阅读说明：本技术 一种基于能量调控原理制备超厚硬质薄膜的方法 (Method for preparing ultra-thick hard film based on energy regulation and control principle ) 是由 邱龙时 赵婧 潘晓龙 张于胜 田丰 黎栋栋 刘璐 王志杰 于 2019-09-20 设计创作，主要内容包括：本发明公开了一种基于能量调控原理制备超厚硬质薄膜的方法,该方法包括：一、将基片清洗后吹干得洁净基片；二、将弧靶和洁净基片装入多弧离子镀设备中,对真空室抽真空后加热；三、对洁净基片进行溅射清洗和活化得活化基片；四、在活化基片上镀制金属打底层；五、在镀制的金属打底层的表面沉积过渡层；六、通过能量调节工艺在过渡层上制备能量调节层,冷却后经退火在基片表面得到超厚硬质薄膜。本发明基于能量调控原理,制备由金属打底层、过渡层和能量调节层组成的超厚硬质薄膜,通过调节能量调节层生长过程中的能量输入,减少了内应力,避免了薄膜开裂和剥落,优化了膜层组织结构,得到厚度大于20μm的超厚硬质薄膜。(The invention discloses a method for preparing an ultra-thick hard film based on an energy regulation and control principle, which comprises the following steps: firstly, cleaning a substrate and then drying the substrate to obtain a clean substrate; secondly, putting the arc target and the clean substrate into multi-arc ion plating equipment, vacuumizing the vacuum chamber and heating; thirdly, carrying out sputtering cleaning and activation on the clean substrate to obtain an activated substrate; fourthly, plating a metal priming coat on the activated substrate; fifthly, depositing a transition layer on the surface of the plated metal priming layer; and sixthly, preparing an energy adjusting layer on the transition layer through an energy adjusting process, cooling, and annealing to obtain the ultra-thick hard film on the surface of the substrate. The invention is based on the energy regulation principle, prepares the ultra-thick hard film consisting of the metal bottom layer, the transition layer and the energy regulation layer, reduces the internal stress, avoids the cracking and the peeling of the film, optimizes the film layer structure and obtains the ultra-thick hard film with the thickness more than 20 mu m by regulating the energy input in the growth process of the energy regulation layer.)

1. A method for preparing an ultra-thick hard film based on an energy regulation and control principle is characterized by comprising the following steps:

step one, putting a substrate into analytically pure acetone and analytically pure ethanol in sequence for ultrasonic cleaning, and then drying the substrate by using a hot air blower to obtain a clean substrate;

step two, fixing the arc target on a target holder of the multi-arc ion plating equipment, loading the clean substrate obtained in the step one into a vacuum chamber of the multi-arc ion plating equipment and fixing the clean substrate on a sample rack of a turntable, then closing a furnace door, and sequentially opening a mechanical pump and a molecular pump to vacuumize the vacuum chamber to the vacuum degree of 1.0 multiplied by 10 ^-3Pa～5.0×10 ^-3When Pa, the switch of the heating device is turned on, and the vacuum chamber is heatedHeating to 200-350 ℃;

step three, continuously vacuumizing the vacuum chamber heated to 200-350 ℃ in the step two until the vacuum degree is lower than 1.0 multiplied by 10 ^-3～5.0×10 ^-3Pa, introducing argon into the vacuum chamber, maintaining the vacuum degree at 3.0Pa, opening a bias power supply to apply negative bias to the substrate to 800V, adjusting the duty ratio to 80%, performing sputtering cleaning and activation on the substrate for 20min, and then closing the negative bias power supply and adjusting the duty ratio to 0 to obtain an activated substrate; the mass purity of the argon is not less than 99.99%;

step four, the vacuum chamber provided with the activated substrate in the step three is vacuumized until the vacuum degree is 1.0 multiplied by 10 ^-3Pa～5.0×10 ^-3Pa, introducing argon gas, maintaining the vacuum degree at 1.0Pa, turning on a bias power supply, adjusting the negative bias to 200V, and turning on an arc target power supply, and plating a metal priming layer on the activated substrate through metal particles sputtered by the arc target; the mass purity of the arc target is not less than 99.99%;

step five, continuously maintaining the negative bias voltage in the vacuum chamber to be 200V, then introducing nitrogen gas to the flow rate of 40sccm within 10-30 min, gradually reducing the flow rate of the argon gas to be 8sccm, maintaining the vacuum degree of the vacuum chamber to be 1.0Pa, turning on an arc target power supply, reacting metal particles sputtered by the arc target with the nitrogen gas, and depositing a transition layer on the surface of the metal priming layer plated in the step four;

step six, continuously maintaining the vacuum degree of the vacuum chamber at 1.0Pa, adjusting the duty ratio to 80%, preparing an energy adjusting layer on the surface of the transition layer deposited in the step five through an energy adjusting process to obtain a substrate with a film on the surface, then closing a gas valve, an arc target power supply, a negative bias power supply and a heating device in sequence, closing a molecular pump and a mechanical pump after the gas in the vacuum chamber is exhausted, cooling the substrate with the film on the surface to room temperature, taking out the substrate and annealing the substrate to obtain an ultra-thick hard film on the surface of the substrate; the thickness of the super-thick hard film is more than 20 mu m.

2. The method for preparing the ultra-thick hard film based on the energy regulation principle as claimed in claim 1, wherein the substrate in the first step is a steel substrate or a Si substrate.

3. The method for preparing the ultra-thick hard film based on the energy regulation and control principle of claim 1, wherein the thickness of the metal base layer in the fourth step is 200nm to 400 nm.

4. The method for preparing the ultra-thick hard film based on the energy regulation and control principle of claim 1, wherein the thickness of the transition layer in the fifth step is 300nm to 600 nm.

5. The method for preparing the ultra-thick hard film based on the energy regulation and control principle as claimed in claim 1, wherein the energy regulation process in the sixth step is to regulate the negative bias voltage and/or the working gas pressure, and the regulation mode is alternate regulation or gradual regulation.

6. The method of claim 5, wherein the gradual adjustment is a gradual increase.

7. The method for preparing the ultra-thick hard film based on the energy regulation and control principle of claim 1, wherein the energy regulation layer in the sixth step is composed of TiN, TiAlN or CrTiAlN.

8. The method for preparing the ultra-thick hard film based on the energy regulation and control principle of claim 1, wherein the annealing treatment in the sixth step is performed at the temperature of 300-400 ℃ for 1-3 h.

Technical Field

The invention belongs to the technical field of metal surface film protection, and particularly relates to a method for preparing an ultra-thick hard film based on an energy regulation and control principle.

Background

The hard film has excellent mechanical property and good physical and chemical properties, is widely used for strengthening the surfaces of cutters, molds and mechanical parts, and is one of effective ways for developing material potential. The application of the hard film on the surface of the metal part can not only greatly improve the service performance of the material, but also save a large amount of production cost. Generally, the thickness of the vapor deposition hard film is only a few micrometers, and the insufficient thickness seriously restricts the application of the vapor deposition hard film in the extreme environments of deep sea, aviation, nuclear energy and the like. In recent years, with the rapid development of the emerging scientific and technological fields, the working environment of the film-coated component is more and more severe, and the requirements on the comprehensive performance of the film are continuously improved, so that the traditional film with the thickness of several micrometers is more and more difficult to meet the requirements of practical engineering application. In the research on the preparation of the ultra-thick vapor deposition hard film, researchers at the beginning try to prepare the ultra-thick hard film with the thickness of more than tens of microns by prolonging the deposition time, but find that the internal energy of the film is increased along with the prolonging of the deposition time, so that the internal stress is gradually accumulated, the stress value can reach several GPa or even tens of GPa, the film is very easy to crack and spontaneously peel due to the overhigh internal stress, and finally the ultra-thick hard film is difficult to prepare. Later, many researchers have prepared multilayer hard films by using a metal insert layer method, and the internal stress of the film is slowly released through a flexible metal layer and an interlayer interface, so that although a certain effect is achieved, the matching problem between layers and the interlayer interface combination problem are also obvious, and the satisfactory film structure and mechanical properties are often difficult to obtain.

For a single-layer hard film, special coating devices and techniques such as ultra-high power and multiple assistance have been developed internationally to prepare a hard film with a thickness of more than 20 μm, and although some results are obtained, a complete technical system is not formed, and equipment purchase consumes a large amount of capital. The essential reason for the difficulty in preparing the ultra-thick hard film is that the ultra-high energy exists in the film, and from the research results of documents, no effective solution is provided for preparing the ultra-thick hard film by the conventional vapor deposition methods such as magnetron sputtering and multi-arc ion plating, and the current domestic and foreign data are rarely reported for preparing the ultra-thick hard film by adopting the energy regulation and control idea.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a method for preparing an ultra-thick hard film based on an energy regulation and control principle aiming at the defects of the prior art. The method is based on an energy regulation principle, the ultra-thick hard film consisting of the metal bottom layer, the transition layer and the energy regulation layer is prepared on the substrate, the energy accumulation mode and the energy accumulation rate are regulated and controlled by regulating the energy input in the growth process of the energy regulation layer, the internal stress is reduced, the problems of film cracking and peeling caused by high stress in a high-energy state are solved, the film layer organization structure of the film is optimized, and the ultra-thick hard film with the thickness of more than 20 mu m is obtained.

In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing an ultra-thick hard film based on an energy regulation and control principle is characterized by comprising the following steps:

step one, putting a substrate into analytically pure acetone and analytically pure ethanol in sequence for ultrasonic cleaning, and then drying the substrate by using a hot air blower to obtain a clean substrate;

step two, fixing the arc target on a target holder of the multi-arc ion plating equipment, and step oneLoading the obtained clean substrate into vacuum chamber of multi-arc ion plating equipment, fixing on sample rack of rotary table, closing furnace door, sequentially opening mechanical pump and molecular pump to vacuum the vacuum chamber to vacuum degree of 1.0 × 10 ^-3Pa～5.0×10 ^-3When Pa, a switch of a heating device is turned on, and the vacuum chamber is heated to 200-350 ℃;

step three, continuously vacuumizing the vacuum chamber heated to 200-350 ℃ in the step two until the vacuum degree is lower than 1.0 multiplied by 10 ^-3～5.0×10 ^-3Pa, introducing argon into the vacuum chamber, maintaining the vacuum degree at 3.0Pa, opening a bias power supply to apply negative bias to the substrate to 800V, adjusting the duty ratio to 80%, performing sputtering cleaning and activation on the substrate for 20min, and then closing the negative bias power supply and adjusting the duty ratio to 0 to obtain an activated substrate; the mass purity of the argon is not less than 99.99%;

step four, the vacuum chamber provided with the activated substrate in the step three is vacuumized until the vacuum degree is 1.0 multiplied by 10 ^-3Pa～5.0×10 ^-3Pa, introducing argon gas, maintaining the vacuum degree at 1.0Pa, turning on a bias power supply, adjusting the negative bias to 200V, and turning on an arc target power supply, and plating a metal priming layer on the activated substrate through metal particles sputtered by the arc target; the mass purity of the arc target is not less than 99.99%;

step five, continuously maintaining the negative bias voltage in the vacuum chamber to be 200V, then introducing nitrogen gas to the flow rate of 40sccm within 10-30 min, gradually reducing the flow rate of the argon gas to be 8sccm, maintaining the vacuum degree of the vacuum chamber to be 1.0Pa, turning on an arc target power supply, reacting metal particles sputtered by the arc target with the nitrogen gas, and depositing a transition layer on the surface of the metal priming layer plated in the step four;

step six, continuously maintaining the vacuum degree of the vacuum chamber at 1.0Pa, adjusting the duty ratio to 80%, preparing an energy adjusting layer on the surface of the transition layer deposited in the step five through an energy adjusting process to obtain a substrate with a film on the surface, then closing a gas valve, an arc target power supply, a negative bias power supply and a heating device in sequence, closing a molecular pump and a mechanical pump after the gas in the vacuum chamber is exhausted, cooling the substrate with the film on the surface to room temperature, taking out the substrate and annealing the substrate to obtain an ultra-thick hard film on the surface of the substrate; the thickness of the super-thick hard film is more than 20 mu m.

The invention adopts multi-arc ion plating equipment which is most commonly applied in the current industrialized production, an ultra-thick hard film consisting of a metal priming layer, a transition layer and an energy regulating layer is prepared on a substrate, the metal priming layer ensures that the ultra-thick hard film and a substrate have good bonding performance, the transition layer forms good component transition between the substrate and the ultra-thick hard film, the peeling of the film caused by large mismatch stress generated by component mutation is avoided, meanwhile, mechanical property support is provided for the energy regulating layer, the energy regulating layer is prepared by adopting an energy regulating process, the energy accumulation mode and the rate are regulated and controlled by regulating the energy input in the growth process of the energy regulating layer, the internal stress is reduced, the problems of film cracking and peeling caused by high stress under a high energy state are avoided, the film layer organization structure of the film is optimized, and the mechanical property of the film is improved, thereby obtaining an ultra-thick hard film with excellent quality and a thickness of more than 20 μm.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that the substrate in the step one is a steel substrate or a Si substrate. The substrate commonly used in the current industrial production and scientific research is adopted, so that the method has good applicability.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that the thickness of the metal priming layer in the fourth step is 200-400 nm. The metal priming layer with the thickness can ensure good bonding performance between the super-thick hard film and the substrate, can avoid the reduction of the hardness value of the super-thick hard film caused by the over-thick metal layer, and simultaneously shortens the deposition period of the super-thick hard film.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that the thickness of the transition layer in the fifth step is 300-600 nm. The transition layer with the thickness forms good component transition, avoids the phenomenon that the peeling of the ultra-thick hard film is caused by large mismatch stress generated by sudden change of components from the base body to the ultra-thick hard film well, and can provide good mechanical property support for a subsequent energy adjusting layer.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that in the sixth step, the energy regulation process is to regulate the negative bias and/or the working air pressure, and the regulation mode is alternative regulation or gradual regulation. The magnitude of the negative bias is in direct proportion to the magnitude of the energy value, the magnitude of the working air pressure is in inverse proportion to the magnitude of the energy value, the working air pressure is the vacuum degree of the vacuum chamber, and the magnitude of the negative bias and the magnitude of the working air pressure directly determine the magnitude of the input energy during the growth of the film. The accumulation mode and the accumulation rate of input energy in the growth process of the energy regulation layer are changed by independently regulating the negative bias and the working air pressure or cooperatively regulating the negative bias and the working air pressure to enable energy to be alternately changed from high to low or gradually increase and gradually decrease, so that the internal energy of the super-thick hard film is well released, the cracking and peeling of the super-thick hard film caused by overhigh energy are avoided, the quality of the film layer is optimized, and the hard film with larger thickness can be obtained.

The method as described above, characterized in that said gradual adjustment is a gradual increase. Preferably, the energy input during the growth of the energy adjusting layer is gradually increased, the accumulation mode and the rate during the growth of the energy adjusting layer are gradually changed, the energy adjusting layer with a uniform structure and a fine surface layer is obtained, the internal energy of the ultra-thick hard film is further slowly released, and the mechanical property of the ultra-thick hard film is improved.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that the energy regulation layer in the sixth step is made of TiN, TiAlN or CrTiAlN. The material which is most widely applied in the current industrial field is adopted, so that the practicability of the invention is further improved.

The method for preparing the ultra-thick hard film based on the energy regulation and control principle is characterized in that the annealing treatment in the sixth step is carried out at the temperature of 300-400 ℃ for 1-3 h. The annealing condition can avoid the occurrence of substrate softening, simultaneously slowly release stress, reduce the energy storage in the film and ensure that the ultra-thick hard film is in a stable low-energy state.

Compared with the prior art, the invention has the following advantages:

1. the method is based on the energy regulation principle, the ultra-thick hard film consisting of the metal bottom layer, the transition layer and the energy regulation layer is prepared on the substrate, the energy accumulation mode and the energy accumulation rate are regulated and controlled by regulating the energy input in the growth process of the energy regulation layer, the internal stress is reduced, the problems of film cracking and peeling caused by high stress in a high-energy state are solved, the film layer organization structure of the film is optimized, the mechanical property of the film is improved, and the ultra-thick hard film with excellent quality and the thickness of more than 20 mu m is obtained.

2. The method can be realized in multi-arc ion plating equipment which is most commonly applied in the current industrial production, does not need equipment transformation, has higher economic value and is suitable for popularization and application.

3. The method has the advantages of simple operation process, various adjustment modes of the energy adjustment process and clear adjustment parameters, and simultaneously realizes the regulation and optimization of the tissue structure and the internal stress of the film to obtain the ultra-thick hard film with excellent tissue and performance.

4. The super-thick film prepared by the method has the advantages of fine and compact structure, no obvious holes and defects and good film quality.

5. The invention is suitable for various vapor deposition hard film systems and has good universality.

The technical solution of the present invention is further described in detail by the accompanying drawings and examples.

Drawings

FIG. 1 is a sectional electron microscope image of an ultra-thick TiN thin film obtained on the surface of high speed steel in example 1 of the present invention.

FIG. 2 is a sectional electron microscopic analysis chart of TiN thin film on the surface of high speed steel according to comparative example 1 of the present invention.

FIG. 3 is a sectional electron microscopic analysis chart of TiN thin film on the surface of high speed steel according to comparative example 2 of the present invention.

FIG. 4 is a cross-sectional electron microscope image of an ultra-thick TiN thin film obtained on the surface of a Si substrate in example 2 of the present invention.

FIG. 5 is a sectional electron microscope image of an ultra-thick TiN thin film obtained on the surface of high speed steel in example 3 of the present invention.

FIG. 6 is a sectional electron microscope image of an ultra-thick TiAlN thin film obtained on the surface of high-speed steel in example 4 of the present invention.

FIG. 7 is a sectional electron microscope image of an ultra-thick TiAlN thin film obtained on the surface of high-speed steel in example 5 of the present invention.

FIG. 8 is a sectional electron microscope image of an ultra-thick CrTiAlN thin film obtained on the surface of high-speed steel in example 6 of the present invention.

Detailed Description