CN108251819A - The method of twin load midfrequent AC PECVD deposition DLC coatings - Google Patents

The method of twin load midfrequent AC PECVD deposition DLC coatings Download PDF

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Publication number
CN108251819A
CN108251819A CN201810065438.6A CN201810065438A CN108251819A CN 108251819 A CN108251819 A CN 108251819A CN 201810065438 A CN201810065438 A CN 201810065438A CN 108251819 A CN108251819 A CN 108251819A
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workpiece
group
midfrequent
dlc coatings
vacuum chamber
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CN201810065438.6A
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Chinese (zh)
Inventor
王向红
黄志宏
李士本
吴骥
吴百中
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Wenzhou Polytechnic
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Wenzhou Polytechnic
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Priority to CN202010645618.9A priority Critical patent/CN111593321A/en
Priority to CN201810065438.6A priority patent/CN108251819A/en
Publication of CN108251819A publication Critical patent/CN108251819A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/26Deposition of carbon only
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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 method of coating
    • C23C16/50Chemical 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 method of coating using electric discharges
    • C23C16/503Chemical 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 method of coating using electric discharges using dc or ac discharges

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention discloses a kind of method of twin load midfrequent AC PECVD deposition DLC coatings, including arranging first group of workpiece and second group of workpiece in vacuum chamber, all workpiece electrical connections in first group of workpiece, all workpiece electrical connections in second group of workpiece;The relative position relation of first group of workpiece and second group of workpiece should meet condition:By the way that first group of workpiece is rotated or translated, first group of workpiece and second group of workpiece can be made regularly to overlap;Using midfrequent AC power supply as plasma exciatiaon source, the two poles of the earth of the midfrequent AC power supply connect first group of workpiece and second group of workpiece respectively;Vacuum chamber is vacuumized and is passed through source gas body, midfrequent AC power supply is opened, DLC coatings is deposited on workpiece using PECVD.The present invention can avoid discharge off and anode disappearance in DLC coating deposition process, bad so as to further eliminate technological fluctuation and product quality as caused by disappearing discharge off and anode.

Description

The method of twin load midfrequent AC PECVD deposition DLC coatings
Technical field
The invention belongs to technical field of vacuum plating more particularly to twin load midfrequent AC PECVD to deposit DLC coatings Method.
Background technology
Currently, plasma deposition technique is widely used in metal surface modification technique, main to include with solid Body target is as the physical vaporous deposition (PVD, Physical Vapour Deposition) of source substance and with gas precursor Plasma-assisted chemical vapour deposition method (PECVD, Plasma enhanced Chemical as source substance VapourDepostion)。
PECVD is one of main method for depositing DLC (diamond-like, Diamond Like Carbon) coating, traditional PECVD deposits DLC techniques using vacuum cavity as anode, using workpiece as cathode, lights glow discharge plasma cracking carburetted hydrogen gas Body, the back bias voltage on workpiece attract ionic hydrocarbon group positively charged in plasma, and deposition forms DLC coatings on workpiece, together The accessory substance (some hydrocarbon fragments) of Shi Fanying can be deposited on the inner wall of cavity.DLC coatings and cavity inner wall on workpiece Accessory substance all be insulation, these insulation substances tendency barrier plasmas discharge channel.
When using direct current as plasma exciatiaon source, in cathode, it is exposed to plasma DLC coating surfaces charge product Tire out to a certain extent, it may occur that capacitance punctures to be formed " electric arc electric discharge ";In anode, the rush step accumulation guiding discharge system of insulating layer Impedance constantly increase at any time, eventually lead to " anode disappearance ".In order to overcome the electric discharge of conventional DC PECVD technique electric arc and sun The adverse effect that pole disappears, has industrially developed DC pulse technology, discharges charge using the gap of pulse.In principle, radio frequency Insulating layer can be penetrated, however there are the risks that radio-frequency leakage brings personal injury.Meanwhile it is loaded between different production batch The impedance of (i.e. workpiece) is different, and radio frequency discharge needs complicated impedance matching network.Fig. 1 show traditional radio frequency PECVD deposits the principle schematic of DLC coatings, is anode with vacuum cavity 1, using workpiece as cathode, workpiece is put in deposition process In on work rest 2, plasma exciatiaon source is used as using radio-frequency power supply 3.
Invention content
In order to solve electric arc electric discharge and anode extinction tests present in PECVD deposition DLC techniques, the present invention provides one The method of the twin load midfrequent AC PECVD depositions DLC coatings of kind.
The present invention installs workpiece, is formed symmetrical twin by being arranged symmetrically two arrays of electrodes in vacuum chamber on electrode Load;The symmetrical twin load refers to can be such that two groups of loads regularly overlap by rotation or translation, this two groups are born The i.e. symmetrical twin load of duty.
The method of the twin load midfrequent AC PECVD depositions DLC coatings of the present invention, including:
First group of workpiece of arrangement and second group of workpiece in vacuum chamber, all workpiece electrical connections in first group of workpiece, second group All workpiece electrical connections in workpiece;Piece count in first group of workpiece and second group of workpiece is n, and described The relative position relation of one group of workpiece and second group of workpiece should meet condition:By the way that first group of workpiece is rotated or is put down It moves, first group of workpiece and second group of workpiece can be made regularly to overlap;
Using midfrequent AC power supply as plasma exciatiaon source, the two poles of the earth of the midfrequent AC power supply connect first group of work respectively Part and second group of workpiece;
Vacuum chamber is vacuumized and is passed through source gas body, midfrequent AC power supply is opened, DLC is deposited on workpiece using PECVD Coating.
It is 2n workpiece is parallel and be equally spacedly arranged in vacuum chamber as a kind of specific embodiment, and sequence is compiled Number;The workpiece of odd-numbered is electrically connected as first group of workpiece, and the workpiece of even-numbered is electrically connected as second group of workpiece.It is described Workpiece is hand-set lid.
As another specific embodiment, 2n workpiece is equally spacedly arranged to centered on vacuum chamber central shaft Circle, it is starting point to select either work, and 2n workpiece is sequentially numbered at same direction, and the workpiece of odd-numbered is electrically connected conduct First group of workpiece, the workpiece of even-numbered are electrically connected as second group of workpiece.The workpiece is watch case.
Compared to the prior art, the present invention has following features and advantageous effect:
So-called twin load refers to spatially symmetrically two groups of loads, i.e., by rotation or translation, can make two groups Load regularly overlaps.During such glow discharge, two groups are supported on whole and part and all have identical plasma density.Such as Fruit cannot form the twin load of symmetrical balance, then can lead to the difference of product coating performance in two loads.Typically, if adopted With small one and large one two workpiece, respectively as two loads, DLC is deposited using midfrequent AC PECVD methods, then on small workpiece Necessarily there is higher plasma density, correspondingly, there is faster deposition velocity, DLC on two workpiece can be brought in this way The deviation of the performance of coating, such as the difference of film thickness, coating hardness, adhesion, color etc..It is given birth in the batch of single type workpiece In production, it is relatively easy to form twin load.
The present invention uses the plasma exciatiaon mode of alternating current discharge, and when so that one group of load is in positive potential, another group is born Load will be in negative potential.Since current potential does not stop to convert over time and space in alternating current discharge plasma system, the previous second is in Load next second of positive potential will be in negative potential, and therefore, in alternating current discharge plasma system current potential is not over time and space It converts with stopping.At a certain moment, the load in negative potential will attract hydrocarbon cation deposition DLC coatings in plasma, and locate Then attract in electronics with the positive charge on surface in the load of positive potential, by the frequency for electricity of increasing exchanges, reduce discharge cycle, it will Within the threshold value that charge accumulated control punctures in capacitance, so that it may eliminate the electric arc because caused by puncturing capacitance and discharge.
As workpiece surface formation DLC, in discharge loop, it is equivalent to and connects between metal works and plasma one Capacitance.In alternating current circuit, capacitance has logical high frequency, the characteristic for hindering low frequency, i.e. capacitance can make height by constantly charging and discharging Frequency current lead-through, so as to be connected entire discharge loop, frequency is more than the medium frequency alternating current of 40kHz, can penetrate more than 10um DLC film layer.Therefore, be not in draw due to insulating layer obstructs in direct-current discharge using midfrequent AC PECVD deposition DLC techniques The discharge off and anode extinction tests risen, so as to further eliminate the technological fluctuation as caused by disappearing discharge off and anode It is bad with product quality.
In the batch production of single type workpiece, twin load is formed relatively easily, therefore, the method for the present invention is especially suitable Close the batch coating treatment of the workpiece surfaces such as clock and watch, mobile phone shell and automobile and weaving parts.
Description of the drawings
Fig. 1 is the principle schematic of traditional radio frequency PECVD deposition DLC coatings;
Fig. 2 is a kind of specific implementation of twin load in the method for the present invention;
Fig. 3 is another specific embodiment of twin load in the method for the present invention.
In figure, 1- vacuum cavities, 2- work rests, 3- radio-frequency power supplies, 4- tube furnaces, 5- stainless steel hand-set lids, 6- intermediate frequencies AC power, 7- vertical heaters, 8- stainless steel watch cases.
Specific embodiment
In order to illustrate the embodiments of the present invention more clearly and/or technical solution of the prior art, attached drawing will be compareed below Illustrate the specific embodiment of the present 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, other are can also be obtained according to these attached drawings Attached drawing, and obtain other embodiments.
Two kinds of specific embodiments of twin load in the present invention are provided below in conjunction with attached drawing.
Fig. 2 show a kind of specific embodiment of twin load in the method for the present invention, available for stainless steel hand-set lid Plated film.Here, stainless steel hand-set lid 5 is workpiece to be coated, and DLC depositions are specifically carried out in tube furnace 4.By 2n not It becomes rusty axial direction of the steel hand-set lid 5 along tube furnace 4, it is parallel and be equally spacedly arranged in tube furnace 4, in present embodiment, n It is 11.2n stainless steel hand-set lid 5 is sequentially numbered is 1,2,3 ... 2n, wherein, the stainless steel hand-set lid 5 of odd-numbered It is electrically connected as first group of workpiece, the stainless steel hand-set lid 5 of even-numbered is electrically connected as second group of workpiece, first group of workpiece It can be overlapped by translation with second group of workpiece, therefore, first group of workpiece and second group of workpiece are for twin load.Two groups of workpiece Two output terminals of connection midfrequent AC power supply 6 respectively connect two electrodes of midfrequent AC power supply 6.
Fig. 3 show a kind of specific embodiment of twin load in the method for the present invention, available for stainless steel watch case Plated film.Here, stainless steel watch case 8 is workpiece to be coated, and DLC depositions are specifically carried out in vertical heater 7.By 2n stainless steel Watch case 8 is installed on hanging rod, hanging rod be fixed in vertical heater 7 so that 2n stainless steel watch case 8 be equally spacedly arranged to Circle centered on 7 central shaft of vertical heater.In present embodiment, n 7.It is starting point to select any stainless steel watch case 8, At same direction (clockwise or counterclockwise), 2n stainless steel watch case 8 sequentially to be numbered be 1,2,3 ... 2n, wherein, odd number The stainless steel watch case 8 of number is electrically connected as first group of workpiece, and the stainless steel watch case 8 of even-numbered is electrically connected as second Group workpiece, in Fig. 3, stainless steel watch case shown in black 8 is first group of workpiece, and stainless steel watch case 8 shown in white is second group Workpiece.First group of workpiece with second group of workpiece by that around 7 center axis rotation certain angle of vertical heater, can be completely superposed, therefore, One group of workpiece and second group of workpiece are for twin load.Two groups of workpiece connect two output terminals of midfrequent AC power supply 6 respectively, that is, connect Connect two electrodes of midfrequent AC power supply 6.
The relative position relation of twin load is only described for convenience above with respect to the explanation of serial number, it, need only in practical operation By the good electrode of this regular arrangement, and the mode that is loaded of workpiece is identical with the mode that is loaded of workpiece in direct current or radio frequency PECVD, will not Extra work is brought when batch is converted.
Traditional DLC coating depositing operations generally comprise plasma etching cleaning, deposition transition zone and deposition DLC functions Three step of layer.The present invention twin load midfrequent AC plasma discharging, can be not only used for plasma deposition, it can also be used to wait from Son etching.When being passed through reactive sources gas, DLC functional layers can be deposited;When being passed through inert gas, workpiece surface can be carried out Plasma etching cleans.Therefore, the method for the present invention is compatible with tradition DLC coating depositing operations.
For ease of understanding, the specific implementation of twin load midfrequent AC PECVD deposition DLC coatings is described more detail below Journey, involved process conditions are merely illustrative in the specific implementation process.
(1) preparation:
Cleaning workpiece according to the symmetrical requirements of twin load, the workpiece after cleaning is installed in vacuum chamber, vacuum chamber can Think the furnace chamber of tube furnace or vertical heater, but not limited to this.The electrode and electrode and vacuum cavity of inspection midfrequent AC power supply Between insulating properties, close vacuum chamber chamber door.
(2) it vacuumizes:
The interlayer of vacuum chamber cavity is passed through 60 degree of cycle warm water, opens vacuum pump and vacuumizes 1 hour, makes gas in vacuum chamber It forces down in 2.0 × 10-3Pa。
(3) Pressure Rise Rate is tested:
It closes vacuum pumping valve one minute, tests air pressure rising in vacuum chamber and must not exceed 1.0 × 10-2Pa。
(4) plasma etching cleans:
The interlayer of vacuum chamber cavity is passed through 20 degree of recirculated cooling water, be filled with into vacuum chamber 200sccm Ar and 50sccmH2, by adjusting valve regulation vacuum pumping speed, air pressure in vacuum chamber is made to reach 1.0Pa.Set voltage 600V, frequency 40kHz opens midfrequent AC power supply point combustion plasma, scavenging period 1 hour.
(5) PECVD deposits Si-DLC adhesion layers:
250sccm TMS (tetramethylsilane) are filled with into vacuum chamber, air pressure in vacuum chamber is adjusted and, to 1.0Pa, sets electricity 400V is pressed, midfrequent AC power supply point combustion plasma is opened, deposits Si-DLC adhesion layers in workpiece surface, sedimentation time 15 divides Clock.
(6) PECVD deposits Si-DLC gradient layers:
Using known to professional technician in the industry method deposit Si-DLC gradient layers, that is, by TMS be filled with flow from 250sccm is progressively decreased to 0, by C2H2The flow that is filled be incrementally increased from 0 to 600sccm, by air pressure in vacuum chamber from 1.0Pa is gradually adjusted to 1.5Pa, and voltage is incrementally increased from 400V to 500V, sedimentation time 30 minutes.
(7) PECVD deposits DLC functional layers:
Maintain C2H2Be filled with flow as 600sccm, air pressure is 1.5Pa, voltage 500V in vacuum chamber, deposits DLC functions Layer, sedimentation time 150 hours.
(8) quality control:
Present embodiment is tested respectively and deposits DLC coatings using nanoindenter, ball hole method, Lip river formula indentation method Hardness, thickness and adhesive force, hardness 15GPa-30GPa, film thickness are 1.5 μm -3.5 μm, adhesive force HF1-HF2.
Whole technological parameters are shown in Table 1 involved by present embodiment.
1 technological parameter of table
Above-described embodiment be used for illustrate the present invention rather than limit the invention, the present invention spirit and In scope of the claims, any modifications and changes are made to the present invention, both fall within protection scope of the present invention.

Claims (5)

1. the method for twin load midfrequent AC PECVD deposition DLC coatings, it is characterized in that, including:
First group of workpiece of arrangement and second group of workpiece in vacuum chamber, all workpiece electrical connections in first group of workpiece, second group of workpiece In the electrical connection of all workpiece;Piece count in first group of workpiece and second group of workpiece is n, and described first group The relative position relation of workpiece and second group of workpiece should meet condition:By the way that first group of workpiece is rotated or is translated, First group of workpiece and second group of workpiece can be made regularly to overlap;
Using midfrequent AC power supply as plasma exciatiaon source, the two poles of the earth of the midfrequent AC power supply connect respectively first group of workpiece and Second group of workpiece;
Vacuum chamber is vacuumized and is passed through source gas body, midfrequent AC power supply is opened, DLC coatings is deposited on workpiece using PECVD.
2. the method for twin load midfrequent AC PECVD deposition DLC coatings as described in claim 1, it is characterized in that:
It is 2n workpiece is parallel and be equally spacedly arranged in vacuum chamber, and serial number;The workpiece of odd-numbered is electrically connected work For first group of workpiece, the workpiece of even-numbered is electrically connected as second group of workpiece.
3. the method for twin load midfrequent AC PECVD deposition DLC coatings as claimed in claim 2, it is characterized in that:
The workpiece is hand-set lid.
4. the method for twin load midfrequent AC PECVD deposition DLC coatings as described in claim 1, it is characterized in that:
2n workpiece is equally spacedly arranged to the circle centered on vacuum chamber central shaft, it is starting point to select either work, is pressed Same direction sequentially numbers 2n workpiece, and the workpiece of odd-numbered is electrically connected as first group of workpiece, the workpiece of even-numbered It is electrically connected as second group of workpiece.
5. the method for twin load midfrequent AC PECVD deposition DLC coatings as claimed in claim 4, it is characterized in that:
The workpiece is watch case.
CN201810065438.6A 2018-01-23 2018-01-23 The method of twin load midfrequent AC PECVD deposition DLC coatings Pending CN108251819A (en)

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CN202010645618.9A CN111593321A (en) 2018-01-23 2018-01-23 Method for depositing DLC coating by twinning load medium-frequency alternating current PECVD
CN201810065438.6A CN108251819A (en) 2018-01-23 2018-01-23 The method of twin load midfrequent AC PECVD deposition DLC coatings

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Application publication date: 20180706