阅读说明：本技术 一种铬硅合金溅射靶材及其制备方法 (Chromium-silicon alloy sputtering target material and preparation method thereof ) 是由 姚力军 潘杰 边逸军 王学泽 杨慧珍 于 2021-09-08 设计创作，主要内容包括：本发明提供了一种铬硅合金溅射靶材及其制备方法,所述制备方法包括以下步骤：(1)筛分纯度≥99.98％的铬硅合金原料,得到铬硅合金粉末；(2)将步骤(1)所得铬硅合金粉末进行真空热压烧结处理,得到铬硅合金靶坯；(3)将步骤(2)所得铬硅合金靶坯进行机加工,得到铬硅合金溅射靶材；其中,步骤(2)所述真空热压烧结处理包括顺次进行的第一保温处理、第二保温处理与保温保压处理,且所述保温保压处理的加压过程分为至少2个加压阶段。本发明提供的制备方法保证了靶材的高密度,改善了微观结构均匀性和溅射性能,同时简化了工艺流程,提升了生产效率,降低了生产成本,拓宽了适用范围。(The invention provides a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder; (2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; (3) machining the chromium-silicon alloy target blank obtained in the step (2) to obtain a chromium-silicon alloy sputtering target material; and (3) performing vacuum hot-pressing sintering treatment in the step (2) by sequentially performing first heat preservation treatment, second heat preservation treatment and heat preservation and pressure preservation treatment, wherein the pressure process of the heat preservation and pressure preservation treatment is divided into at least 2 pressure stages. The preparation method provided by the invention ensures the high density of the target material, improves the microstructure uniformity and sputtering performance, simplifies the process flow, improves the production efficiency, reduces the production cost and widens the application range.)

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

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) at the sintering temperature of 1000-1300 ℃ and the pressing pressure of 30-40MPa to obtain a chromium-silicon alloy target blank;

(3) machining the chromium-silicon alloy target blank obtained in the step (2) to obtain a chromium-silicon alloy sputtering target material;

and (3) performing vacuum hot-pressing sintering treatment in the step (2) by sequentially performing first heat preservation treatment, second heat preservation treatment and heat preservation and pressure preservation treatment, wherein the pressure process of the heat preservation and pressure preservation treatment is divided into at least 2 pressure stages.

2. The preparation method according to claim 1, wherein the mass ratio of the silicon element in the chromium-silicon alloy raw material in the step (1) is 50-55%;

preferably, the average grain size of the chromium-silicon alloy powder in the step (1) is less than or equal to 200 mu m.

3. The production method according to claim 1 or 2, wherein the vacuum hot pressing sintering process in step (2) includes mold filling, compacting, vacuum pumping, first temperature raising, first heat preservation, second temperature raising, second heat preservation, pressurizing, heat preservation and pressure preservation, pressure removal and cooling, which are performed in this order.

4. The preparation method according to claim 3, wherein the mold filling body is: the chromium-silicon alloy powder is filled into a graphite die, and the flatness is ensured to be less than or equal to 0.5mm after the die is filled;

preferably, the compacting is in particular: putting the graphite mould into a vacuum sintering furnace, and applying pressure of 0.8-1.2MPa to a pressure head on the top;

preferably, the pressure is applied for a time of 4-6 min;

preferably, the vacuum pumping is carried out until the absolute pressure in the furnace is less than or equal to 100 Pa.

5. The production method according to claim 3 or 4, characterized in that the rate of temperature rise of the first temperature rise is 6 to 8 ℃/min;

preferably, the target temperature of the first temperature rise is 1000-1200 ℃;

preferably, the time of the first heat preservation treatment is 40-80 min;

preferably, the temperature rise rate of the second temperature rise is 2-4 ℃/min;

preferably, the target temperature of the second temperature rise is 1250-1300 ℃;

preferably, the time of the second heat preservation treatment is 60-100 min.

6. The production method according to any one of claims 3 to 5, wherein the pressurization process is divided into 2 pressurization stages, i.e., a first pressurization stage and a second pressurization stage, which are sequentially performed;

preferably, the first pressing stage has a pressing rate of 0.3 to 0.5 MPa/min;

preferably, the target pressure of the first pressurization stage is 20-30 MPa;

preferably, the rate of pressurization of the second pressurization stage is from 0.2 to 0.3 MPa/min;

preferably, the target pressure of the second pressurization stage is 35-40 MPa;

preferably, the time of the heat preservation and pressure maintaining treatment is 100-150 min.

7. The preparation method according to any one of claims 3 to 6, wherein the pressure removal is specifically: filling nitrogen and/or argon into the vacuum sintering furnace until the absolute pressure in the furnace is 0.02-0.04 MPa;

preferably, the cooling is specifically: and taking out the mold when the mold is cooled to the temperature of less than or equal to 200 ℃ along with the furnace, and cooling to room temperature.

8. The method according to any one of claims 1 to 7, wherein the machining in step (3) comprises grinding, cutting, finishing, surface treatment, cleaning, drying and packaging which are performed in sequence.

9. The method of any one of claims 1 to 8, comprising the steps of:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder with the average particle size of less than or equal to 200 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 50-55%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) the chromium-silicon alloy powder is filled into a graphite die, and the flatness is ensured to be less than or equal to 0.5mm after the die is filled;

(B) putting the graphite mold into a vacuum sintering furnace, and applying pressure of 0.8-1.2MPa to a pressure head on the top of the vacuum sintering furnace for 4-6 min;

(C) vacuumizing until the absolute pressure in the furnace is less than or equal to 100 Pa;

(D) raising the temperature to 1000-1200 ℃ at the speed of 6-8 ℃/min, and preserving the temperature for 40-80 min;

(E) heating to 1250-;

(F) pressurizing to 20-30MPa at the rate of 0.3-0.5MPa/min, then pressurizing to 35-40MPa at the rate of 0.2-0.3MPa/min, and keeping the temperature and pressure for 150 min;

(G) filling nitrogen and/or argon into the vacuum sintering furnace until the absolute pressure in the furnace is 0.02-0.04 MPa;

(H) cooling the mold along with the furnace to a temperature of less than or equal to 200 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially carrying out grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging on the chromium-silicon alloy target blank obtained in the step (2) to obtain the chromium-silicon alloy sputtering target.

10. A chromium-silicon alloy sputtering target material prepared by the preparation method according to any one of claims 1 to 9.

Technical Field

The invention belongs to the technical field of sputtering targets, relates to a chromium-silicon alloy sputtering target, and particularly relates to a chromium-silicon alloy sputtering target and a preparation method thereof.

Background

In recent years, with the rapid advance of the 5G technology, the demand of the communication and chip industry for high-purity chromium-silicon targets is greatly increased, however, the chromium-silicon targets produced by various enterprises at present generally have the defects of low density and uneven microstructure, cannot meet the requirements of the high-end electronic industry on the quality of the targets, and are only suitable for manufacturing low-end products. In addition, most of the chromium-silicon targets have high production cost and complex flow, cannot improve the production efficiency and further cannot meet the requirements of wider industrial fields.

CN 105331939A discloses a silicon-containing alloy target material and a preparation method thereof, wherein the preparation method comprises five steps of prealloying powder preparation, cold isostatic pressing treatment after die filling, degassing treatment after re-covering, hot isostatic pressing treatment and machining treatment. Although the preparation method can prepare the target material with low impurity element content, high purity, high density, fine crystal grains and uniform microstructure, the preparation method needs at least two times of die filling treatment and pressing treatment combining cold isostatic pressing, degassing and hot isostatic pressing, and has the defects of complex process, high energy consumption and high cost.

CN 110257781A discloses a Cr-Al-Si-Ni quaternary alloy target material and a preparation method thereof, wherein the preparation method comprises the steps of mixing powder, cold isostatic pressing and pre-pressing after die filling, crushing pre-pressed alloy blocks into metal particles, vacuum sintering and pre-alloying, crushing pre-alloyed blocks into metal powder, packing and degassing, hot isostatic pressing and machining. Although the chromium-aluminum-silicon-nickel quaternary alloy target material prepared by the preparation method has the advantages of high density, no air holes, no looseness, no segregation, fine grains, uniform structure and the like, and can be suitable for sputtering of hard coatings required by various tools and dies, the process flow of the invention is too complex, the application range is limited, and the risk of oxidation of products can be increased by multi-step operation.

Therefore, how to provide the chromium-silicon alloy sputtering target and the preparation method thereof can ensure the high density of the target, improve the microstructure uniformity and the sputtering performance, simplify the process flow, improve the production efficiency, reduce the production cost and widen the application range, and becomes a problem which needs to be solved by technical personnel in the field at present.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method ensures the high density of the target material, improves the microstructure uniformity and the sputtering performance, simplifies the process flow, improves the production efficiency, reduces the production cost and widens the application range.

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 chromium-silicon alloy sputtering target, comprising the following steps:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) at the sintering temperature of 1000-1300 ℃ and the pressing pressure of 30-40MPa to obtain a chromium-silicon alloy target blank;

(3) and (3) machining the chromium-silicon alloy target blank obtained in the step (2) to obtain the chromium-silicon alloy sputtering target.

And (3) performing vacuum hot-pressing sintering treatment in the step (2) by sequentially performing first heat preservation treatment, second heat preservation treatment and heat preservation and pressure preservation treatment, wherein the pressure process of the heat preservation and pressure preservation treatment is divided into at least 2 pressure stages.

According to the invention, the sintering temperature and the pressing pressure of the vacuum hot-pressing sintering treatment are reasonably controlled, the density of the obtained chromium-silicon alloy sputtering target material is increased to more than 99%, the first heat preservation treatment, the second heat preservation treatment and the heat and pressure preservation treatment are sequentially carried out at the same time, and the pressurizing process of the heat and pressure preservation treatment is divided into at least 2 pressurizing stages, so that the uniformity and the sputtering stability of crystal grains in the target material are further improved, the target material cracking phenomenon is avoided, and the microstructure is uniform and has no pores.

In the present invention, the purity of the raw material of the chromium-silicon alloy in step (1) is not less than 99.98%, for example, 99.98%, 99.99% or 99.999%, but the purity is not limited to the recited values, and other values not recited in the above range are also applicable.

In the present invention, the sintering temperature in step (2) is 1000-1300 ℃, for example, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃ or 1300 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

In the present invention, the pressing pressure in the step (2) is 30 to 40MPa, and may be, for example, 30MPa, 31MPa, 32MPa, 33MPa, 34MPa, 35MPa, 36MPa, 37MPa, 38MPa, 39MPa or 40MPa, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.

Preferably, the mass ratio of the silicon element in the raw material of the chromium-silicon alloy in the step (1) is 50% to 55%, for example, 50%, 50.5%, 51%, 51.5%, 52%, 52.5%, 53%, 53.5%, 54%, 54.5% or 55%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the chromium-silicon alloy powder of step (1) has an average particle size of 200 μm or less, and may be, for example, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm or 200 μm, but is not limited to the recited values, and other values not recited in this range are also applicable.

Preferably, the vacuum hot-pressing sintering treatment in the step (2) includes mold filling, compacting, vacuumizing, first temperature raising, first heat preservation treatment, second temperature raising, second heat preservation treatment, pressurizing, heat preservation and pressure maintaining treatment, pressure removing and cooling which are sequentially performed.

Preferably, the die filling specifically comprises: the chromium-silicon alloy powder is charged into a graphite mold and the flatness after mold charging is ensured to be less than or equal to 0.5mm, for example, 0.1mm, 0.15mm, 0.2mm, 0.25mm, 0.3mm, 0.35mm, 0.4mm, 0.45mm or 0.5mm, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.

Preferably, the compacting is in particular: the graphite mold is placed in a vacuum sintering furnace and a pressure of 0.8 to 1.2MPa, for example, 0.8MPa, 0.85MPa, 0.9MPa, 0.95MPa, 1MPa, 1.05MPa, 1.1MPa, 1.15MPa or 1.2MPa is applied to the top head, but the pressure is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.

Preferably, the pressure is applied for a period of 4-6min, for example 4min, 4.2min, 4.4min, 4.6min, 4.8min, 5min, 5.2min, 5.4min, 5.6min, 5.8min or 6min, but is not limited to the recited values, and other values not recited in this range are equally applicable.

Preferably, the vacuum is applied until the absolute pressure in the furnace is less than or equal to 100Pa, such as 10Pa, 20Pa, 30Pa, 40Pa, 50Pa, 60Pa, 70Pa, 80Pa, 90Pa or 100Pa, but the vacuum is not limited to the values listed, and other values not listed in the range are also applicable.

Preferably, the first temperature rise rate is 6 to 8 ℃/min, and may be, for example, 6 ℃/min, 6.2 ℃/min, 6.4 ℃/min, 6.6 ℃/min, 6.8 ℃/min, 7 ℃/min, 7.2 ℃/min, 7.4 ℃/min, 7.6 ℃/min, 7.8 ℃/min, or 8 ℃/min, but is not limited to the values listed, and other values not listed within the range of values are also applicable.

Preferably, the target temperature of the first temperature rise is 1000-1200 ℃, for example, 1000 ℃, 1020 ℃, 1040 ℃, 1060 ℃, 1080 ℃, 1100 ℃, 1120 ℃, 1140 ℃, 1160 ℃, 1180 ℃ or 1200 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the first heat preservation time is 40-80min, such as 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min or 80min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the second temperature rise rate is 2-4 ℃/min, for example, 2 ℃/min, 2.2 ℃/min, 2.4 ℃/min, 2.6 ℃/min, 2.8 ℃/min, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min, or 4 ℃/min, but is not limited to the values listed, and other values not listed within the range of values are also applicable.

Preferably, the target temperature of the second temperature rise is 1250-.

Preferably, the time of the second heat-preservation treatment is 60-100min, such as 60min, 65min, 70min, 75min, 80min, 85min, 90min, 95min or 100min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the pressurization process is divided into 2 pressurization stages, namely a first pressurization stage and a second pressurization stage, which are performed in sequence.

Preferably, the first pressing stage has a pressing rate of 0.3 to 0.5MPa/min, and may be, for example, 0.3MPa/min, 0.32MPa/min, 0.34MPa/min, 0.36MPa/min, 0.38MPa/min, 0.4MPa/min, 0.42MPa/min, 0.44MPa/min, 0.46MPa/min, 0.48MPa/min or 0.5MPa/min, but is not limited to the values listed, and other values not listed within this range are equally applicable.

Preferably, the target pressure in the first pressurization stage is 20 to 30MPa, and may be, for example, 20MPa, 21MPa, 22MPa, 23MPa, 24MPa, 25MPa, 26MPa, 27MPa, 28MPa, 29MPa or 30MPa, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the second pressing stage has a pressing rate of 0.2-0.3MPa/min, such as 0.2MPa/min, 0.21MPa/min, 0.22MPa/min, 0.23MPa/min, 0.24MPa/min, 0.25MPa/min, 0.26MPa/min, 0.27MPa/min, 0.28MPa/min, 0.29MPa/min or 0.3MPa/min, but not limited to the values listed, and other values not listed within this range are equally applicable.

Preferably, the target pressure in the second pressing stage is 35 to 40MPa, and may be, for example, 35MPa, 35.5MPa, 36MPa, 36.5MPa, 37MPa, 37.5MPa, 38MPa, 38.5MPa, 39MPa, 39.5MPa or 40MPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.

Preferably, the time for the heat and pressure holding treatment is 100-150min, and may be, for example, 100min, 105min, 110min, 115min, 120min, 125min, 130min, 135min, 140min, 145min or 150min, but is not limited to the enumerated values, and other unrecited values within the range of the enumerated values are also applicable.

Preferably, the pressure removing is specifically as follows: the nitrogen gas and/or argon gas is introduced into the vacuum sintering furnace to an absolute pressure of 0.02 to 0.04MPa, for example, 0.02MPa, 0.022MPa, 0.024MPa, 0.026MPa, 0.028MPa, 0.03MPa, 0.032MPa, 0.034MPa, 0.036MPa, 0.038MPa or 0.04MPa, but the values are not limited to the values mentioned above, and other values not mentioned above are also applicable within the range.

Preferably, the cooling is specifically: when the mold is cooled to a temperature of 200 ℃ or less, the mold is removed and cooled to room temperature, which may be, for example, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ or 200 ℃, but is not limited to the values listed, and other values not listed within the range of values are also applicable.

Preferably, the machining in step (3) comprises grinding, cutting, finishing, surface treatment, cleaning, drying and packaging which are sequentially carried out.

As a preferred technical solution of the first aspect of the present invention, the preparation method comprises the steps of:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder with the average particle size of less than or equal to 200 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 50-55%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) the chromium-silicon alloy powder is filled into a graphite die, and the flatness is ensured to be less than or equal to 0.5mm after the die is filled;

(B) putting the graphite mold into a vacuum sintering furnace, and applying pressure of 0.8-1.2MPa to a pressure head on the top of the vacuum sintering furnace for 4-6 min;

(C) vacuumizing until the absolute pressure in the furnace is less than or equal to 100 Pa;

(D) raising the temperature to 1000-1200 ℃ at the speed of 6-8 ℃/min, and preserving the temperature for 40-80 min;

(E) heating to 1250-;

(F) pressurizing to 20-30MPa at the rate of 0.3-0.5MPa/min, then pressurizing to 35-40MPa at the rate of 0.2-0.3MPa/min, and keeping the temperature and pressure for 150 min;

(G) filling nitrogen and/or argon into the vacuum sintering furnace until the absolute pressure in the furnace is 0.02-0.04 MPa;

(H) cooling the mold along with the furnace to a temperature of less than or equal to 200 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially carrying out grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging on the chromium-silicon alloy target blank obtained in the step (2) to obtain the chromium-silicon alloy sputtering target.

In a second aspect, the invention provides a chromium-silicon alloy sputtering target material prepared by the preparation method in the first aspect.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, the sintering temperature and the pressing pressure of the vacuum hot-pressing sintering treatment are reasonably controlled, the density of the obtained chromium-silicon alloy sputtering target material is increased to more than 99%, the first heat preservation treatment, the second heat preservation treatment and the heat and pressure preservation treatment are sequentially carried out at the same time, and the pressurizing process of the heat and pressure preservation treatment is divided into at least 2 pressurizing stages, so that the uniformity and the sputtering stability of crystal grains in the target material are further improved, the target material cracking phenomenon is avoided, and the microstructure is uniform and has no pores.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Example 1

The embodiment provides a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.99 percent to obtain chromium-silicon alloy powder with the average particle size of 100 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 52%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) loading chromium-silicon alloy powder into a graphite die, and ensuring that the flatness is 0.3 +/-0.1 mm after die loading;

(B) putting the graphite mold into a vacuum sintering furnace, and applying pressure 1MPa to a pressure head on the top of the vacuum sintering furnace for 5 min;

(C) vacuumizing until the absolute pressure in the furnace is 80 Pa;

(D) heating to 1100 deg.C at a rate of 7 deg.C/min, and maintaining for 60 min;

(E) heating to 1270 deg.C at a rate of 3 deg.C/min, and maintaining for 80 min;

(F) pressurizing to 25MPa at the speed of 0.4MPa/min, pressurizing to 38MPa at the speed of 0.25MPa/min, and keeping the temperature and the pressure for 120 min;

(G) filling nitrogen into the vacuum sintering furnace until the absolute pressure in the furnace is 0.03 MPa;

(H) cooling the mold with the furnace to 150 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging the chromium-silicon alloy target blank obtained in the step (2) according to the specified size of a customer to obtain the chromium-silicon alloy sputtering target.

Example 2

The embodiment provides a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder with the average particle size of 150 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 50%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) loading chromium-silicon alloy powder into a graphite die, and ensuring that the flatness is 0.3 +/-0.1 mm after die loading;

(B) putting the graphite mold into a vacuum sintering furnace, and applying pressure of 0.8MPa to a pressure head on the top of the vacuum sintering furnace for 6 min;

(C) vacuumizing until the absolute pressure in the furnace is 90 Pa;

(D) heating to 1000 deg.C at a rate of 6 deg.C/min, and maintaining for 80 min;

(E) heating to 1250 ℃ at the speed of 2 ℃/min, and preserving heat for 100 min;

(F) pressurizing to 20MPa at the speed of 0.3MPa/min, then pressurizing to 35MPa at the speed of 0.2MPa/min, and preserving heat and pressure for 150 min;

(G) filling argon into the vacuum sintering furnace until the absolute pressure in the furnace is 0.02 MPa;

(H) cooling the mold with the furnace to 150 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging the chromium-silicon alloy target blank obtained in the step (2) according to the specified size of a customer to obtain the chromium-silicon alloy sputtering target.

Example 3

The embodiment provides a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.98 percent to obtain chromium-silicon alloy powder with the average particle size of 200 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 55%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) loading chromium-silicon alloy powder into a graphite die, and ensuring that the flatness is 0.4 +/-0.1 mm after die loading;

(B) putting the graphite mold into a vacuum sintering furnace, and pressing a pressure head on the top to apply pressure of 1.2MPa for 4 min;

(C) vacuumizing until the absolute pressure in the furnace is 100 Pa;

(D) heating to 1200 deg.C at a rate of 8 deg.C/min, and maintaining for 40 min;

(E) heating to 1300 deg.C at a rate of 4 deg.C/min, and maintaining for 60 min;

(F) pressurizing to 30MPa at the speed of 0.5MPa/min, then pressurizing to 40MPa at the speed of 0.3MPa/min, and preserving heat and pressure for 100 min;

(G) filling nitrogen into the vacuum sintering furnace until the absolute pressure in the furnace is 0.04 MPa;

(H) cooling the mold with the furnace to 200 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging the chromium-silicon alloy target blank obtained in the step (2) according to the specified size of a customer to obtain the chromium-silicon alloy sputtering target.

Example 4

The present embodiment provides a chromium-silicon alloy sputtering target and a preparation method thereof, wherein the preparation method is the same as that in embodiment 1 except that the heat preservation time in step (D) is changed to 30min, and therefore, the details are not repeated herein.

Example 5

The present embodiment provides a chromium-silicon alloy sputtering target and a preparation method thereof, wherein the preparation method is the same as that in embodiment 1 except that the heat preservation time in step (E) is changed to 50min, and therefore, the details are not repeated herein.

Example 6

This embodiment provides a chromium-silicon alloy sputtering target and a preparation method thereof, wherein the preparation method is the same as that in embodiment 1 except that the heat-preserving and pressure-maintaining time in step (F) is changed to 90min, and therefore, the details are not repeated herein.

Comparative example 1

The comparative example provides a chromium-silicon alloy sputtering target material and a preparation method thereof, and the preparation method is the same as that of example 1 except that the target temperature of temperature rise in the step (D) is changed to 900 ℃, so that the details are not repeated.

Comparative example 2

The comparative example provides a chromium-silicon alloy sputtering target material and a preparation method thereof, and the preparation method is the same as that of example 1 except that the target temperature of temperature rise in the step (E) is changed to 1400 ℃, so that details are not repeated herein.

Comparative example 3

The comparative example provides a chromium-silicon alloy sputtering target and a preparation method thereof, and the preparation method is the same as that of example 1 except that the final pressing pressure for pressurizing in the step (F) is changed to 28MPa, so that the details are not repeated.

Comparative example 4

The comparative example provides a chromium-silicon alloy sputtering target and a preparation method thereof, and the preparation method is the same as that of example 1 except that the final pressing pressure for pressurization in step (F) is changed to 45MPa, so that the details are not repeated herein.

Comparative example 5

The present comparative example provides a chromium-silicon alloy sputtering target and a preparation method thereof, except that the step (F) is changed to: pressurizing to 38MPa at the rate of 0.4MPa/min, and keeping the temperature and pressure for 120min, wherein the rest conditions are the same as those in example 1, and thus the details are not repeated herein.

Comparative example 6

The embodiment provides a chromium-silicon alloy sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps:

(1) screening the chromium-silicon alloy raw material with the purity of more than or equal to 99.99 percent to obtain chromium-silicon alloy powder with the average particle size of 100 mu m; the mass ratio of silicon element in the chromium-silicon alloy raw material is 52%;

(2) carrying out vacuum hot-pressing sintering treatment on the chromium-silicon alloy powder obtained in the step (1) to obtain a chromium-silicon alloy target blank; the vacuum hot-pressing sintering treatment specifically comprises the following steps:

(A) loading chromium-silicon alloy powder into a graphite die, and ensuring that the flatness is 0.3 +/-0.1 mm after die loading;

(B) putting the graphite mold into a vacuum sintering furnace, and applying pressure 1MPa to a pressure head on the top of the vacuum sintering furnace for 5 min;

(C) vacuumizing until the absolute pressure in the furnace is 80 Pa;

(D) heating to 1270 deg.C at a rate of 7 deg.C/min, pressurizing to 38MPa at a rate of 0.4MPa/min, and maintaining the temperature and pressure for 260 min;

(E) filling nitrogen into the vacuum sintering furnace until the absolute pressure in the furnace is 0.03 MPa;

(F) cooling the mold with the furnace to 150 ℃, taking out the mold and airing to room temperature;

(3) and (3) sequentially grinding, cutting, finish machining, surface treatment, cleaning, drying and packaging the chromium-silicon alloy target blank obtained in the step (2) according to the specified size of a customer to obtain the chromium-silicon alloy sputtering target.

The results of the performance tests of the tungsten carbide targets obtained in examples 1 to 6 and comparative examples 1 to 6 are shown in Table 1.

TABLE 1

In the table, the density of the target was measured by archimedes drainage method; measuring the purity of the target material by a GDMS method; and (4) observing whether the microstructure has pores or not by combining with a scanning electron microscope photo of the surface of the target material.

As can be seen from Table 1: the chromium-silicon alloy sputtering target obtained in the embodiments 1-6 has excellent performance, the density is more than or equal to 99%, no cracking phenomenon exists, and the microstructure is uniform and has no bubbles; comparative examples 1-4 show that the unreasonable settings of sintering temperature and pressing pressure in the vacuum hot-pressing sintering treatment can bring adverse effects to the target material performance; comparative example 5 the pressurizing process was changed to 1 pressurizing stage on the basis of example 1, resulting in a significant decrease in the density of the target material and a certain number of pores in the microstructure; comparative example 6 the temperature rise process and the pressurization process were performed simultaneously on the basis of example 1, i.e., the first and second heat-preservation processes were removed, which also reduced the overall performance of the target and affected its microstructure uniformity.

Therefore, the invention reasonably controls the sintering temperature and the pressing pressure of the vacuum hot-pressing sintering treatment, improves the density of the obtained chromium-silicon alloy sputtering target material to more than 99 percent, simultaneously sequentially performs the first heat preservation treatment, the second heat preservation treatment and the heat and pressure preservation treatment, and divides the pressurizing process of the heat and pressure preservation treatment into at least 2 pressurizing stages, thereby further improving the uniformity and the sputtering stability of crystal grains in the target material, avoiding the cracking phenomenon of the target material, and having uniform microstructure and no pores.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.