阅读说明：本技术 一种掺杂亚微米金刚石碳化钨溅射靶材及其制备方法 (Submicron diamond-doped tungsten carbide sputtering target material and preparation method thereof ) 是由 曾路 陈会培 刘文迪 李保强 黄志民 于 2020-07-10 设计创作，主要内容包括：本发明公开了一种掺杂亚微米金刚石碳化钨溅射靶材及其制备方法,其相对密度为95.3-98.6％,平均晶粒尺寸为1.1-4.5μm,原料由纯度≥3N5的碳化钨粉、纯度≥3N的钨粉、纯度≥3N的石墨粉和金刚石粉组成,且钨粉的含量为0.5-5wt％,石墨粉的含量为0.1-1wt％,金刚石粉的含量为0.1-0.7wt％,余量为碳化钨粉,该碳化钨粉的粒径为0.2-0.6μm,该钨粉的粒径为0.02-0.1μm,该石墨粉的粒径为2-4μm,该金刚石粉的粒度为W0-W0.25。本发明通过控制原料粉末掺杂与配比、球磨混粉以及热压烧结工艺,从而制备出尺寸较大、晶粒较细、致密度较高、无Co的碳化钨溅射靶材。(The invention discloses a submicron diamond-doped tungsten carbide sputtering target material and a preparation method thereof, wherein the relative density is 95.3-98.6%, the average grain size is 1.1-4.5 μm, the raw materials comprise tungsten carbide powder with the purity of more than or equal to 3N5, tungsten powder with the purity of more than or equal to 3N, graphite powder with the purity of more than or equal to 3N and diamond powder, the content of the tungsten powder is 0.5-5 wt%, the content of the graphite powder is 0.1-1 wt%, the content of the diamond powder is 0.1-0.7 wt%, and the balance is the tungsten carbide powder, the grain size of the tungsten carbide powder is 0.2-0.6 μm, the grain size of the tungsten powder is 0.02-0.1 μm, the grain size of the graphite powder is 2-4 μm, and the grain size of the diamond powder is W0-W0.25. According to the invention, the tungsten carbide sputtering target material with larger size, finer crystal grain, higher density and no Co is prepared by controlling the doping and proportioning of the raw material powder, the ball milling and powder mixing and the hot pressing sintering process.)

1. A submicron diamond-doped tungsten carbide sputtering target material is characterized in that: the tungsten carbide powder has the relative density of 95.3-98.6 percent and the average grain size of 1.1-4.5 microns, and is prepared from tungsten carbide powder with the purity of more than or equal to 3N5, tungsten powder with the purity of more than or equal to 3N, graphite powder with the purity of more than or equal to 3N and diamond powder, wherein the tungsten powder content is 0.5-5wt percent, the graphite powder content is 0.1-1wt percent, the diamond powder content is 0.1-0.7wt percent, and the balance is the tungsten carbide powder, the tungsten carbide powder particle size is 0.2-0.6 microns, the tungsten powder particle size is 0.02-0.1 microns, the graphite powder particle size is 2-4 microns, and the diamond powder particle size is W0-W0.25.

2. The submicron diamond-doped tungsten carbide sputtering target according to claim 1 wherein: the tungsten powder comprises 1.5-4 wt% of tungsten powder, 0.2-0.5 wt% of graphite powder, 0.3-0.7 wt% of diamond powder and the balance of tungsten carbide powder, wherein the particle size of the tungsten carbide powder is 0.3-0.5 mu m, the particle size of the tungsten powder is 0.08-0.1 mu m, and the particle size of the graphite powder is 3-4 mu m.

3. The method of preparing a submicron diamond-doped tungsten carbide sputtering target material according to claim 1 or 2, wherein the method comprises the following steps: the method comprises the following steps:

(1) carrying out high-energy ball milling on the tungsten carbide powder, the tungsten powder, the graphite powder and the diamond powder in vacuum or inert gas atmosphere to uniformly mix, and then carrying out vacuum sieving to obtain mixed powder;

(2) filling the mixed powder into a prepared die, carrying out cold pressing and hot-pressing sintering, cooling and demoulding to obtain a blank;

(3) and carrying out corresponding linear cutting and surface treatment on the blank to obtain the submicron diamond-doped tungsten carbide sputtering target material.

4. The method of claim 2, wherein: the rotation speed of the high-energy ball mill is 100-150rpm, the time is 12-24h, the ball-material ratio is 5-10: 1, the used grinding balls are hard alloy balls with single specification or mixed specifications, and the used ball mill tank is a nylon tank.

5. The method of claim 2, wherein: the inert gas atmosphere is argon atmosphere.

6. The method of claim 2, wherein: the cold pressing is mechanical oil pressure or cold isostatic pressing; wherein the pressure of the mechanical oil pressure is 5-20t, the time is 5-60s, the pressure of the cold isostatic pressure is 100-200MPa, and the time is 3-5 min.

7. The method of claim 2, wherein: the hot-pressing sintering comprises a front section temperature rise stage, a middle section temperature rise and pressurization and heat preservation and pressure preservation stage and a rear section temperature reduction and pressure reduction stage.

8. The method of claim 7, wherein: the front-stage heating stage comprises: heating to 800-1000 ℃ at the speed of 10-30 ℃/min.

9. The method of claim 7, wherein: the middle section heating and pressurizing and heat preservation and pressure maintaining stage comprises the following steps: heating to 1850 ℃ at the speed of 30-50 ℃/min, pressurizing from 0MPa to 200MPa at the same time, and then maintaining the temperature and pressure for 10-60 min.

10. The method of claim 7, wherein: the rear-section cooling and depressurizing stage comprises: and (4) air cooling to below 1000 ℃, then beginning to release pressure, and cooling to room temperature along with the furnace.

Technical Field

The invention belongs to the technical field of ceramic and hard alloy sintering, and particularly relates to a submicron diamond-doped tungsten carbide sputtering target material and a preparation method thereof.

Background

With the rapid development of various industrial fields, advanced industrial tools, dies, wear-resistant parts and the like put higher demands on the surface properties thereof. The WC coating prepared by the magnetron sputtering coating can effectively improve the hardness and the high-temperature hardness, the corrosion resistance, the wear resistance and the like of the surface of the component, thereby improving the comprehensive performance and greatly prolonging the service life of the component. At present, the WC target containing 2% -6% of Co element is used, although the Co element can effectively promote the sintering process; however, the hardness, wear resistance and other properties of the prepared coating can be reduced due to the existence of Co, and the magnetic property of Co can also influence the actual sputtering process; meanwhile, the WC target material is also applied to a diffusion barrier layer of a semiconductor to a certain extent, so that corresponding requirements on the purity of the WC target material are also put forward; therefore, the preparation of the pure WC target without Co becomes the main trend of future development.

As a target material used for magnetron sputtering, the compactness, the size of crystal grain and the uniformity of the structure of the target material all meet certain requirements to effectively prepare a hard film with required performance. In order to meet the required performance of the target material, the sintering process used at the present stage mainly comprises three main types: spark plasma sintering SPS, hot isostatic pressing HIP, and hot pressing HP. The discharge plasma sintering SPS is used as a novel power-on pressurizing instantaneous sintering, so that a pure WC target material with high density and fine grains can be obtained, but the requirement on size is limited, the productivity is low, and the cost is high; for the hot isostatic pressing sintering HIP, the process flow is long, the operation is complex, and the production cost is high, so the hot isostatic pressing sintering HIP is not suitable for the existing production requirement; therefore, the spark plasma sintering SPS and the hot isostatic pressing sintering HIP have certain limitations in practical production requirements.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a submicron diamond-doped tungsten carbide sputtering target material.

The invention also aims to provide a preparation method of the submicron diamond-doped tungsten carbide sputtering target material.

The technical scheme of the invention is as follows:

the submicron diamond-doped tungsten carbide sputtering target material has a relative density of 95.3-98.6% and an average grain size of 1.1-4.5 microns, and is prepared from tungsten carbide powder with a purity of not less than 3N5, tungsten powder with a purity of not less than 3N, graphite powder with a purity of not less than 3N and diamond powder, wherein the tungsten powder content is 0.5-5 wt%, the graphite powder content is 0.1-1 wt%, the diamond powder content is 0.1-0.7 wt%, and the balance is tungsten carbide powder, the tungsten carbide powder particle size is 0.2-0.6 microns, the tungsten powder particle size is 0.02-0.1 microns, the graphite powder particle size is 2-4 microns, and the diamond powder particle size is W0-W0.25.

In a preferred embodiment of the present invention, the content of the tungsten powder is 1.5 to 4 wt%, the content of the graphite powder is 0.2 to 0.5 wt%, the content of the diamond powder is 0.3 to 0.7 wt%, and the balance is tungsten carbide powder, and the particle size of the tungsten carbide powder is 0.3 to 0.5 μm, the particle size of the tungsten powder is 0.08 to 0.1 μm, and the particle size of the graphite powder is 3 to 4 μm.

The preparation method of the submicron diamond-doped tungsten carbide sputtering target material comprises the following steps:

(1) carrying out high-energy ball milling on the tungsten carbide powder, the tungsten powder, the graphite powder and the diamond powder in vacuum or inert gas atmosphere to uniformly mix, and then carrying out vacuum sieving to obtain mixed powder;

(2) filling the mixed powder into a prepared die, carrying out cold pressing and hot-pressing sintering, cooling and demoulding to obtain a blank;

(3) and carrying out corresponding linear cutting and surface treatment on the blank to obtain the submicron diamond-doped tungsten carbide sputtering target material.

In a preferred embodiment of the invention, the rotation speed of the high-energy ball mill is 100-150rpm, the time is 12-24h, the ball-material ratio is 5-10: 1, the grinding balls are hard alloy balls with single specification or mixed specifications, and the ball mill tank is a nylon tank.

In a preferred embodiment of the present invention, the inert gas atmosphere is an argon atmosphere.

In a preferred embodiment of the invention, the cold pressing is mechanical oil pressure or cold isostatic pressing; wherein the pressure of the mechanical oil pressure is 5-20t, the time is 5-60s, the pressure of the cold isostatic pressure is 100-200MPa, and the time is 3-5 min.

In a preferred embodiment of the present invention, the hot-pressing sintering includes a front-stage heating stage, a middle-stage heating and pressurizing and holding stage, and a rear-stage cooling and depressurizing stage.

More preferably, the first-stage temperature raising stage is: heating to 800-1000 ℃ at the speed of 10-30 ℃/min.

Further preferably, the middle temperature raising and pressurizing and heat preservation and pressure maintaining stage is as follows: heating to 1850 ℃ at the speed of 30-50 ℃/min, pressurizing from 0MPa to 200MPa at the same time, and then maintaining the temperature and pressure for 10-60 min.

Further preferably, the rear-stage cooling and depressurizing stage is as follows: and (4) air cooling to below 1000 ℃, then beginning to release pressure, and cooling to room temperature along with the furnace.

The invention has the beneficial effects that:

1. according to the invention, the tungsten carbide sputtering target material with larger size, finer crystal grain, higher density and no Co is prepared by controlling the doping and proportioning of the raw material powder, the ball milling and powder mixing and the hot pressing sintering process.

2. The invention can effectively save the production cost, meet the industrial requirements on size and quantity, and can effectively improve the efficiency of magnetron sputtering and the quality of coating because of the characteristics of high compactness, fine grains and no doping of other metal elements.

Drawings

Fig. 1 is a scanning electron micrograph of a doped submicron diamond tungsten carbide sputtering target prepared in example 8.

Detailed Description

The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.