CN107779839B - DLC film plating process based on anode technology - Google Patents
DLC film plating process based on anode technology Download PDFInfo
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- CN107779839B CN107779839B CN201711133112.4A CN201711133112A CN107779839B CN 107779839 B CN107779839 B CN 107779839B CN 201711133112 A CN201711133112 A CN 201711133112A CN 107779839 B CN107779839 B CN 107779839B
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000007747 plating Methods 0.000 title claims abstract description 13
- 238000005516 engineering process Methods 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 26
- 238000010891 electric arc Methods 0.000 claims abstract description 22
- 238000001020 plasma etching Methods 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 16
- 238000010586 diagram Methods 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000000992 sputter etching Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000003574 free electron Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 238000004886 process control Methods 0.000 description 1
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- 238000005488 sandblasting Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/029—Graded interfaces
Abstract
The invention discloses a kind of, and the DLC film plating process based on anode technology is included at least using DLC coating apparatus progress plated film: step 1, under an inert atmosphere, being that cathode carries out arc discharge using magnetic control target as anode, electric arc target, is generated plasma；It is that anode is biased substrate using substrate as cathode, magnetic control target, plasma etching cleaning is carried out to substrate；It step 2, under an inert atmosphere, is that anode carries out magnetron sputtering using rotary magnetron target as cathode, rotating the arc target；It is that cathode is biased using rotating the arc target as anode, workpiece, in deposited on substrates intermediate metal；Step 3, it is passed through hydrocarbon class unstrpped gas, is that cathode is biased using electric arc target as anode, workpiece, DLC layer is deposited on intermediate metal using PaCVD method.The present invention is remarkably improved the stability of DLC coating process and the performance of DLC coated product.
Description
Technical field
The invention belongs to technical field of vacuum plating more particularly to a kind of DLC film plating process based on anode technology.
Background technique
In order to reduce the fuel consumption of automobile, it is desirable that reduce the resistance to sliding for the slide unit being mounted on automobile.It has been known that there is
Construction for this purpose, i.e., using diamond-like carbon film (DLC, the Diamond Like with low frictional properties and wear resistance
Carbon) slide unit surface cladding is got up.DLC is the meta-stable form that there is the carbon atom of sp3 hydridization to account for very big ratio
Amorphous carbon.DLC generally has high rigidity and a smooth surface, also have good wearability, chemical stability, thermal conductivity and
Mechanical performance.
Currently, DLC coating can be prepared on various substrates, to develop new component.The known main side for preparing DLC coating
Method has PVD method (Physical Vapor Deposition, physical vapor deposition) and PaCVD method (Plasma assisted
Chemical Vapor Deposition, plasma-assisted chemical vapour deposition method) two kinds.Wherein, PaCVD method is because of film forming speed
Faster, and the workpiece of complicated shape is adapted to, PaCVD method is made to become the main stream approach for preparing DLC coating.In PaCVD technique
Plasma can be excited by DC pulse power source.In DC pulse plasma processing unit, place in process chamber
It is raw in process chamber by applying DC pulse voltage to substrate under the negative pressure state containing hydrocarbon class unstrpped gas environment
It deposits to form DLC coating in substrate surface so that hydrocarbon class unstrpped gas is in plasma at plasma.
Very high residual compressive stress in DLC coating, DLC coating phase directly will be will lead in substrate surface deposition DLC coating
Adhesive force weak for the adhesive force of substrate, for enhancing DLC layer with respect to substrate, a kind of known method are in substrate and DLC layer
Between buffering of the evaporation metal transition zone as stress, cross plating process control be DLC coating process one of key technology.
For the requirements at the higher level for adapting to industrial development, the stability of DLC coating process and the performance of DLC coated product need into
One step improves.
Summary of the invention
The object of the present invention is to provide it is a kind of be remarkably improved technology stability and properties of product based on anode technology
DLC film plating process.
A kind of DLC film plating process based on anode technology provided by the invention carries out plated film using DLC coating apparatus, until
Include: less
Step 1, substrate is cleaned using plasma etching method, specifically:
Under an inert atmosphere, it is that cathode carries out arc discharge using magnetic control target as anode, electric arc target, generates plasma；With
Substrate is cathode, magnetic control target is that anode is biased substrate, carries out plasma etching cleaning to substrate；
Step 2, using magnetron sputtering method in deposited on substrates intermediate metal, specifically:
It under an inert atmosphere, is that anode carries out magnetron sputtering using rotary magnetron target as cathode, rotating the arc target；With electric rotating
Arc target is anode, workpiece is that cathode is biased, in deposited on substrates intermediate metal；
Step 3, DLC layer is deposited on intermediate metal using PaCVD method, specifically:
It is passed through hydrocarbon class unstrpped gas, is that cathode is biased using electric arc target as anode, workpiece, using PaCVD method in gold
Belong to and deposits DLC layer on transition zone.
Further, described in deposited on substrates intermediate metal in step 2, further comprise:
Under an inert atmosphere, in deposited on substrates metal layer；
It is passed through hydrocarbon class unstrpped gas, on the metal layer deposited metal-metal-carbide gradient layer, metal-carbide one by one
Layer；
Metal layer, the gradient layer of metal-carbon metal, metal-carbide layer constitute intermediate metal.
Further, the DLC coating apparatus include vacuum chamber, rotational workpieces frame, rotating the arc target, rotary magnetron target,
Gas handling system, pumped vacuum systems, heating system and power-supply system, the vacuum chamber ground connection, the power-supply system includes that magnetic control splashes
Radio source, arc power, grid bias power supply, first contactor, second contactor, third contactor and the 4th contactor；Wherein:
Grid bias power supply cathode connection rotational workpieces frame on workpiece, by first contactor connect grid bias power supply anode and
Rotating the arc target connects the anode and rotary magnetron target of grid bias power supply by second contactor；
The cathode of magnetron sputtering power supply connects rotary magnetron target, and the anode of magnetron sputtering power supply is connected by third contactor
With rotating the arc target；
The cathode of arc power connects rotating the arc target, and the anode and rotary magnetic of arc power are connected by the 4th contactor
Control target.
The film plating process using above-mentioned DLC coating apparatus, includes at least:
(1) substrate is placed on rotational workpieces frame, is vacuumized and is heated to vacuum chamber；
(2) it is connected to second contactor and the 4th contactor, disconnects first contactor and third contactor, opens arc power
And grid bias power supply, plasma etching cleaning is carried out to substrate under an inert atmosphere；
(3) it is connected to first contactor and third contactor, disconnects second contactor and the 4th contactor, opens magnetron sputtering
Power supply and grid bias power supply, under an inert atmosphere in deposited on substrates intermediate metal；
(4) it is connected to first contactor, disconnects second contactor, third contactor and the 4th contactor, it is former to be passed through hydrocarbon class
Expect gas, opens grid bias power supply, DLC layer is deposited on intermediate metal.
Further, in step (1), vacuum chamber is vacuumized and is heated, air pressure in vacuum chamber is made to be lower than 5.0*10-3Pa,
Temperature reaches 100 degree~300 degree.
Especially it is noted that the DLC layer only refers to that carbon-coating, the DLC coating include carbon-coating and metal mistake in the present invention
Layer is crossed, i.e., the described DLC coating includes DLC layer and intermediate metal.
Currently, the DLC film plating process of DLC layer adhesive force can be enhanced known to one kind, step is included at least:
Step 1, substrate is cleaned using plasma etching method；
Step 2, using magnetron sputtering method on substrate evaporation metal transition zone；
Step 3, DLC layer is deposited on intermediate metal using PaCVD method.
Traditional DLC coating process is using vacuum chamber as anode, and using workpiece or target as cathode, industry is general to be just more concerned about yin
Pole process and less focus on anode.The present invention is based on known DLC film plating process, and make full use of anode characteristic, Lai Tisheng DLC
The stability of coating process and the performance of DLC coated product.
About step 1, substrate surface oxide can be eliminated by cleaning to substrate, so as in enhancing base materials coating it is attached
Put forth effort.Various ion etching methods can be used in the cleaning of known substrate, specifically include that 1) glow discharge argon ion etching, 2) arc is put
Electric metal ion etching method and 3) ion source auxiliary etch.
To avoid introducing new pollution in cleaning process, the present invention is carried out using arc auxiliary glow discharge plasma etching method
Substrate surface cleaning.The plasma etching method of the present invention has hardware similar with arc discharge metal ion etching method, by changing
Become pole orientation, plate washer and anode setting, the principle and effect and conventional arc discharge metal ion of etching are etched with essential distinction.
When arc discharge, cathode surface becomes clear scorching hot cathode protection to external spatial emission metal ion and free electron, further includes
The drop not gasified sufficiently.Apply the metal ion in back bias voltage acceleration plasma to workpiece, metal ion bombards workpiece table
Face.Since the motion profile of cathode protection is by magnetically confined, make evaporating surface towards workpiece by the magnetic pole of face workpiece, to obtain
Maximum etching effect.Workpiece is equal to substrate in the present invention.
It is different from traditional arc discharge metal ion etching method, the arc auxiliary glow discharge plasma etching method of the present invention
In, the pole orientation of electric arc target is back to workpiece, and the metal ion and drop of arc discharge generation are shielded by shielding case, and free electron
It is extracted by anode.Free electron generates plasma to ionization Ar atom during anode movement, on workpiece plus back bias voltage, inhales
Draw Ar ion pair workpiece and performs etching cleaning.
The present invention has an advantage in that the pollution that can eliminate drop in arc discharge using plasma etching cleaning, to improve DLC
The adhesive force of layer further reduces the coefficient of friction of DLC layer, enhances the corrosion resistance of DLC layer.
About step 2, conventional magnetron sputtering method as anode and is grounded using sputtering target as cathode using vacuum chamber.Due to yin
Pole and anode spacing are close, are easy to be more readily captured by the anode from electric secondary electron in plasma, and cause plasma from
Rate is high, coating consistency deficiency disadvantage.Currently, generally being asked using closed field unbalanced magnetron sputtering method to solve this
Topic.The core of closed field unbalanced magnetron sputtering method is: constraint and free secondary electron using magnetic field to free secondary electron
Along the rule of magnetic line of force screw, increases the free path and collision probability of free secondary electron, improve the ionization of plasma
Rate.
The present invention uses method of the impressed current anode far from cathode in magnetron sputtering technique, is prolonged by simpler method
The free path of long free secondary electron, increases electron collision probability, improves the density of plasma, to obtain finer and close painting
Layer structure.
About step 3, conventional PaCVD method deposits DLC layer, using workpiece as cathode, forms DLC for receiving CH ion
Layer.Meanwhile byproduct of reaction also can be piled into insulating film in anode, the insulating layer of accumulation will affect the plasma of yin-yang electrode systems
Impedance causes the deviation of technical process.DLC coating deposition uses batch furnace, and the processing time is 4 hours~8 hours, plasma resistance
Anti- variation will cause the fluctuation of product quality between batch.To guarantee that DLC coating product quality in tolerance interval, needs periodically clear
Manage anode.When the use of vacuum chamber being anode, the cleaning work of anode needs the anode that will be exposed in plasma in vacuum chamber
(including interior lining panel, plate washer, heater etc.) dismounting sandblasting, is cleaned, is reinstalled, and carrying out precoated shet aging process, and anode is clear
Manage intricate operation and difficulty.
The present invention is when depositing DLC layer, using impressed current anode, realizes the automated cleaning of anode with can be convenient in this way.This
Invention is deposited in the insulating film meeting on its surface when target is anode alternately as cathode and anode using electric arc target and magnetic control target
Removing is evaporated when target makees cathode.Specifically, have in step 3 as the electric arc target of anode and pass through step 1 plasma etching
Fresh surface after arc discharge is processed.
In summary, the invention has the advantages that and the utility model has the advantages that
(1) substrate is cleaned using plasma etching method, the pollution of drop produced by arc discharge can be eliminated, to can be improved
The adhesive force of DLC coating reduces the coefficient of friction of DLC coating, enhances the corrosion resistance of DLC coating.
(2) in the step of magnetron sputtering method evaporation metal transition zone, method using impressed current anode far from cathode extends
The free path of free secondary electron increases electron collision probability, the density of plasma is improved, to improve the cause of coating structure
Close property.
(3) it using electric arc target and magnetic control target alternately as cathode and anode, is convenient to realize the automatic clear of anode in this way
It is clean, to can avoid the product quality fluctuation caused by adhering to insulating layer because of anode, improve technology stability.
Detailed description of the invention
Fig. 1 is the horizontal cross-section schematic diagram of conventional DLC coating apparatus；
Fig. 2 is the horizontal cross-section schematic diagram of DLC coating apparatus of the present invention；
Fig. 3 is the contactor connection schematic diagram of plasma etching stage DLC coating apparatus of the present invention；
Fig. 4 is the contactor connection schematic diagram of magnetron sputtering stage DLC coating apparatus of the present invention；
Fig. 5 is the contactor connection schematic diagram of PaCVD depositional phase DLC coating apparatus in the present invention；
Fig. 6 is the electromicroscopic photograph of DLC coating prepared by the present invention；
Fig. 7 is the Lip river formula impression photo of DLC coating prepared by the present invention.
In figure: 1- vacuum chamber, 2- rotational workpieces frame, 3- rotating the arc target, 4- rotary magnetron target, 5- plate washer, 6- magnetic control splash
Radio source, 7- arc power, 8- grid bias power supply, 9- first contactor, 10- second contactor, 11- third contactor, 12- the 4th
Contactor.
Specific embodiment
In order to illustrate the embodiments of the present invention more clearly and/or technical solution in the prior art, attached drawing will be compareed below
Illustrate a specific embodiment of the invention.It should be evident that the accompanying drawings in the following description is only the embodiment of the present invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing, and obtain other embodiments.
Fig. 1 show the horizontal cross-section schematic diagram of conventional DLC coating apparatus, including vacuum chamber 1, rotational workpieces frame 2, rotation
Electric arc target 3, rotary magnetron target 4, plate washer 5, gas handling system, pumped vacuum systems, heating system, evaporation source power-supply system.Rotate work
Part frame 2, rotating the arc target 3 and rotary magnetron target 4 are set in vacuum chamber 1, are equipped with by rotating the arc target 3 and rotary magnetron target 4
Plate washer 5；Gas handling system is used to be passed through unstrpped gas into vacuum chamber 1, and pumped vacuum systems is used to vacuumize vacuum chamber 1, heat
System is used to heat to vacuum chamber.The power-supply system includes magnetron sputtering power supply 6, arc power 7 and grid bias power supply 8, wherein
The cathode (i.e. cathode) of magnetron sputtering power supply 6 connects rotary magnetron target 4, and the cathode of arc power 7 connects rotating the arc target 3, partially
Voltage source 8 cathode connection rotary work frame 2 on workpiece, magnetron sputtering power supply 6, arc power 7, grid bias power supply 8 anode (i.e.
Anode) it is grounded.
Fig. 2 show the horizontal cross-section schematic diagram of DLC coating apparatus of the present invention, and the difference of routine DLC coating apparatus
It is that power-supply system further includes 4 contactors switched for cathode and anode, grid bias power supply 8 is connected by first contactor 9
Anode and rotating the arc target 3, by second contactor 10 connect grid bias power supply 8 anode and rotary magnetron target 4, pass through third
Contactor 11 connects the anode and rotating the arc target 3 of magnetron sputtering power supply 6, connects arc power 7 by the 4th contactor 12
Anode and rotary magnetron target 4.In the present invention, rotating the arc target 3 and rotary magnetron target 4 are preferably Style Columu Talget, but can also be used
Rectangle plane target or circular planar target.
It is anode with vacuum chamber 1, and be grounded in conventional DLC coating apparatus；Also, the magnetic direction of rotating the arc target 3 is just
To workpiece.It with rotating the arc target 3 or rotary magnetron target 4 is then anode in DLC coating apparatus of the present invention, and rotating the arc target 3
Magnetic direction back to workpiece.
Fig. 3 show the connection schematic diagram of contactor in plasma etching stage DLC coating apparatus of the present invention, wherein the
Two contactors 10 are connected to the 4th contactor 12, and first contactor 9 and third contactor 11 disconnect.Fig. 4 show magnetron sputtering
The contactor in stage, DLC coating apparatus of the present invention is connected to schematic diagram, wherein and first contactor 9 is connected to third contactor 11,
Second contactor 10 and the 4th contactor 12 disconnect.Fig. 5 show PaCVD depositional phase, the contact of DLC coating apparatus of the present invention
Device is connected to schematic diagram, wherein first contactor 9 is connected to, and second contactor 10, third contactor 11, the 4th contactor 12 are disconnected
It opens.
The technical process that DLC plated film is carried out using DLC coating apparatus of the present invention is provided below.
Different intermediate metals can be prepared from unstrpped gas using different targets, for example, target can choose Ti
Target, Cr target, WC target etc., but not limited to this；Unstrpped gas can be in Ar, N2、CH2、H2, CH4Middle selection, but not limited to this, according to
The difference of intermediate metal, DLC can have a variety of structures, for example, Cr/CrC/DLC, Cr/CrN/CrCN/CrC/DLC, Ti/
TiN/TiCN/TiC/DLC, Cr/CrWC/WC-C/DLC.
Below by by taking the DLC coating of Cr/CrC/DLC structure as an example, illustrate its preparation process.
1) it vacuumizes and heats
Workpiece is placed on rotational workpieces frame 3, vacuum chamber 1 is closed, to vacuumizing and heating degasification in vacuum chamber 1, by vacuum
Temperature is heated to 100 degree~300 degree in chamber 1, and vacuum pressure is lower than 5.0*10-3Pa.Close heating system.Here, 1 temperature of vacuum chamber
Preferably 150 degree~250 degree of degree, vacuum pressure is preferably shorter than 2.0*10-3Pa。
2) plasma etching method cleaning workpiece
Ar gas and H are poured to vacuum chamber 12Vacuum pressure reaches 0.5Pa in the mixed gas of gas to vacuum chamber 1, wherein Ar
Gas and H2The volume ratio of gas is 4:1.It is connected to contactor according to mode shown in Fig. 3, at this point, rotating the arc target 3 is cathode, rotary magnetic
Control target 4 is anode, opens arc power 7, sets target current as 100A~200A, target voltage is 15V~30V at this time.With workpiece
For cathode, rotary magnetron target 4 is biased for anode, sets back bias voltage 100V~200V, frequency 120KHz, duty ratio 80%.
Plasma etching cleaning is carried out to workpiece, cleans duration 10min~30min.
3) magnetron sputtering method deposited metal transition zone
It is filled with vacuum pressure in Ar gas to vacuum chamber and is maintained 0.3Pa, be connected to contactor according to mode shown in Fig. 4, at this time
Rotary magnetron target 4 is cathode, and rotating the arc target 3 is anode, opens magnetron sputtering power supply 6, sets power as 10KW.With electric rotating
Arc target 3 is anode, and workpiece is that cathode is biased 100V, frequency 120KHz, duty ratio 80%.The deposited metal Cr on workpiece
Layer, about 0.3 μm of sedimentation time 30min, Cr thickness degree.
Then, Cr-CrC gradient layer is deposited on Cr layer in method known to industry.Promote gradually, to be filled with C2H2, and reduce Ar
Flow, maintaining vacuum pressure in vacuum chamber is 0.4Pa, finally makes Ar and C2H2Volume ratio reach 2:1, and reduce and be biased into
60V.The sedimentation time of Cr-CrC gradient layer be 20min, about 0.2 μm of Cr-CrC Thickness of Gradient Layer.
Finally, maintaining the filming parameter of deposition Cr-CrC gradient layer constant, CrC layers are deposited on Cr-CrC gradient layer, are sunk
Long-pending time 30min, about 0.3 μm of CrC thickness degree.
4) PaCVD method deposits DLC layer
C is filled with to vacuum chamber2H2Vacuum degree reaches 1.0Pa~1.5Pa in vacuum chamber, is connected to and connects according to mode shown in Fig. 5
Tentaculum is anode with rotating the arc target 3, and workpiece is cathode, is biased 400V~600V, frequency 120KHz, duty ratio 80%.
Sedimentation time 120min, root Ju load state, gained DLC layer is with a thickness of 2 μm~4 μm.
DLC coating hardness is tested using nanoindenter, using the thickness of ball hole method test DLC coating, using scanning electricity
The cross section structure of sem observation DLC coating, is shown in Fig. 6；Using the coating adhesion of Lip river formula indentation method test DLC coating, Fig. 7 is seen.This
The hardness for inventing prepared DLC coating is 15GPa~30GPa, DLC coating with a thickness of 1.5 μm~3.5 μm.
Fig. 6 is the electromicroscopic photograph of DLC coating prepared by the present invention, is successively Cr layers of metal base, CrC from top to bottom in figure
Gradient layer and DLC layer, Cr layers are in the form of a column crystal structure and have a clear longitudinal stripe, Cr layers of columnar crystal structure of CrC extension, and face
The variation of the bright ingredient of color more superficial, DLC layer are glassy states, and surface is smooth, compact structure.Entire membrane system Coating combination is good
It is good.
Fig. 7 is the Lip river formula impression photo of prepared DLC coating, be can be seen that in figure, there is subtle radial split around impression
Line, uncoated peeling show that coated film base is well combined.
Present invention difference is anode using vacuum chamber with existing DLC coating process, uses magnetic control in the plasma etching stage
Target is anode, uses electric arc target for anode in the magnetron sputtering stage and with the PaCVD depositional phase, is improved by this anode technology
The cleaning effect of plasma etching improves the consistency of intermediate metal, and improves the process stabilizing of PaCVD deposition process
Property.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and
In scope of protection of the claims, any modifications and changes are made to the present invention, both fall within protection scope of the present invention.
Claims (2)
1. a kind of DLC film plating process based on anode technology carries out plated film using DLC coating apparatus, characterized in that at least wrap
It includes:
Step 1, substrate is cleaned using plasma etching method, specifically:
Under an inert atmosphere, it is that cathode carries out arc discharge using rotary magnetron target as anode, rotating the arc target, generates plasma
Body；It is that anode is biased substrate using substrate as cathode, rotary magnetron target, plasma etching cleaning is carried out to substrate；
Step 2, using magnetron sputtering method in deposited on substrates intermediate metal, specifically:
It under an inert atmosphere, is that anode carries out magnetron sputtering using rotary magnetron target as cathode, rotating the arc target；With rotating the arc target
It is that cathode is biased for anode, workpiece, in deposited on substrates intermediate metal；
Step 3, DLC layer is deposited on intermediate metal using PaCVD method, specifically:
It is passed through hydrocarbon class unstrpped gas, is that cathode is biased using rotating the arc target as anode, workpiece, using PaCVD method in gold
Belong to and deposits DLC layer on transition zone；
The DLC coating apparatus includes vacuum chamber, rotational workpieces frame, rotating the arc target, rotary magnetron target, gas handling system, takes out very
Empty set system, heating system and power-supply system, the vacuum chamber ground connection, the power-supply system include magnetron sputtering power supply, electric arc electricity
Source, grid bias power supply, first contactor, second contactor, third contactor and the 4th contactor；Wherein: the cathode of grid bias power supply
Workpiece on rotational workpieces frame is connected, the anode and rotating the arc target of grid bias power supply are connected by first contactor, is connect by second
The anode and rotary magnetron target of tentaculum connection grid bias power supply；The cathode of magnetron sputtering power supply connects rotary magnetron target, passes through third
The anode and rotating the arc target of contactor connection magnetron sputtering power supply；The cathode of arc power connects rotating the arc target, by the
The anode and rotary magnetron target of four contactors connection arc power；
When cleaning in step 1 to substrate, it is connected to second contactor and the 4th contactor, first contactor is disconnected and third connects
Tentaculum；In step 2 in deposited on substrates intermediate metal, it is connected to first contactor and third contactor, disconnects the second contact
Device and the 4th contactor；In step 3 when depositing DLC layer on intermediate metal, it is connected to first contactor, disconnects the second contact
Device, third contactor and the 4th contactor.
2. the DLC film plating process based on anode technology as described in claim 1, it is characterized in that:
It is described in deposited on substrates intermediate metal in step 2, further comprise:
Under an inert atmosphere, in deposited on substrates metal layer；
Under an inert atmosphere, be passed through hydrocarbon class unstrpped gas, on the metal layer one by one deposited metal-metal-carbide gradient layer,
Metal-carbide layer；
Metal layer, the gradient layer of metal-carbon metal, metal-carbide layer constitute intermediate metal.
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| CN109338322B (en) * | 2018-11-19 | 2020-12-29 | 宁波甬微集团有限公司 | Surface coating of sliding vane of compressor and preparation method thereof |
| CN113151797B (en) * | 2021-04-26 | 2023-03-28 | 东北大学 | Ion cleaning process based on ta-C film plated on surface of hard alloy |
| CN114351141A (en) * | 2021-12-11 | 2022-04-15 | 深圳森丰真空镀膜有限公司 | Processing and preparing method for high-corrosion-resistance rose gold coating |
| CN114481017B (en) * | 2022-02-11 | 2023-10-27 | 松山湖材料实验室 | Coating device and cleaning process |
| CN114481071B (en) * | 2022-02-11 | 2023-10-27 | 松山湖材料实验室 | Coating device and DLC coating process |
| CN115466928A (en) * | 2022-09-02 | 2022-12-13 | 东莞市华升真空镀膜科技有限公司 | Composite coating equipment, composite coating method and coated workpiece |
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