protective layer does not have the characteristic of high heat conductivity, in the moment that the working voltage stops printing and adding, a large amount of heat residual in the protective layer is conducted away through the thermal printing head, one part of the residual heat is conducted away through the printing medium, and the other part of the residual heat is conducted away through the printing medium, so that the trailing phenomenon appears in the printing process and the printing quality is influenced. If the thickness of the protective layer is reduced, although the heat transfer efficiency is improved, the wear resistance of the thermal head is greatly reduced, which seriously affects the performance of the thermal head.

Meanwhile, due to the material characteristics of the insulating layer and the wear-resistant layer, the wear-resistant layer cannot be in direct contact with the lead electrode, so that the insulating layer must exist, but when the insulating layer is in direct contact with the wear-resistant layer, the wear-resistant layer often falls off, the wear resistance of the wear-resistant layer cannot be fully exerted, and the wear resistance of the printing head is greatly reduced.

CN203651201U discloses a thermal print head, which comprises a substrate made of insulating material, a base layer is arranged on the substrate, and is characterized in that a lead electrode is formed on the base layer, a heating resistor strip along the main printing direction is formed on the lead electrode, a protective layer is arranged above the lead electrode and the heating resistor strip, the protective layer is divided into three layers, the bottom layer is an insulating layer with low wear resistance, the middle layer is a high heat conducting layer with the heat conductivity at least 2 times that of the insulating layer, the top layer is a wear-resistant layer, the thermal response speed of the upper surface of the thermal print head is improved, the heat transferred upwards during temperature rise is increased, the middle layer is a transition layer, the adhesive force between the insulating layer and the wear-resistant layer is increased, the characteristic of large hardness of the wear-resistant layer can be fully exerted, and the wear resistance of the thermal print head is ensured.

CN112010675A and CN108409330A also disclose printed ceramic materials, respectively, supporting the development of thermal printing, 3D printing. However, along with the expansion of the thermal printing and 3D printing markets, the demand for the silicon carbide target material capable of improving the printing equipment and the working efficiency in the industry is increasing day by day, and meanwhile, in order to ensure the stable performance of the silicon carbide target material during vacuum sputtering and the wear resistance of the film layer, the target material is required to have higher density and uniform microstructure without pores.

However, because the silicon carbide target material has special material properties, great difficulty in production technology and difficulty in post-processing, the silicon carbide target material with high density and stable performance is difficult to produce at present, and the requirement of the heat-sensitive industry on the quality of the target material cannot be met.

Therefore, it is necessary to develop a method for preparing a carbon silicon carbide target material with high density and uniform microstructure without pores.

Disclosure of Invention

In order to solve the technical problems, the invention provides a silicon carbide target material and a preparation method and application thereof, wherein the preparation method of the silicon carbide target material can be used for preparing the silicon carbide target material with high density and high purity; the obtained silicon carbide carbon target has uniform microstructure and excellent sputtering performance, can effectively improve the working efficiency and the service life of printing equipment when being applied to the printing field, and has wide application prospect.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a method for preparing a silicon carbide target, the method comprising the steps of:

(1) mixing carbon powder and silicon carbide powder, and performing first ball milling in a solvent environment to obtain a first mixture;

(2) drying the first mixture obtained in the step (1), mixing the dried first mixture with a solvent and polyhydric alcohol, and performing second ball milling to obtain a second mixture;

(3) and (3) sequentially carrying out die filling, sintering and cooling on the second mixture in the step (2) to obtain the silicon carbide target material.

According to the preparation method of the carbon silicon carbide target material, the solvent, the carbon powder and the silicon carbide powder are mixed and ball-milled, so that the mixing uniformity of the carbon powder and the silicon carbide powder is improved, the second ball milling is carried out after the drying, the polyol is added, and the effect similar to granulation is achieved, so that the fluidity of the second mixture is improved, the second mixture is favorably and tightly compacted in the subsequent die filling and sintering processes, the surface uniformity of a final product is improved, the surface defects are reduced, and the density of the carbon silicon carbide target material is improved.

Preferably, the particle size of the carbon powder in step (1) is less than 20 μm, and may be, for example, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the particle size of the silicon carbide powder in step (1) is less than 10 μm, and may be, for example, 5 μm, 5.6 μm, 6.2 μm, 6.7 μm, 7.3 μm, 7.8 μm, 8.4 μm, 8.9 μm, 9.5 μm, or 10 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.

The invention preferably selects the particle sizes of the carbon powder and the silicon carbide powder within the range, is more favorable for uniform mixing of the first ball mill and control of the particle size of the second mixture in the second ball mill, and can effectively ensure the compactness of the silicon carbide target material.

Preferably, the carbon powder in step (1) is high purity carbon powder with purity of 99.995% or more, and the purity can be, for example, 99.995%, 99.999%, 99.9994%, 99.9996%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the silicon carbide powder in step (1) is high purity silicon carbide powder with a purity of 99.9% or more, for example, 99.9%, 99.92%, 99.95%, 99.96%, 99.98%, 99.99%, 99.992%, 99.995%, 99.998%, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the mass ratio of the carbon powder and the silicon carbide powder in the step (1) is 40 to 50:60 to 50, and may be, for example, 40:60, 45:60, 48:60, 50:60, 40:58, 42:58, 44:59, 45:55, 48:52 or 50:50, but is not limited to the enumerated values, and other values not enumerated within the range are also applicable.

Preferably, the solvent in step (1) is ethanol.

Preferably, the first ball milling in step (1) has a ball ratio of 1 to 3:1, for example, 1:1, 1.2:1, 1.5:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, or 3.0:1, but not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the time of the first ball milling in the step (1) is not less than 24h, such as 24h, 25h, 26h, 28h, 30h, 32h or 35h, but not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the ball milling media of the first ball milling in the step (1) is silicon carbide balls.

Preferably, the first ball milling in step (1) is performed in a sealed condition.

Preferably, the drying of step (2) comprises drying.

Preferably, the drying temperature in step (2) is 100 to 140 ℃, for example, 100 ℃, 105 ℃, 109 ℃, 114 ℃, 118 ℃, 123 ℃, 127 ℃, 132 ℃, 136 ℃ or 140 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the drying time in step (2) is 8-16 h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16h, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the solvent is added in the step (2) in an amount of 0.1 to 1wt% of the first mixture, and may be, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1wt%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the solvent in step (2) is ethanol.

Preferably, the amount of the polyol added in step (2) is 0.1 to 5wt% of the first mixture, and may be, for example, 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.8 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 4 wt%, 4.5 wt%, or 5wt%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.

The polyhydric alcohol of the invention comprises glycerol or propylene glycol, and the like, and the glycerol is preferably adopted, so that the particle size of the second mixture can be better controlled.

Preferably, the second ball milling in step (2) has a ball ratio of 1 to 3:1, for example, 1:1, 1.2:1, 1.5:1, 1.8:1, 2.0:1, 2.2:1, 2.5:1, or 3.0:1, but not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the time of the second ball milling in the step (2) is not less than 24h, such as 24h, 25h, 26h, 28h, 30h, 32h or 35h, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the second ball-milling medium in step (2) is silicon carbide balls.

According to the invention, the ball milling media of the first ball milling and the second ball milling are preferably silicon carbide balls, so that the higher purity of the powder can be ensured.

Preferably, the second ball milling in step (2) is performed in a sealed condition.

The first ball milling and the second ball milling are carried out under the sealed condition, which is favorable for preventing slurry from leaking in the powder mixing process and improving the purity of the product.

Preferably, the second ball-milled material in the step (2) is sieved to obtain a second mixture.

Preferably, the particle size of the second mixture in step (2) is 200 μm or less, and may be, for example, 200 μm, 190 μm, 180 μm, 170 μm, 165 μm, 160 μm, 150 μm, 120 μm or 100 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the flatness of the surface of the second mixture after the molding in step (3) is 0.5mm or less, and may be, for example, 0.1mm, 0.15mm, 0.19mm, 0.20mm, 0.28mm, 0.30mm, 0.37mm, 0.40mm, 0.46mm, or 0.5mm, but is not limited to the values listed, and other values not listed in this range may be similarly applied.

The invention can improve the performance of the sintered silicon carbide target material by ensuring that the flatness is less than or equal to 0.5mm after the mould is filled.

Preferably, the die-filling of step (3) includes: and filling the second mixture into a mold, tightly wrapping by using a wrapping material, and compacting.

Because the carbon silicon carbide powder is light and smooth, the coating material can further effectively prevent the powder from being drawn out of the die in the sintering process, and the sintering performance and the yield are improved.

Preferably, the wrapping material in the step (3) is carbon fiber cloth.

Preferably, cold pressing is further included between the die filling and sintering in the step (3).

Preferably, the cold pressing in the step (3) comprises manually applying pressure to the mold until the mold cannot be pressed.

Preferably, step (3) includes evacuation and filling with protective gas between the mold filling and sintering.

Preferably, the vacuum is applied in step (3) to an absolute vacuum degree of 100Pa or less, such as 50Pa, 56Pa, 62Pa, 67Pa, 73Pa, 78Pa, 84Pa, 89Pa, 95Pa or 100Pa, but not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the time period of the vacuum pumping in step (3) is not less than 40min, such as 40min, 42min, 43min, 45min, 48min, 50min, 52min, 55min, 60min, 65min or 70min, but not limited to the recited values, and other values not recited in the range are also applicable.

The invention controls the vacuumizing speed by controlling the total vacuumizing time, prevents powder from being pumped out in the vacuumizing process, obviously improves the density of the final silicon carbide target material and reduces the cracking risk of the target material.

Preferably, the shielding gas in step (3) is filled to a gauge pressure of-0.08 to-0.1 MPa, for example, -0.08MPa, -0.082MPa, -0.085MPa, -0.09MPa, -0.095MPa or-0.1 MPa, but not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the shielding gas of step (3) comprises argon.

Preferably, the sintering in step (3) comprises: under the condition of protective gas filling, the temperature is increased to a first temperature through a first temperature rise; then, the temperature is increased to a second temperature for second heat preservation; carrying out second pressure rise to a second pressure while carrying out second heat preservation, and keeping the pressure until the second heat preservation is finished; continuing to increase the temperature to a third temperature through a third temperature increase, and vacuumizing in the third temperature increase process until the third temperature increase is finished; and keeping the third temperature, raising the pressure to a third pressure through a third pressure, and then carrying out third heat preservation.

The invention preferably adopts three-stage pressure rising and two-stage pressure rising steps to match, which is more favorable for improving the sintering effect and finally improving the density of the silicon carbide target material.

Preferably, in step (3), the third temperature rise rate is smaller than the second temperature rise rate and smaller than the first temperature rise rate.

Preferably, the first temperature raising rate in the step (3) is 8 to 12 ℃/min, for example, 8 ℃/min, 8.5 ℃/min, 8.9 ℃/min, 9.4 ℃/min, 9.8 ℃/min, 10.3 ℃/min, 10.7 ℃/min, 11.2 ℃/min, 11.6 ℃/min, or 12 ℃/min, etc., but not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the first temperature in step (3) is 1400 to 1500 ℃, and may be 1400 ℃, 1412 ℃, 1423 ℃, 1434 ℃, 1445 ℃, 1456 ℃, 1467 ℃, 1478 ℃, 1489 ℃ or 1500 ℃, for example, but not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the second temperature raising rate in the step (3) is 4 to 6 ℃/min, for example, 4 ℃/min, 4.3 ℃/min, 4.5 ℃/min, 4.7 ℃/min, 4.9 ℃/min, 5.2 ℃/min, 5.4 ℃/min, 5.6 ℃/min, 5.8 ℃/min, or 6 ℃/min, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the duration of the second heat preservation in step (3) is 40-100 min, such as 40min, 47min, 54min, 60min, 67min, 74min, 80min, 87min, 94min or 100min, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the second temperature in step (3) is 1750 to 1850 ℃, and may be, for example, 1750 ℃, 1762 ℃, 1773 ℃, 1784 ℃, 1795 ℃, 1806 ℃, 1817 ℃, 1828 ℃, 1839 ℃ or 1850 ℃, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the second pressure increasing time period in step (3) is 12-25 min, such as 12min, 14min, 15min, 17min, 18min, 20min, 21min, 23min, 24min or 25min, but not limited to the enumerated values, and other unrecited values in the range are also applicable.

Preferably, the second pressure in step (3) is 7 to 9MPa, and may be, for example, 7MPa, 7.3MPa, 7.5MPa, 7.7MPa, 7.9MPa, 8.2MPa, 8.4MPa, 8.6MPa, 8.8MPa or 9MPa, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the rate of the third temperature rise in the step (3) is 1 to 3.5 ℃/min, for example, 1 ℃/min, 1.3 ℃/min, 1.6 ℃/min, 1.9 ℃/min, 2.2 ℃/min, 2.5 ℃/min, 2.7 ℃/min, 3 ℃/min, 3.3 ℃/min, or 3.5 ℃/min, etc., but is not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the third temperature in step (3) is 1950-2050 ℃, and may be 1950 ℃, 1962 ℃, 1973 ℃, 1984 ℃, 1995 ℃, 2006 ℃, 2017 ℃, 2028 ℃, 2039 ℃ or 2050 ℃, for example, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the third temperature raising process in step (3) is performed under vacuum to an absolute vacuum degree of 100Pa or less, such as 100Pa, 95Pa, 90Pa, 85Pa, 80Pa, 75Pa or 70Pa, but not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the third pressure increasing time period in the step (3) is 40-80 min, such as 40min, 45min, 50min, 54min, 58min, 60min, 67min, 70min, 76min or 80min, but not limited to the enumerated values, and other non-enumerated values in the range are also applicable.

Preferably, the third pressure in step (3) is 30 to 40MPa, and may be, for example, 30MPa, 32MPa, 33MPa, 34MPa, 35MPa, 36MPa, 37MPa, 38MPa, 39MPa or 40MPa, but is not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the duration of the third heat preservation in step (3) is 150-220 min, such as 150min, 160min, 166min, 170min, 180min, 189min, 197min, 205min, 213min or 220min, but not limited to the values listed, and other values not listed in this range are also applicable.

Preferably, the cooling of step (3) comprises: and after sintering, stopping heating, cooling to a second temperature, relieving pressure, introducing protective gas, cooling to a fourth temperature along with the furnace, and finishing cooling.

Preferably, the temperature reduction in the step (3) is natural temperature reduction along with the furnace.

Preferably, the protective gas of step (3) comprises argon.

Preferably, the fourth temperature in step (3) is 200 ℃ or lower, and may be, for example, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, or 200 ℃, but is not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, after the cooling in step (3), the method further comprises: and machining the silicon carbide target.

As a preferable technical scheme of the invention, the preparation method comprises the following steps:

(1) mixing carbon powder with the granularity of less than 20 microns and silicon carbide powder with the granularity of less than 10 microns according to the mass ratio of 40-50: 60-50, and carrying out first ball milling on the mixture in an ethanol environment in a sealed condition for more than or equal to 24 hours by using silicon carbide balls, wherein the material-ball ratio is 1-3: 1 to obtain a first mixture;

(2) drying the first mixture obtained in the step (1), mixing the dried first mixture with ethanol and polyhydric alcohol, wherein the addition amount of the ethanol is 0.1-1 wt% of the first mixture, the addition amount of the polyhydric alcohol is 0.1-5 wt% of the first mixture, performing second ball milling on the mixture by using silicon carbide balls in a sealed condition, the time of the second ball milling is more than or equal to 24 hours, and sieving the ball-milled material to obtain a second mixture;

(3) filling the second mixture in the step (2) into a mold, wherein the flatness of the surface of the second mixture after mold filling is less than or equal to 0.5mm, cold pressing, vacuumizing after cold pressing until the absolute vacuum degree is less than or equal to 100Pa, filling protective gas until the gauge pressure is-0.08 to-0.1 MPa, and first heating to 1400-1500 ℃ at the speed of 8-12 ℃/min under the condition of protective gas filling;

secondly heating to 1750-1850 ℃ at a speed of 4-6 ℃/min, and carrying out second heat preservation for 40-100 min; secondly, increasing the pressure to 7-9 MPa within 12-25 min while carrying out second heat preservation, and keeping the pressure until the second heat preservation is finished;

continuing to heat to 1950-2050 ℃ at a rate of 1-3.5 ℃/min for the third time, vacuumizing in the third heating process until the third heating is finished, and vacuumizing until the absolute vacuum degree is less than or equal to 100 Pa; keeping 1950-2050 ℃, performing third pressure rise to 30-40 MPa within 40-80 min, and performing third heat preservation for 150-220 min; and after the third heat preservation is finished, stopping heating, cooling to 1750-1850 ℃, decompressing, introducing protective gas, and cooling to less than or equal to 200 ℃ along with the furnace to obtain the silicon carbide target.

The preparation method provided by the invention improves the uniformity of the microstructure on the surface of the product and reduces the surface defects by improving the mixing mode of the carbon powder and the silicon carbide powder, and obviously improves the density of the product by combining the specific three-step heating and three-step boosting processes in sintering.

In a second aspect, the present invention provides a silicon carbide target material, which is prepared according to the method for preparing the silicon carbide target material of the first aspect.

The target material prepared by the first aspect of the invention has high density and purity, excellent performance and good application prospect.

In a third aspect, the present invention provides use of the silicon carbide carbon target of the second aspect in thermal printing or 3D printing.

The density of the silicon carbide carbon target material prepared by the invention is more than or equal to 95.9%, the density is more than or equal to 99% under better conditions, the purity is more than or equal to 99.7%, the requirements of magnetron sputtering on the purity and the density of the target material are met, and the silicon carbide carbon target material is used for a wear-resistant layer of a thermal printing head, can improve the working efficiency of the thermal printing equipment and can prolong the service life of the thermal printing equipment.

The percentages relating to purity and component content in the present invention are mass percentages.

Compared with the prior art, the invention has at least the following beneficial effects:

(1) according to the preparation method of the carbon silicon carbide target material, provided by the invention, the secondary ball milling step is adopted, the granularity of the second mixture is controlled, the uniformity of the surface of the carbon silicon carbide target material is finally improved, and the surface defects are reduced;

(2) the preparation method of the carbon silicon carbide target material further adopts three-stage temperature rise and two-stage pressure rise operation for sintering, so that the density of the product is guaranteed, and the performance is excellent;

(3) the density of the carbon silicon carbide target material provided by the invention is not less than 95.9%, the density is not less than 99% under better conditions, and the purity is not less than 99.7%, so that the requirement of the heat-sensitive industry on the target material is met.

Drawings

Fig. 1 is a surface structure diagram of a silicon carbide carbon target provided in embodiment 1 of the present invention.

FIG. 2 is a surface texture map of a silicon carbide carbon target material provided in comparative example 3 of the present invention.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

First, an embodiment

Example 1

The embodiment provides a preparation method of a carbon silicon carbide target, which comprises the following steps:

(1) mixing carbon powder with the granularity of less than 20 microns and silicon carbide powder with the granularity of less than 10 microns according to the mass ratio of 45:55, and carrying out first ball milling on the mixture in an ethanol environment for 48 hours in a sealed condition, wherein the material-ball ratio is 2:1, so as to obtain a first mixture;

(2) drying the first mixture in the step (1) at 120 ℃ for 12 hours, mixing the dried first mixture with ethanol and glycerin, wherein the addition amount of the ethanol is 0.5 wt% of the first mixture, the addition amount of the glycerin is 1wt% of the first mixture, performing second ball milling on the mixture by using silicon carbide balls in a sealed condition, wherein the time of the second ball milling is 48 hours, and sieving the ball-milled material to obtain a second mixture, wherein the particle size range of the second mixture is 120-160 mu m;

(3) filling the second mixture into a graphite mold, wrapping the second mixture with dense carbon fiber cloth, compacting, ensuring that the flatness of the surface of the second mixture after mold filling is below 0.35mm, then putting the mold into a vacuum sintering furnace, ensuring the mold to be horizontal after placement, manually applying pressure to the mold, cold-pressing until the mold cannot be pressed, vacuumizing for 60min after cold-pressing until the absolute vacuum degree is reduced to below 90Pa, stopping vacuumizing, filling argon into the vacuum sintering furnace until the gauge pressure is-0.09 MPa, stopping filling the argon, and first heating to 1450 ℃ at a rate of 10 ℃/min while filling the argon;

secondly heating to 1800 ℃ at the speed of 5 ℃/min, and carrying out second heat preservation for 60 min; after the temperature is raised to 1800 ℃, the pressure is increased to 8MPa within 20min for the second time while the temperature is maintained for the second time, and the pressure is maintained until the second temperature is maintained;

continuing to heat to 2000 ℃ at a third temperature of 3 ℃/min, vacuumizing in the third temperature rise process until the third temperature rise is finished, and vacuumizing to reduce the absolute vacuum degree to below 100 Pa; keeping the temperature at 2000 ℃ and increasing the pressure to 35MPa within 60min for the third time, and then carrying out the third heat preservation for 180 min; and after the third heat preservation is finished, stopping heating, cooling to 1800 ℃, decompressing, introducing argon, cooling to 100 ℃ along with the furnace, taking out, and processing to the required size in a grinding processing mode, a linear cutting mode and the like to obtain the silicon carbide target material.

Example 2

(1) mixing carbon powder with the granularity of less than 20 microns and silicon carbide powder with the granularity of less than 10 microns according to the mass ratio of 40:60, and carrying out first ball milling on the mixture in an ethanol environment for 24 hours in a sealed condition, wherein the material-ball ratio is 1:1, so as to obtain a first mixture;

(2) drying the first mixture obtained in the step (1) at 100 ℃ for 16 hours, mixing the dried first mixture with ethanol and glycerol, wherein the addition amount of the ethanol is 0.1 wt% of the first mixture, the addition amount of the glycerol is 5wt% of the first mixture, performing second ball milling on the mixture by using silicon carbide balls in a sealed condition, the time of the second ball milling is 28 hours, and sieving the ball-milled material to obtain a second mixture, wherein the particle size range of the second mixture is 130-180 mu m;

(3) putting the second mixture into a graphite mold, wrapping the second mixture by dense carbon fiber cloth, compacting, ensuring that the flatness of the surface of the second mixture after mold filling is below 0.5mm, putting the mold into a vacuum sintering furnace, keeping the mold horizontal after placement, manually applying pressure to the mold, cold-pressing until the mold cannot be pressed, vacuumizing for 50min after cold pressing until the absolute vacuum degree is reduced to below 100Pa, stopping vacuumizing, filling argon into the vacuum sintering furnace until the gauge pressure is-0.08 MPa, stopping filling the argon, and first heating to 1400 ℃ at 8 ℃/min while filling the argon;

secondly heating to 1750 ℃ at the speed of 4 ℃/min, and carrying out second heat preservation for 40 min; after the temperature is increased to 1750 ℃, the pressure is increased to 7MPa within 12min for the second heat preservation, and the pressure is maintained until the second heat preservation is finished;

continuing to heat to 2000 ℃ at a rate of 1 ℃/min for the third time, vacuumizing in the third temperature rise process until the third temperature rise is finished, and vacuumizing to a vacuum degree until the absolute vacuum degree is reduced to below 90 Pa; keeping the temperature at 2000 ℃ and carrying out third heat preservation for 280min after third pressure rise to 30MPa within 80 min; and after the third heat preservation is finished, stopping heating, cooling to 1750 ℃, decompressing, introducing argon, cooling to 200 ℃ along with the furnace, taking out, and processing to the required size in a grinding processing mode, a linear cutting mode and the like to obtain the silicon carbide target material.

Example 3

(1) mixing carbon powder with the granularity of less than 18 mu m and silicon carbide powder with the granularity of less than 9 mu m according to the mass ratio of 50:50, and carrying out first ball milling on the mixture in an ethanol environment for 36 hours in a sealed condition, wherein the material-ball ratio is 3:1, so as to obtain a first mixture;

(2) drying the first mixture obtained in the step (1) at 140 ℃ for 8 hours, mixing the dried first mixture with ethanol and glycerol, wherein the addition amount of the ethanol is 1wt% of the first mixture, the addition amount of the glycerol is 0.1 wt% of the first mixture, performing second ball milling on the mixture by using silicon carbide balls in a sealed condition for 36 hours, and sieving the ball-milled material to obtain a second mixture, wherein the particle size of the second mixture is 140-200 microns;

(3) putting the second mixture into a graphite mold, wrapping the second mixture by using dense carbon fiber cloth, compacting, ensuring that the flatness of the surface of the second mixture after mold filling is below 0.4mm, putting the mold into a vacuum sintering furnace, keeping the mold horizontal after placement, manually applying pressure to the mold, cold-pressing until the mold cannot be pressed, vacuumizing for 55min after cold-pressing until the absolute vacuum degree is reduced to below 90Pa, stopping vacuumizing, filling argon into the vacuum sintering furnace until the gauge pressure is-0.1 MPa, stopping filling the argon, and first heating to 1500 ℃ at the speed of 12 ℃/min while filling the argon;

secondly heating to 1850 ℃ at the speed of 6 ℃/min, and carrying out second heat preservation for 100 min; after the temperature is raised to 1850 ℃, the pressure is raised to 9MPa within 25min for the second time while the temperature is maintained for the second time, and the second temperature is maintained;

continuing to heat to 2050 ℃ at a third temperature rise rate of 3.5 ℃/min, vacuumizing in the third temperature rise process until the third temperature rise is finished, and vacuumizing to a vacuum degree until the absolute vacuum degree is reduced to below 90 Pa; keeping 2050 ℃ and carrying out third heat preservation for 150min after third pressure rise to 40MPa within 40 min; and after the third heat preservation is finished, stopping heating, cooling to 2050 ℃, decompressing, introducing argon, cooling to 200 ℃ along with the furnace, taking out, and processing to the required size in a grinding processing mode, a linear cutting mode and the like to obtain the silicon carbide target material.

Example 4

The embodiment provides a preparation method of a carbon silicon carbide target, which is the same as that in the embodiment 1 except that the particle size range of carbon powder in the step (1) is 5-30 μm.

Example 5

The embodiment provides a preparation method of a silicon carbide target, which is the same as that in the embodiment 1 except that the particle size range of the silicon carbide powder in the step (1) is 5-20 μm.

Example 6

The embodiment provides a preparation method of a carbon silicon carbide target, which is the same as that in the embodiment 1 except that glycerol is replaced by propylene glycol in the step (2).

Example 7

The embodiment provides a preparation method of a carbon-silicon carbide target, which is the same as that in the embodiment 1 except that in the step (3), the temperature is maintained for the second time, the second pressure is increased to 35MPa, and the third pressure is not increased.

Example 8

The embodiment provides a preparation method of a carbon-silicon carbide target, which is the same as that in embodiment 1 except that in step (3), third temperature rise is not performed, second temperature rise to 2050 ℃ is directly performed, second heat preservation is performed for 250min, and second pressure rise and third pressure rise are sequentially performed in the second heat preservation.

Example 9

The embodiment of the present invention provides a method for preparing a silicon carbide target, which is the same as that in embodiment 1 except that the vacuum pumping time after cold pressing is 34 min.

Compared with example 9, in example 1, the vacuum-pumping time is longer, the powder is not easy to be pumped out, and the density of the final product is obviously higher than that of the silicon carbide target material in example 9.

Second, comparative example

Comparative example 1

The comparative example provides a preparation method of a carbon-silicon carbide target, which is the same as that in example 1 except that the step (2) is not performed, and the first ball milling is performed for 96 hours.

Comparative example 2

The comparative example provides a preparation method of a carbon-silicon carbide target, which is the same as that in example 1 except that glycerin is not added in the step (2).

Comparative example 3

The comparative example provides a preparation method of a carbon-silicon carbide target, which is the same as that in example 1 except that the step (1) is not performed, and the step (2) is performed by directly using two kinds of powder as a first mixture.

Third, test and results

The morphology of the surface of the formed silicon carbide target is observed, wherein the surfaces of the silicon carbide targets prepared in the example 1 and the comparative example 3 are respectively shown in fig. 1 and fig. 2, and it can be seen that the powder mixing mode of the secondary ball milling is adopted in the example 1, the surface is smooth, the microstructure is uniform, the defect is obviously smaller than that of the comparative example 3, the density in the comparative example 3 is only 98.0%, the density in the example 1 is higher, and the sputtering performance is excellent.

The uniformity of the structure of the surface of the formed silicon carbide target in the comparative examples 1 and 2 is poorer than that of the example 1, and the compactness in the comparative examples 1 and 2 is only 98.4 percent and 97.9 percent respectively, the surface defects are obviously more than those in the example 1, and the sputtering performance of the target is poorer.

The structure uniformity of the surfaces of the carbon silicon carbide targets in the embodiments 2-9 is better than that of the comparative examples 1-2, and the defects of the surface microstructures are few.

In comparison with examples 1 and 4 to 5, the carbon powder and the silicon carbide powder with smaller particle sizes are used in example 1, and compared with examples 4 to 5, the uniformity of the surface structure is higher and the number of defects is less, which shows that the particle size ranges of the carbon powder and the silicon carbide powder raw materials are further controlled, and the silicon carbide target with less surface defects can be obtained.

The densities of the silicon carbide targets prepared in the above examples and comparative examples were measured by a water discharge method and glow discharge mass spectrometry, and the results are shown in table 1.

TABLE 1

	Density (%)	Whether or not to crack
			Example 1	99.8	Whether or not
Example 2	99.3	Whether or not
			Example 3	99.1	Whether or not
Example 4	99.0	Whether or not
			Example 5	99.1	Whether or not
Example 6	99.6	Whether or not
			Example 7	97.3	Cracking of
Example 8	95.9	Whether or not

From table 1, the following points can be seen:

(1) it can be seen from the comprehensive examples 1 to 6 that the carbon silicon carbide target provided by the invention further integrates the process conditions and the secondary ball milling method, can obtain the carbon silicon carbide target which is not cracked and has the density of more than or equal to 99.0%, and the surface microstructure of the carbon silicon carbide target is uniform, the defects are few, and the sputtering performance is excellent;

(2) it can be seen from the combination of the embodiment 1 and the embodiment 7 that, compared with the two-step boosting in the embodiment 7, the density of the target in the embodiment 1 is as high as 99.8% and does not crack in the embodiment 1 by adopting the three-step boosting mode in the embodiment 1, and the density in the embodiment 7 is only 97.3% and has a cracking risk, so that the invention obviously improves the density and reduces the cracking problem by further optimizing the boosting mode in sintering;

(3) it can be seen from the combination of the embodiment 1 and the embodiment 8 that, compared with the two-step pressure increase adopted in the embodiment 8, the density of the target material in the embodiment 1 is as high as 99.8% and does not crack, and the density in the embodiment 8 is only 95.9%, which indicates that the density is significantly improved by further optimizing the temperature increase mode in sintering.

In conclusion, the carbon silicon carbide target material provided by the invention can obviously reduce the surface defects and improve the uniformity of a microstructure by a secondary ball milling method, the density can reach 95.9%, the density can reach more than 99.0% under a better condition, the sputtering performance is excellent, and the application prospect is wide.

The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The preparation method of the silicon carbide carbon target is characterized by comprising the following steps of:

(1) mixing carbon powder with the granularity of less than 20 microns and silicon carbide powder with the granularity of less than 10 microns according to the mass ratio of 40-50: 60-50, and performing first ball milling in an ethanol environment to obtain a first mixture;

(2) drying the first mixture in the step (1), mixing the dried first mixture with ethanol and polyhydric alcohol, wherein the addition amount of the ethanol is 0.1-1 wt% of the first mixture, the addition amount of the polyhydric alcohol is 0.1-5 wt% of the first mixture, and performing second ball milling to obtain a second mixture with the particle size range of less than or equal to 200 mu m;

(3) sequentially performing die filling on the second mixture in the step (2), wherein the flatness of the surface of the second mixture after die filling is less than or equal to 0.5mm, performing cold pressing, vacuumizing after cold pressing until the absolute vacuum degree is less than or equal to 100Pa, filling protective gas until the gauge pressure is within-0.08 to-0.1 MPa, sintering and cooling to obtain the silicon carbide target material;

the sintering in the step (3) comprises the following steps: under the condition of protective gas filling, firstly heating to 1400-1500 ℃ at the speed of 8-12 ℃/min;

secondly heating to 1750-1850 ℃ at the speed of 4-6 ℃/min, and carrying out second heat preservation for 40-100 min; performing second pressure rise to 7-9 MPa within 12-25 min while performing the second heat preservation, and maintaining the pressure until the second heat preservation is finished;

continuing to heat to 1950-2050 ℃ at a rate of 1-3.5 ℃/min for the third time, vacuumizing in the third heating process until the third heating is finished, and vacuumizing until the absolute vacuum degree is less than or equal to 100 Pa; keeping 1950-2050 ℃, performing third pressure rise to 30-40 MPa within 40-80 min, and performing third heat preservation for 150-220 min;

the cooling comprises the following steps: after sintering, stopping heating, cooling to a second temperature, relieving pressure, introducing protective gas, and cooling to a fourth temperature along with the furnace to finish cooling;

the density of the silicon carbide target is more than 99%.

2. The preparation method of claim 1, wherein the first ball milling in step (1) has a ball-to-ball ratio of 1-3: 1.

3. The preparation method of claim 1, wherein the time of the first ball milling in the step (1) is not less than 24 h.

4. The preparation method of claim 1, wherein the ball milling media of the first ball milling in step (1) are silicon carbide balls.

5. The method of claim 1, wherein the first ball milling of step (1) is performed in a sealed condition.

6. The preparation method according to claim 1 or 2, characterized in that the ratio of the second ball-milled material balls in the step (2) is 1-3: 1.

7. The preparation method of claim 1 or 2, wherein the time of the second ball milling in the step (2) is not less than 24 h.

8. The preparation method according to claim 1 or 2, characterized in that the ball milling media of the second ball milling in step (2) are silicon carbide balls.

9. The method of manufacturing according to claim 1 or 2, characterized in that the second ball milling of step (2) is performed in a sealed condition.

10. The preparation method according to claim 1 or 2, wherein the second ball-milled material in the step (2) is sieved to obtain a second mixture.

11. The preparation method according to claim 1, wherein the time of vacuumizing after cold pressing in step (3) is not less than 40 min.

12. The method according to claim 1, wherein the shielding gas of step (3) comprises argon gas.

13. The preparation method according to claim 1, wherein the temperature reduction in the step (3) is natural temperature reduction along with a furnace.

14. The method of claim 1, wherein the shielding gas of step (3) comprises argon.

15. The method of claim 1, wherein the fourth temperature of step (3) is 200 ℃ or less.

16. The preparation method according to claim 1, characterized in that in the step (1), the material-ball ratio of the first ball milling is 1-3: 1, the time of the first ball milling is not less than 24h, the ball milling medium of the first ball milling is silicon carbide balls, and the first ball milling is carried out in a sealed condition;

in the step (2), the ratio of material balls to ball balls of the second ball milling is 1-3: 1, the time of the second ball milling is not less than 24h, the ball milling medium of the second ball milling is silicon carbide balls, and the second ball milling is carried out in a sealed condition; sieving the second ball-milled material to obtain a second mixture;

and (3) vacuumizing for more than or equal to 40min after cold pressing, wherein the protective gas comprises argon, the temperature reduction is natural temperature reduction along with the furnace, the protective gas comprises argon, and the fourth temperature is less than or equal to 200 ℃.

17. A silicon carbide target material, characterized in that the silicon carbide target material is prepared by the method for preparing the silicon carbide target material according to any one of claims 1 to 16.

18. Use of the silicon carbide target according to claim 17 in thermal printing or 3D printing.