CN113061845B - Preparation process of ultra-black high-performance Ti-DLC coating - Google Patents
Preparation process of ultra-black high-performance Ti-DLC coating Download PDFInfo
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- CN113061845B CN113061845B CN202110298324.8A CN202110298324A CN113061845B CN 113061845 B CN113061845 B CN 113061845B CN 202110298324 A CN202110298324 A CN 202110298324A CN 113061845 B CN113061845 B CN 113061845B
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- C23C14/0021—Reactive sputtering or evaporation
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
The invention relates to a preparation process of an ultra-black high-performance Ti-DLC coating, which comprises the steps of placing a workpiece in a vacuum chamber, performing air extraction treatment on the vacuum chamber, performing impurity removal treatment on the vacuum chamber and/or the workpiece after the air extraction treatment, filling Ar into the vacuum chamber after the impurity removal treatment, preparing a primer layer on the surface of the workpiece by adopting a medium-frequency power supply twin Ti target, and adding C into the vacuum chamber after the primer layer is prepared 2 H 2 Preparing a transition layer on the priming layer, and regulating and controlling preparation parameters of the transition layer to change according to requirements in the process of preparing the transition layer, wherein the regulated and controlled preparation parameters of the transition layer comprise Ar filling amount and C 2 H 2 One or more of a charge amount, a workpiece bias voltage, and a Ti target voltage; and after the transition layers are prepared, keeping the preparation parameters of each transition layer stable and continuously coating the film, thereby preparing a stable color layer on the transition layers. According to the scheme provided by the invention, the prepared coating film has excellent performance, the L value of DLC is lower than 30, and the application range can be effectively expanded.
Description
Technical Field
The invention relates to the field of sputtering coating, in particular to a preparation process of an ultra-black high-performance Ti-DLC coating.
Background
The Diamond-Like Carbon-DLC film contains Diamond phase (sp) 3 Bond or sp 3 Hybrid) amorphous carbon film. Wherein the carbon atoms are partly in sp of diamond 3 In the hybridized state, partially in sp of graphite 2 Hybrid state with very few sp 1 In the hybrid state, in sp 3 Diamond-like films with predominantly (more than 70%) bonds are also known as Tetrahedral Amorphous Carbon (ta-C) films. The diamond-like film has high hardness and high strengthThe material has the advantages of high thermal conductivity, low friction coefficient, excellent corrosion resistance, optical permeability and biocompatibility, and is an ideal material in the fields of machinery, electronics, automobiles, aviation, medicine, optics and the like. Although DLC films have so many excellent properties, there are many problems to be improved in practical engineering applications, mainly:
1) Poor binding to certain material-specific substrates. For example, the DLC film has very poor adhesion to zinc sulfide, insufficient adhesion to glass, plastic, and resin, and strong adhesion to silicon wafers and steel due to incompatibility of lattice structure and physical properties such as thermal expansion coefficient, elastic modulus, etc., between the DLC film and the substrate.
2) The internal stress is large. The DLC mainly contains carbon, the higher the diamond content is, the larger the internal stress of the film layer is, and when a tool plated with the DLC coating is used for processing a hard material, the huge internal stress can cause the coating to crack and fail in advance.
3) The thermal stability is poor. DLC films containing hydrogen have poorer thermal stability, sp, than DLC films without hydrogen 3 DLC film ratio sp with low bond content 3 Films with high bond content are more thermally less stable. In air, high quality hydrogen-free DLC films will start to graphitize and oxidize at around 500 ℃, while some lower quality DLC films start to graphitize even only at 250 ℃.
4) The color is grayish. DLC coatings prepared by existing CVD and PVD techniques are grayish black in color, with L values typically above 50, and DLC L values below 30 are required in certain areas such as decorative plating and military.
For the above problems, research personnel improve the performance by changing the preparation process of the DLC coating and doping elements such as Si, ti, cr, al, N and the like in the DLC, and have a great breakthrough, so that the application field of the DLC is expanded.
Disclosure of Invention
The object of the present invention is to provide a process for the preparation of an ultra-black high-performance Ti-DLC coating which at least ameliorates one of the above problems.
A preparation process of an ultra-black high-performance Ti-DLC coating is characterized by comprising the following operations:
placing a workpiece in a vacuum chamber, performing air exhaust treatment on the vacuum chamber, performing impurity removal treatment on the vacuum chamber and/or the workpiece to be plated after the air exhaust treatment, filling Ar into the vacuum chamber after the impurity removal treatment, preparing a primer layer on the surface of the workpiece by adopting a medium-frequency power twin Ti target coating film, and adding C into the vacuum chamber after the primer layer is prepared 2 H 2 Preparing a transition layer on the priming coat, regulating and controlling the preparation parameters of the transition layer to change according to the requirements in the process of preparing the transition layer, wherein the regulated and controlled preparation parameters of the transition layer comprise Ar filling amount and C 2 H 2 One or more of a charge amount, a workpiece bias voltage, and a Ti target voltage; and after the transition layers are prepared, keeping the preparation parameters of each transition layer stable and continuously coating the film, thereby preparing a stable color layer on the transition layers.
The further scheme is as follows: the intermediate frequency power supply twin Ti target coating is that the output end of the intermediate frequency power supply is respectively connected on two twin Ti targets, and the two twin Ti targets alternately work to sputter and coat.
Adjusting Ar filling amount to gradually decrease C when preparing the transition layer 2 H 2 The charging amount is gradually increased, the bias voltage of the workpiece is gradually reduced, and the voltage of the Ti target is gradually increased.
The thickness of the bottom layer is 0.3-0.6 micron, the thickness of the transition layer is 1.0-1.1 micron, the thickness of the stable color layer is 1-2 micron, and the L value range is 21-30.
And the impurity removal treatment comprises the steps of filling Ar into the vacuum cavity for heating treatment and carrying out ion source etching cleaning on the workpiece.
The detailed operation is as follows:
when preparing the bottom layer, controlling the background vacuum to be less than 8 multiplied by 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 210-950V, the current is 3-8A, and the frequency is 2000-40000Hz; the vacuum chamber is at 80-200 deg.C, and filled with 40-300sccmAr under 2.6 × 10 - 1 Pa-1.5 multiplied by 100Pa, workpiece bias voltage of 0-1000V, bias power supply working frequency of 500-40000Hz, bias power supply working duty ratio of 10-90 percent and coating time of 1000-2000s.
During the preparation of the transition layer, the vacuum chamber is filled with C 2 H 2 Thereafter, the vacuum of the vacuum chamber is adjustedThe degree is 3Pa, the coating time is 120 minutes, and the preparation parameters of the transition layer are regulated and controlled to change according to the following requirements:
| time/min | C 2 H 2 Flow/sccm | Ar flow/sccm | Workpiece bias voltage/V | voltage/V of Ti target |
| 0 | 20 | 500 | 800 | 200 |
| 10 | 60 | 460 | 750 | 250 |
| 20 | 100 | 420 | 700 | 300 |
| 30 | 140 | 380 | 650 | 350 |
| 40 | 180 | 340 | 600 | 400 |
| 50 | 220 | 300 | 550 | 450 |
| 60 | 260 | 260 | 500 | 500 |
| 70 | 300 | 220 | 450 | 550 |
| 80 | 340 | 180 | 400 | 600 |
| 90 | 380 | 140 | 350 | 650 |
| 100 | 420 | 100 | 300 | 700 |
| 110 | 460 | 60 | 250 | 750 |
| 120 | 500 | 20 | 200 | 800 |
。
Preparation of the Stable color layer, maintaining C 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of the workpiece is 200V, the sputtering voltage of the Ti target is stabilized at 800V, the air pressure of the vacuum chamber is 3Pa, and the coating time is 4000-8000s.
The air extraction treatment comprises clamping the surface-cleaned workpiece on a fixture, pumping 10-50Pa vacuum by starting a rotary vane pump after the workpiece enters a vacuum chamber, and pumping to 1 × 10 -2 -9×10 -2 Pa。
The heating treatment comprises the following steps: charging 0-500sccmAr into vacuum chamber at pressure of 1 × 10 -2 3 multiplied by 100Pa, starting a vacuum chamber heater and a magnetic filtering power supply, setting the heating temperature to be 150-350 ℃ and the time to be 0.5-3 h;
the ion source etching cleaning treatment comprises the following steps: adjusting the heating temperature of the vacuum chamber to 110-260 deg.C, and vacuumizing to 1 × 10 when the background is vacuum -2 Introducing 10-400sccmAr from ion source inlet under Pa, and maintaining vacuum degree at 6 × 10 -2 Pa-2.4X 100Pa, opening distanceSource power supply and bias power supply, ion source voltage: 300-10000V, ion source current: 0.1-2A, workpiece bias: 20-4000V, workpiece bias flow: 0.1-5A, etching cleaning time: 0.5-5h.
According to the scheme provided by the invention, the prepared coating film has excellent performance, the L value of DLC is lower than 30, and the application range can be effectively expanded.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is a schematic view of the structure of the plating layer of the present invention.
Detailed Description
In order to make the objects and advantages of the present invention more apparent, the present invention will be described in detail with reference to the following examples. It is to be understood that the following text is merely illustrative of one or more specific embodiments of the invention and does not strictly limit the scope of the invention as specifically claimed.
Example 1
As shown in fig. 1:
1) The pump group performs air exhaust on the vacuum chamber
Clamping the surface-cleaned workpiece on a special fixture, starting a rotary vane pump to pump vacuum to 10Pa after the workpiece enters a vacuum chamber, starting a molecular pump to pump air pressure to 1 × 10 -2 Pa。
2) Heating in vacuum for 1h
Charging 0sccmAr into the vacuum chamber at a pressure of 1X 10 -2 And Pa, starting a vacuum chamber heater and a magnetic filtering power supply, and setting the heating temperature to 350 ℃ for 0.5h.
The function is as follows: the chamber heater is mainly used for desorbing gas molecules such as water vapor and the like attached to the inner wall of the chamber, the lining plate, the rotating frame and the workpiece, and the heat generated by the magnetic filtering power supply can be used for baking and degassing the inner wall of the magnetic filtering elbow and the corrugated pipe lining. The function of charging Ar into the vacuum chamber is mainly as follows: firstly, desorbed gas molecules can be rapidly discharged under the drive of a gas pump set and Ar gas; secondly, ar is inert gas under heating condition, and gas molecules such as water vapor can be prevented from adhering to the workpiece under Ar atmosphere.
3) Ion source etch cleaning
The heating temperature of the chamber is adjusted to 260 ℃, and when the background is vacuumized to 1 x 10 -2 Below Pa, 10sccmAr is charged from the ion source gas inlet, and the vacuum degree is kept at 6X 10 -2 Pa, starting the ion source power supply and the bias power supply, and the ion source voltage: 300V, ion source current: 0.1A, workpiece bias: 20V, workpiece bias flow: 0.1A, etching cleaning time: and 5h.
The function is as follows: the ultrasonic cleaning can only remove macroscopic pollutants on the surface of a workpiece, and microscopic oxide layers and pollutants are only removed by an ion bombardment method, so that an ultra-clean product surface is obtained, and a foundation is laid for subsequent film-substrate binding force. The principle of anode layer ion source for removing microscopic stains is as follows: by applying voltage between the positive plate and the negative plate of the anode layer ion source, ar gas is ionized to generate glow discharge when passing through the slit of the anode layer ion source, ar plasma is emitted from the slit of the anode layer ion source, and positively charged ions in the Ar plasma bombard the surface of a workpiece under the action of negative bias of the workpiece, so that the surface of a product is etched and cleaned, and the effect of removing microcosmic pollutants is achieved.
4) Prime layer prepared by intermediate frequency power supply twin Ti target
The twin Ti targets of the medium-frequency power supply are formed by respectively connecting the output ends of the medium-frequency power supply to the two Ti targets, and the twin Ti targets alternately work to sputter and coat films. The specific parameters are as follows: background vacuum less than 8 x 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 950V, the current is 8A, and the frequency is 40000Hz; the temperature of the vacuum chamber is 150 ℃, 300sccmAr is filled, the air pressure is 1.5 multiplied by 100Pa, the workpiece bias voltage is 1000V, the working frequency of a bias power supply is 30000Hz, the working duty ratio of the bias power supply is 20 percent, the coating time is 1000s, and the coating thickness is as follows: 0.3 micron.
The function is as follows: the priming layer of pure metal Ti is beneficial to improving the binding force between the matrix and the Ti-DLC transition layer.
5) Twin Ti target + C of medium frequency power supply 2 H 2 Preparation of Ti-DLC transition layer
Keeping the parameters of the above steps unchanged, charging C into the vacuum chamber 2 H 2 The vacuum degree is 3Pa, the coating time is 120 minutes, and the coating thickness is as follows: 1.0 micron. Gradually changing every 10minThe parameters varied were: c 2 H 2 The charging amount of Ar, and the workpiece bias voltage are as follows:
| time/min | C 2 H 2 Flow rate/sccm | Ar flow/sccm | Workpiece bias voltage/V | voltage/V of Ti target |
| 0 | 20 | 500 | 800 | 200 |
| 10 | 60 | 460 | 750 | 250 |
| 20 | 100 | 420 | 700 | 300 |
| 30 | 140 | 380 | 650 | 350 |
| 40 | 180 | 340 | 600 | 400 |
| 50 | 220 | 300 | 550 | 450 |
| 60 | 260 | 260 | 500 | 500 |
| 70 | 300 | 220 | 450 | 550 |
| 80 | 340 | 180 | 400 | 600 |
| 90 | 380 | 140 | 350 | 650 |
| 100 | 420 | 100 | 300 | 700 |
| 110 | 460 | 60 | 250 | 750 |
| 120 | 500 | 20 | 200 | 800 |
The function is as follows:
1. the DLC coating is doped with metal Ti, so that the internal stress of the coating can be reduced;
2. by doping metal Ti in the DLC coating, the high-temperature stability of the coating can be improved;
3. the twin Ti target can improve the deposition rate and release the charge on the surface of the target material, so that the poisoned target material can be continuously carried out;
4. gradually increasing C every 10min under the condition of keeping the air pressure in the vacuum chamber basically unchanged 2 H 2 The flow rate and the Ar flow rate were reduced, and the Ti target surface was observed to be poisoned, and the sputtering voltage was substantially stabilized at 800V, based on the sputtering occurring in 1/10 area of the target surface.
During the coating process, the ion source is kept in an on state, C 2 H 2 The molecules are continuously broken and ionized, the ionized C element and sputtered Ti element can generate a Ti-DLC coating in the plasma atmosphere, the higher the content of the Ti element is, the lighter the color of the coating is, the higher the bias voltage is, and sp is 3 The higher the bond content, the more grey the coating tends to be.
6) Medium frequency power twin Ti target + C 2 H 2 Preparation of stable color of Ti-DLC
After the above step is stabilized, keep C 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of a workpiece is 200V, the sputtering voltage of a Ti target is stabilized at 800V, the air pressure is 3Pa, the coating time is 4000s, a stable color layer of the Ti-DLC coating is prepared, and the coating thickness is as follows: 1 micron.
Example 2
As shown in fig. 1:
1) The pump group performs air exhaust on the vacuum chamber
Clamping the surface-cleaned workpiece on a special fixture, starting a rotary vane pump to pump the workpiece into a vacuum chamber to vacuum to 20Pa, starting a molecular pump to pump the air pressure to 9 x 10 -2 Pa。
2) Heating in vacuum for 1h
Filling 500sccmAr into the vacuum chamber, wherein the air pressure is 3 multiplied by 100Pa, starting a heater and a magnetic filtering power supply of the vacuum chamber, and setting the heating temperature at 260 ℃ for 0.75h.
The function is as follows: the chamber heater is mainly used for desorbing gas molecules such as water vapor and the like attached to the inner wall of the chamber, the lining plate, the rotating frame and the workpiece, and the heat generated by the magnetic filtering power supply can be used for baking and degassing the inner wall of the magnetic filtering elbow and the corrugated pipe lining. The function of charging Ar into the vacuum chamber is mainly as follows: firstly, desorbed gas molecules can be rapidly discharged under the drive of a gas pump set and Ar gas; and secondly, ar is inert gas under the heating condition, and gas molecules such as water vapor and the like can be prevented from being attached to the workpiece under the Ar atmosphere.
3) Ion source etch cleaning
The heating temperature of the chamber is adjusted to 200 ℃, and when the background is vacuumized to 1 x 10 -2 Under Pa, 400sccmAr is filled from the ion source air inlet, the vacuum degree is kept at 2.4 multiplied by 100Pa, the ion source power supply and the bias power supply are started, and the ion source voltage is: 10000V, ion source current: 2A, workpiece bias: 2000V, workpiece bias flow: 2.5A, etching cleaning time: 2.5h.
The function is as follows: the ultrasonic cleaning can only remove macroscopic pollutants on the surface of a workpiece, and microscopic oxide layers and pollutants are only removed by an ion bombardment method, so that an ultra-clean product surface is obtained, and a foundation is laid for subsequent film-substrate binding force. The principle of anode layer ion source for removing microscopic stains is as follows: by applying voltage between the positive plate and the negative plate of the anode layer ion source, ar gas is ionized to generate glow discharge when passing through the slit of the anode layer ion source, ar plasma is emitted from the slit of the anode layer ion source, and positively charged ions in the Ar plasma bombard the surface of a workpiece under the action of negative bias of the workpiece, so that the surface of a product is etched and cleaned, and the effect of removing microcosmic pollutants is achieved.
4) Prime layer prepared by intermediate frequency power supply twin Ti target
The twin Ti targets of the medium-frequency power supply are formed by respectively connecting the output ends of the medium-frequency power supply to the two Ti targets, and the twin Ti targets alternately work to sputter and coat films. The specific parameters are as follows: background vacuum of less than 8 x 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 210V, the current is 3A, and the frequency is 30000Hz; the vacuum chamber was heated to 200 ℃ and charged with 150sccmAr under a pressure of 7.5X 10 -1 Pa, workpiece bias voltage 500V, bias power supply working frequency 40000Hz, bias power supply working duty ratio 40%, coating time 2000s, coating thickness: 0.6 micron.
The function is as follows: the priming layer of pure metal Ti is beneficial to improving the binding force between the matrix and the Ti-DLC transition layer.
5) Medium frequency power twin Ti target + C 2 H 2 Preparation of Ti-DLC transition layer
Keeping the parameters of the above steps unchanged, charging C into the vacuum chamber 2 H 2 The vacuum degree is 3Pa, the coating time is 120 minutes, and the coating thickness is as follows: 1.0 micron. The parameters that change stepwise every 10min are: c 2 H 2 The charging amount of Ar, and the workpiece bias voltage are as follows:
| time/min | C 2 H 2 Flow/sccm | Ar flow/sccm | Workpiece bias voltage/V | voltage/V of Ti target |
| 0 | 20 | 500 | 800 | 200 |
| 10 | 60 | 460 | 750 | 250 |
| 20 | 100 | 420 | 700 | 300 |
| 30 | 140 | 380 | 650 | 350 |
| 40 | 180 | 340 | 600 | 400 |
| 50 | 220 | 300 | 550 | 450 |
| 60 | 260 | 260 | 500 | 500 |
| 70 | 300 | 220 | 450 | 550 |
| 80 | 340 | 180 | 400 | 600 |
| 90 | 380 | 140 | 350 | 650 |
| 100 | 420 | 100 | 300 | 700 |
| 110 | 460 | 60 | 250 | 750 |
| 120 | 500 | 20 | 200 | 800 |
The function is as follows:
1. the DLC coating is doped with metal Ti, so that the internal stress of the coating can be reduced;
2. the DLC coating is doped with metal Ti, so that the high-temperature stability of the coating can be improved;
3. the twin Ti target can improve the deposition rate and release the charge on the surface of the target material, so that the poisoned target material can be continuously carried out;
4. gradually increasing C every 10min under the condition of keeping the air pressure in the vacuum chamber unchanged basically 2 H 2 The flow rate and the Ar flow rate were reduced, and the Ti target surface was observed to be poisoned, and the sputtering voltage was substantially stabilized at 800V, based on the sputtering occurring in 1/10 area of the target surface.
During the coating process, the ion source is kept in an open state, C 2 H 2 The molecules are continuously broken and ionized, the ionized C element and sputtered Ti element can generate a Ti-DLC coating in the plasma atmosphere, the higher the content of the Ti element is, the lighter the color of the coating is, the higher the bias voltage is, and sp is 3 The higher the bond content, the coating tends to be gray.
6) Medium frequency power twin Ti target + C 2 H 2 Preparation of stable color of Ti-DLC
After the above step is stabilized, keep C 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of a workpiece is 200V, the sputtering voltage of a Ti target is stabilized at 800V, the air pressure is 3Pa, the coating time is 4000s, a stable color layer of the Ti-DLC coating is prepared, and the coating thickness is as follows:1 micron.
Example 3
As shown in fig. 1:
1) The pump group performs air exhaust on the vacuum chamber
Clamping the workpiece with the cleaned surface on a special fixture, starting a rotary vane pump to pump the vacuum to 28Pa after the workpiece enters a vacuum chamber, starting a molecular pump to pump the air pressure to 5 multiplied by 10 -2 Pa。
2) Heating in vacuum for 1h
And (3) filling 250sccmAr into the vacuum chamber, wherein the air pressure is 1.5 multiplied by 100Pa, starting a heater and a magnetic filtration power supply of the vacuum chamber, and setting the heating temperature at 200 ℃ for 1.5h.
The function is as follows: the chamber heater is mainly used for desorbing gas molecules such as water vapor and the like attached to the inner wall of the chamber, the lining plate, the rotating frame and the workpiece, and the heat generated by the magnetic filtering power supply can be used for baking and degassing the inner wall of the magnetic filtering elbow and the corrugated pipe lining. The charging of Ar into the vacuum chamber mainly has the following functions: firstly, desorbed gas molecules can be rapidly discharged under the drive of a gas pump set and Ar gas; and secondly, ar is inert gas under the heating condition, and gas molecules such as water vapor and the like can be prevented from being attached to the workpiece under the Ar atmosphere.
3) Ion source etch cleaning
The heating temperature of the chamber is adjusted to 180 ℃, and when the background is vacuumized to 1 x 10 -2 Charging 200sccmAr from the ion source gas inlet under Pa, keeping the vacuum degree at 1.2 multiplied by 100Pa, starting the ion source power supply and the bias power supply, and keeping the ion source voltage: 1500V, ion source current: 0.8A, workpiece bias: 1500V, workpiece bias flow: 2A, etching and cleaning time: and 3h.
The function is as follows: the ultrasonic cleaning can only remove macroscopic pollutants on the surface of a workpiece, and microscopic oxide layers and pollutants are only removed by an ion bombardment method, so that an ultra-clean product surface is obtained, and a foundation is laid for subsequent film-substrate binding force. The principle of anode layer ion source for removing microscopic stains is as follows: by applying voltage between the positive plate and the negative plate of the anode layer ion source, ar gas is ionized to generate glow discharge when passing through the slit of the anode layer ion source, ar plasma is emitted from the slit of the ion source, and ions with positive charges in the Ar plasma bombard the surface of a workpiece under the action of negative bias of the workpiece, so that the surface of a product is etched and cleaned, and the effect of removing microcosmic pollutants is achieved.
4) Prime layer prepared by intermediate frequency power supply twin Ti target
The twin Ti targets of the medium-frequency power supply are formed by respectively connecting the output ends of the medium-frequency power supply to the two Ti targets, and the twin Ti targets alternately work to sputter and coat films. The specific parameters are as follows: background vacuum less than 8 x 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 500V, the current is 5A, and the frequency is 20000Hz; the vacuum chamber is at 120 deg.C, and filled with 100sccmAr under 5 × 10 -1 Pa, workpiece bias voltage 300V, bias power supply working frequency 20000Hz, bias power supply working duty cycle 70%, coating time 1200s, coating thickness: 0.36 micron.
The function is as follows: the priming layer of pure metal Ti is beneficial to improving the binding force between the matrix and the Ti-DLC transition layer.
5) Medium frequency power twin Ti target + C 2 H 2 Preparation of Ti-DLC transition layer
Keeping the parameters of the above steps unchanged, charging C into the vacuum chamber 2 H 2 The vacuum degree is 3Pa, the coating time is 120 minutes, and the coating thickness is as follows: 1.1 micron. The parameters that change stepwise every 10min are: c 2 H 2 The charging amount of Ar, and the workpiece bias voltage are as follows:
the function is as follows:
1. the DLC coating is doped with metal Ti, so that the internal stress of the coating can be reduced;
2. the DLC coating is doped with metal Ti, so that the high-temperature stability of the coating can be improved;
3. the twin Ti target can improve the deposition rate and release the charge on the surface of the target material, so that the poisoned target material can be continuously carried out;
4. gradually increasing C every 10min under the condition of keeping the air pressure in the vacuum chamber unchanged basically 2 H 2 The flow rate and the Ar flow rate were reduced, and the Ti target surface was observed to be poisoned, and the sputtering voltage was substantially stabilized at 800V, based on the sputtering occurring in 1/10 area of the target surface.
During the coating process, the ion source is kept in an open state, C 2 H 2 The molecules are broken and ionized continuously, the ionized C element and the sputtered Ti element can generate a Ti-DLC coating in the plasma atmosphere, the higher the content of the Ti element is, the lighter the color of the coating is, the higher the bias voltage is, and sp is 3 The higher the bond content, the coating tends to be gray.
6) Twin Ti target + C of medium frequency power supply 2 H 2 Preparation of stable color of Ti-DLC
After the above step is stabilized, keep C 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of a workpiece is 200V, the sputtering voltage of a Ti target is stabilized at 800V, the air pressure is 3Pa, the coating time is 4000s, a stable color layer of the Ti-DLC coating is prepared, and the coating thickness is as follows: 1.1 micron.
Example 4
As shown in fig. 1:
1) The pump group performs air exhaust on the vacuum chamber
Clamping the surface-cleaned workpiece on a special fixture, starting a rotary vane pump to pump the vacuum to 50Pa after the workpiece enters a vacuum chamber, starting a molecular pump to pump the air pressure to 5 multiplied by 10 -2 Pa。
2) Heating in vacuum for 1h
Charging 100sccmAr into the vacuum chamber at 6X 10 -1 And Pa, starting a vacuum chamber heater and a magnetic filtering power supply, and setting the heating temperature at 150 ℃ for 3h.
The function is as follows: the chamber heater is mainly used for desorbing gas molecules such as water vapor and the like attached to the inner wall of the chamber, the lining plate, the rotating frame and the workpiece, and the heat generated by the magnetic filtering power supply can be used for baking and degassing the inner wall of the magnetic filtering elbow and the corrugated pipe lining. The charging of Ar into the vacuum chamber mainly has the following functions: firstly, desorbed gas molecules can be rapidly discharged under the drive of a gas pump set and Ar gas; secondly, ar is inert gas under heating condition, and gas molecules such as water vapor can be prevented from adhering to the workpiece under Ar atmosphere.
3) Ion source etch cleaning
The heating temperature of the chamber is adjusted to 150 ℃, and when the background is vacuumized to 1 x 10 -2 Under Pa, 100sccmAr is filled from the ion source gas inlet, and the vacuum degree is kept at 6X 10 -1 Pa, starting an ion source power supply and a bias power supply, and enabling the ion source voltage: 1000V, ion source current: 0.5A, workpiece bias: 1000V, workpiece bias flow: 1.3A, etching cleaning time: and 5h.
The function is as follows: the ultrasonic cleaning can only remove macroscopic pollutants on the surface of a workpiece, and the microscopic oxide layer and pollutants are only removed by an ion bombardment method, so that an ultra-clean product surface is obtained, and a foundation is laid for the subsequent film-substrate binding force. The principle of anode layer ion source for removing microscopic stains is as follows: by applying voltage between the positive plate and the negative plate of the anode layer ion source, ar gas is ionized to generate glow discharge when passing through the slit of the anode layer ion source, ar plasma is emitted from the slit of the anode layer ion source, and positively charged ions in the Ar plasma bombard the surface of a workpiece under the action of negative bias of the workpiece, so that the surface of a product is etched and cleaned, and the effect of removing microcosmic pollutants is achieved.
4) Prime layer prepared by intermediate frequency power supply twin Ti target
The twin Ti targets of the medium-frequency power supply are formed by respectively connecting the output ends of the medium-frequency power supply to the two Ti targets, and the twin Ti targets alternately work to sputter and coat films. The specific parameters are as follows: background vacuum less than 8 x 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 800V, the current is 7A, and the frequency is 18000Hz; the vacuum chamber is filled with 60sccmAr at 100 ℃ and the air pressure is 3X 10 -1 Pa, workpiece bias voltage 100V, bias power supply working frequency 10000Hz, bias power supply working duty ratio 90%, coating time 1500s, coating thickness: 0.45 micron.
The function is as follows: the priming layer of pure metal Ti is beneficial to improving the binding force between the matrix and the Ti-DLC transition layer.
5) Medium frequency power twin Ti target + C 2 H 2 Preparation of Ti-DLCTransition layer
Keeping the parameters of the above steps unchanged, charging C into the vacuum chamber 2 H 2 The vacuum degree is 3Pa, the coating time is 120 minutes, and the coating thickness is as follows: 1.1 micron. The parameters that change stepwise every 10min are: c 2 H 2 The charging amount of Ar, and the workpiece bias voltage are as follows:
| time/min | C 2 H 2 Flow/sccm | Ar flow/sccm | Workpiece bias voltage/V | voltage/V of Ti target |
| 0 | 20 | 500 | 800 | 200 |
| 10 | 60 | 460 | 750 | 250 |
| 20 | 100 | 420 | 700 | 300 |
| 30 | 140 | 380 | 650 | 350 |
| 40 | 180 | 340 | 600 | 400 |
| 50 | 220 | 300 | 550 | 450 |
| 60 | 260 | 260 | 500 | 500 |
| 70 | 300 | 220 | 450 | 550 |
| 80 | 340 | 180 | 400 | 600 |
| 90 | 380 | 140 | 350 | 650 |
| 100 | 420 | 100 | 300 | 700 |
| 110 | 460 | 60 | 250 | 750 |
| 120 | 500 | 20 | 200 | 800 |
The function is as follows:
1. the DLC coating is doped with metal Ti, so that the internal stress of the coating can be reduced;
2. the DLC coating is doped with metal Ti, so that the high-temperature stability of the coating can be improved;
3. the twin Ti target can improve the deposition rate and release the charge on the surface of the target material, so that the poisoned target material can be continuously carried out;
4. gradually increasing C every 10min under the condition of keeping the air pressure in the vacuum chamber unchanged basically 2 H 2 The flow rate and the Ar flow rate were reduced, and the surface poisoning of the Ti target was observed, and the sputtering voltage was substantially stabilized at 800V based on 1/10 area of the target surface to generate sputtering.
During the coating process, the ion source is kept in an open state，C 2 H 2 The molecules are broken and ionized continuously, the ionized C element and the sputtered Ti element can generate a Ti-DLC coating in the plasma atmosphere, the higher the content of the Ti element is, the lighter the color of the coating is, the higher the bias voltage is, and sp is 3 The higher the bond content, the coating tends to be gray.
6) Medium frequency power twin Ti target + C 2 H 2 Preparation of stable color of Ti-DLC
After the above step is stabilized, keep C 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of a workpiece is 200V, the sputtering voltage of a Ti target is stabilized at 800V, the air pressure is 3Pa, the coating time is 4000s, a stable color layer of the Ti-DLC coating is prepared, and the coating thickness is as follows: 1.1 micron.
Example 5
The film structures of the products prepared in examples 1 to 4 are shown in fig. 2, and the properties of the products prepared in examples 3 and 4 (respectively marked as product a and product B) and the products prepared by the conventional DLC process were measured, and the measurement methods and the measurement results are shown in the following table:
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (1)
1. A preparation process of an ultra-black high-performance Ti-DLC coating is characterized by comprising the following operations:
placing the workpiece in a vacuum chamberPerforming air extraction treatment on the vacuum chamber, performing impurity removal treatment on the vacuum chamber and/or the workpiece to be plated after the air extraction treatment, filling Ar into the vacuum chamber after the impurity removal treatment, preparing a pure metal Ti priming layer on the surface of the workpiece by adopting a twin Ti target coating of a medium-frequency power supply, and filling C into the vacuum chamber after the pure metal Ti priming layer is prepared 2 H 2 Preparing a Ti-DLC transition layer on a pure metal Ti priming coat, regulating and controlling the preparation parameters of the Ti-DLC transition layer to change according to requirements in the process of preparing the Ti-DLC transition layer, wherein the regulated and controlled preparation parameters of the Ti-DLC transition layer comprise Ar filling amount and C 2 H 2 One or more of a charge amount, a workpiece bias voltage, and a Ti target voltage; after the Ti-DLC transition layer is prepared, keeping the preparation parameters of each Ti-DLC transition layer stable and continuously coating the film, thereby preparing a Ti-DLC stable color layer on the Ti-DLC transition layer; the intermediate frequency power supply twin Ti target coating is to connect the output end of the intermediate frequency power supply on two twin Ti targets respectively, the two twin Ti targets work alternately to sputter coating; when preparing Ti-DLC transition layer, adjusting Ar filling amount to gradually decrease C 2 H 2 The charging amount is gradually increased, the workpiece bias voltage is gradually reduced, and the Ti target voltage is gradually increased; the thickness of the pure metal Ti priming layer is 0.3-0.6 micron, the thickness of the Ti-DLC transition layer is 1.0-1.1 micron, the thickness of the Ti-DLC stabilizing color layer is 1-2 micron, and the L value range is 21-30;
when preparing pure metal Ti priming coat, controlling the background vacuum to be less than 8 multiplied by 10 -3 Pa, the voltage of two Ti targets of the intermediate frequency power supply is 210-950V, the current is 3-8A, and the frequency is 2000-40000Hz; the vacuum chamber is at 80-200 deg.C, and filled with 40-300sccmAr under 2.6 × 10 -1 Pa ～1.5×10 0 Pa, workpiece bias voltage is 0-1000V, bias power supply working frequency is 500-40000Hz, bias power supply working duty ratio is 10-90%, and coating time is 1000-2000s;
when preparing the Ti-DLC transition layer, the vacuum chamber is filled with C 2 H 2 Then, the vacuum degree of the vacuum chamber is initially adjusted to 3Pa and C 2 H 2 The flow rate is 20sccm, the Ar flow rate is 500sccm, the workpiece bias voltage is 800V, and the Ti target voltage is 200V;
adjusting C every 10min 2 H 2 The flow gradient is increased by 40sccm and the Ar flow gradient is decreased by 40sccm, the gradient of the bias voltage of the workpiece is decreased by 50V, and the gradient of the voltage of the Ti target is increased by 50V;
the coating time of the Ti-DLC transition layer is 120min, and after the coating time reaches 120min, C is adjusted 2 H 2 The flow rate is 500sccm, the Ar flow rate is 20sccm, the workpiece bias voltage is 200V, and the Ti target voltage is 800V;
maintenance of C in the preparation of a stable Ti-DLC colored layer 2 H 2 The flow is charged into 500sccm, the Ar flow is charged into 20sccm, the bias voltage of the workpiece is 200V, the sputtering voltage of the Ti target is stabilized at 800V, the air pressure of the vacuum chamber is 3Pa, and the coating time is 4000-8000s;
the air extraction treatment comprises clamping the surface-cleaned workpiece on a fixture, pumping vacuum to 10-50Pa by starting a rotary vane pump after the workpiece enters a vacuum chamber, and pumping air pressure to 1 × 10 by starting a molecular pump -2 -9×10 -2 Pa；
The impurity removal treatment comprises the steps of filling Ar into a vacuum cavity, carrying out heating treatment, and carrying out ion source etching cleaning treatment on a workpiece;
the heating treatment comprises the following steps: charging 0-500sccmAr into the vacuum chamber under 1 × 10 -2 ～3×10 0 Pa, starting a vacuum chamber heater and a magnetic filtering power supply, setting the heating temperature at 150-350 ℃ and the time at 0.5-3 h;
the ion source etching cleaning treatment comprises the following steps: adjusting the heating temperature of the vacuum chamber to 110-260 deg.C, and vacuumizing to 1 × 10 when the background is vacuum -2 Introducing 10-400sccmAr from ion source inlet under Pa, and maintaining vacuum degree at 6 × 10 -2 Pa -2.4×10 0 Pa, starting an ion source power supply and a bias power supply, and enabling the ion source voltage: 300-10000V, ion source current: 0.1-2A, workpiece bias: 20-4000V, workpiece bias flow: 0.1-5A, etching cleaning time: 0.5-5h.
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