CN108677144A - A method of it preparing aluminium nitrogen and is co-doped with diamond-like carbon composite film - Google Patents
A method of it preparing aluminium nitrogen and is co-doped with diamond-like carbon composite film Download PDFInfo
- Publication number
- CN108677144A CN108677144A CN201810556974.6A CN201810556974A CN108677144A CN 108677144 A CN108677144 A CN 108677144A CN 201810556974 A CN201810556974 A CN 201810556974A CN 108677144 A CN108677144 A CN 108677144A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- cathode
- diamond
- arc
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- IWBUYGUPYWKAMK-UHFFFAOYSA-N [AlH3].[N] Chemical compound [AlH3].[N] IWBUYGUPYWKAMK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 239000010439 graphite Substances 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004411 aluminium Substances 0.000 claims abstract description 23
- 238000001704 evaporation Methods 0.000 claims abstract description 20
- 230000008020 evaporation Effects 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 238000005137 deposition process Methods 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- 239000012495 reaction gas Substances 0.000 claims abstract description 3
- 238000004062 sedimentation Methods 0.000 claims abstract description 3
- 238000004544 sputter deposition Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 63
- 229910052786 argon Inorganic materials 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 239000004519 grease Substances 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010884 ion-beam technique Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 210000001367 artery Anatomy 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 229910017083 AlN Inorganic materials 0.000 abstract description 8
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000008187 granular material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 86
- 230000035882 stress Effects 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910018509 Al—N Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012876 topography Methods 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
- 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
- C23C14/0605—Carbon
- C23C14/0611—Diamond
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
-
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of methods for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film.Using ion source auxiliary cathode arc deposited technology, the bidifly of two different characteristics of configuration rises cathode arc coating apparatus, one of them is DC arc-plasma evaporation cathode source, and for installing aluminium target, another is pulsed arc evaporation cathode source, for installing graphite target；With nitrogen as reaction gas in deposition process, using ion source by nitrogen (N2) ionize as ionic nitrogen (N+), by rotational workpieces, make the aluminium target and graphite target mounted on DC arc-plasma evaporation cathode source and pulsed arc evaporation cathode source, realize the sputtering sedimentation in workpiece surface, obtains the controllable aluminium nitrogen of ingredient and be co-doped with diamond-like carbon composite film.In the present invention, N is mixed in the form of an ion, promotes to form hard aluminium nitride in diamond-like carbon composite film（AlN）With metal Al nano-crystalline granules；Have the advantages that smooth surface, high rigidity, high tenacity, low stress.
Description
Technical field
The present invention relates to a kind of methods for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, belong to diamond-like carbon composite film
Preparing technical field.
Background technology
DLC film is widely used as most important one kind film in solid lubricant coating in high-speed cutting
Cutter and mold protection etc..However, DLC film itself still has the problem of some urgent need to resolve such as：Eka-gold
The high internal stress and high internal stress of hard rock film and layering occurs the problems such as cause film substrate bond strength low, peels off or failure；Together
When be doped to solve its internal stress the film hardness caused by metallic element decline the problems such as.Therefore, it solves above-mentioned
The problem of restricting DLC film application seems particularly critical and urgent.
Interfacial stress or thermal stress are film bases caused by the coefficient of thermal expansion of DLC film and basis material mismatches
Low one of the reason of bond strength.Synthesis is researched and analysed both at home and abroad, in order to reduce physical difference between film base, often in diamond-like
Heterogeneous element is mixed in film come the problem of alleviating the accumulation of DLC film internal stress and film brittleness.Studies have shown that passing through
Rationally control bonding mode, the film surface chemistry shape of the carbon matrix network that is cross-linked with each other in doped chemical and DLC film
State, thin film composition can improve film substrate bond strength and mechanical strength.It is thin firstly, for metal element A l doped diamonds
For film, in the Al elements incorporation DLC film of " medium hardness ", weak bond can be formed with carbon and close carbide, will significantly be carried
The toughness of high film, but the hardness of film can be reduced to a certain extent.Nonmetalloid N is mixed in DLC film
Afterwards, the carbon atom in C-C keys in substitution film is promoted the sp in film by N atoms2Hybrid bond is to sp3Hybrid bond changes, and improves
The diamond characteristic of film, but not it is obviously improved the toughness of film.However, being co-doped with DLC film for Al, N dual element
Research it is rare.
Invention content
The present invention is intended to provide a kind of method for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, in conjunction with metal-doped and non-
The advantage of metal-doped DLC film selects non-metal N element and metal Al elements as dopant, and this method passes through conjunction
The microstructure and ingredient of reason regulation and control film, can prepare comprising AlN reinforced by nanoparticles phase, simple substance Al nano particle toughenings
The aluminium nitrogen of phase is co-doped with diamond-like carbon composite film.
In the present invention, N is mixed in the form of an ion, promotes to form aluminium nitride AlN and metal Al in diamond-like carbon composite film
Nano-crystalline granule；Aluminum Nitride Nanocrystals particle can mutually improve the hardness of DLC film as mechanical enhancer, and Al is nanocrystalline
Particle is uniformly embedded in amorphous carbon network matrix, can be given full play to metal plastic deformation effect, be strained by discharging, greatly
Improve the toughness of film in ground.During being co-doped with DLC film using Cathodic Arc Plasma Deposition Technology preparation Al, N dual element,
Metal targets and graphite target easy to produce a large amount of macroscopic particles under the action of high-temperature electric arc, and film surface is caused to become thick
Performance that is rough and greatly reducing film.In order to eliminate adverse effect of the macroscopic particles in DLC film deposition process,
The present invention changes the adding mode of nitrogen source, using ion source auxiliary cathode arc deposited technology by inert nitrogen (N2) ionization
For highly active ion nitrogen (N+), coordinate direct current and pulse bidifly to rise cathode plasma precipitation equipment, is prepared in workpiece surface
Surface smooth aluminium nitrogen is co-doped with diamond-like carbon composite film.It, can by rationally controlling the content of two kinds of elements of aluminium nitrogen in film
Toughness to reach DLC film is matched with hardness optimal.This applies DLC film in engineering field further
It promotes most important.
The present invention provides a kind of methods for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, using ion source auxiliary cathode
The bidifly of arc deposited technology, two different characteristics of configuration rises cathode arc coating apparatus, one of them is direct-current arc steaming
Cathode source is sent out, for installing aluminium target, another is pulsed arc evaporation cathode source, for installing graphite target；Film deposits it
Before, first it is passed through Ar and N2Mixed gas carries out sputter clean using ion source to workpiece surface；In film deposition process, with nitrogen
Gas is as reaction gas, using ion source by nitrogen (N2) ionize as ionic nitrogen (N+), by rotational workpieces, make to be mounted on direct current
The aluminium target and graphite target in arc evaporation cathode source and pulsed arc evaporation cathode source realize the sputtering sedimentation in workpiece surface,
It is multiple that the controllable aluminium nitrogen comprising AlN reinforced by nanoparticles phase, simple substance Al nano particle toughening phases of acquisition ingredient is co-doped with diamond-like
Close film.
The bidifly rises cathode arc coating apparatus, which includes vacuum chamber, direct current aluminium cathode target, pulse graphite
Cathode target；Vacuum chamber rear wall installs direct current aluminium cathode arc power supply and pulse graphite cathode arc power supply, is set outside aluminium cathode target
There are the upper next group deflection magnetic filter being combined, vacuum chamber bottom that circular rotating sample stage is housed, sample stage lower end is true
Empty room external connection grid bias power supply；Pulse graphite anode target is equipped with below pulse graphite cathode target；It is equipped with below DC cathode target
Plasma sputter source；Bleed-off passage is equipped with below vacuum chamber rear wall, outside connects vacuum extractor, vacuum chamber top and side difference
Setting argon gas and nitrogen air admission hole, air admission hole are externally connected to gas flowmeter.
Above-mentioned aluminium nitrogen is co-doped with the preparation method of diamond-like carbon composite film, specifically includes following steps：
(1) workpiece surface is handled：Workpiece is sequentially placed into acetone soln, ethanol solution and deionized water and carries out ultrasound respectively
10 min are cleaned, the grease and other pollutants on surface are removed, it is for use that matrix is then placed in oven drying；
(2) by processed workpiece be fixed on bidifly rise cathode arc coating apparatus vacuum chamber on specimen rotating holder, it is high
Pure aluminum target and graphite target are separately mounted on the evaporator of DC cathode electric arc and pulsed cathode electric arc；
(3) vacuum degree is made to reach 4 × 10 vacuum chamber with vacuum extractor−4~6×10−4Pa；It is logical by air inlet
Enter in argon gas to vacuum chamber, argon flow amount is controlled by flowmeter, adjusts argon flow amount meter charge flow rate, gas pressure in vacuum is made to stablize
3 × 10−2~8×10−2Pa；Specimen rotating holder is opened, sputter clean is carried out to workpiece surface using ion source, is then cooled down
To room temperature；
(4) argon inlet mouth is closed, nitrogen inlet is opened, nitrogen stream gauge charge flow rate is adjusted, gas pressure in vacuum is made to stablize
3 × 10−2~8×10−2Pa；Using ion source ionization nitrogen (N2) generate nitrogen ion beam (N+)；DC cathode electricity is opened simultaneously
Arc evaporates power supply and pulsed cathode arc evaporation source, and adjustings DC cathode voltage is 60 ~ 90 V, DC cathode electric current for 60 ~
70A；Adjusting pulsed cathode voltage is 300 ~ 350 V, and pulse frequency is 3 ~ 10 Hz, and deposition of aluminum nitrogen is co-doped on the workpiece of rotation
Diamond-like carbon composite film.
In above-mentioned preparation method, the step（3）In, the ion source of sputter clean is argon ion, argon flow amount is 30 ~
The time of 60sccm, sputter clean are 10 ~ 15 min, and the energy and beam current density of argon ion are respectively 2 ~ 4 keV and 15 ~ 25
A/m2。
In above-mentioned preparation method, the step（4）In, it is passed through 20 ~ 50sccm of nitrogen flow, Nitrogen ion energy is 120 ~
150 eV。
In above-mentioned preparation method, when pulse cathode arc prepares diamond-film-like in the step (4), umber of pulse 370-
3000。
In above-mentioned preparation method, the sputter clean and rotating speed of sample stage is 1-3 when deposition film in the step (3), (4)
r/min。
In above-mentioned preparation method, the film thickness of gained laminated film is 1.0 μm ~ 1.2 μm.
The aluminium nitrogen prepared using the present invention, which is co-doped in diamond-like carbon composite film, can form thermodynamically stable aluminium nitride
Nanocrystalline, which can be isolated by amorphous carbon matrix, be easy to discharge internal stress, prevent the further expansion of crackle
Exhibition, on the other hand can prevent the sliding of dislocation and crystal boundary, so as to effectively improve the hardness of laminated film, reduce film
Internal stress.
Beneficial effects of the present invention：
（1）The present invention installs ion source on conventional cathodes arc deposited device, for exciting N2Generate N+, make nitrogen with ion shape
Formula mixes, and is conducive to improve the bonding action in film between Al, C, N atom, reduces the roughness of film surface, greatly change
It has been apt to film surface quality.
（2）Preparation method using the present invention, can by change pulsed cathode arc evaporation source current pulse frequency and
DC cathode arc evaporation source current size, control energy density of plasma, regulate and control film in aluminium, nitrogen content,
Realize the preparation of the diamond-like carbon composite film of high rigidity, high tenacity.
（3）The Al atoms not being bonded with carbon can be further increased thin by the characteristic of performance metal forced plasticity deforming
The toughness of film.Compared with simple DLC film, the residual stress that aluminium nitrogen is co-doped with diamond-like carbon composite film is substantially reduced,
Hardness and toughness increase substantially, antiwear property enhancing.
Description of the drawings
Fig. 1 is coating apparatus structural schematic diagram of the present invention；
Fig. 2 is the atomic force microscope 3-d photographs that aluminium nitrogen prepared by embodiment 1 is co-doped with diamond-like carbon composite film surface；
Fig. 3 is the atomic force microscope 3-d photographs that aluminium nitrogen prepared by embodiment 2 is co-doped with diamond-like carbon composite film surface；
Fig. 4 is that aluminium nitrogen prepared by embodiment 1 is co-doped with Al2p XPS spectrums and its fitting peak in diamond-like carbon composite film；
Fig. 5 is that aluminium nitrogen prepared by embodiment 2 is co-doped with Al2p XPS spectrums and its fitting peak in diamond-like carbon composite film；
Fig. 6 is the cut microscope photo that aluminium nitrogen prepared by embodiment 1 is co-doped with diamond-like carbon composite film surface；
Fig. 7 is the cut microscope photo that aluminium nitrogen prepared by embodiment 2 is co-doped with diamond-like carbon composite film surface；
In Fig. 1：1, vacuum chamber；2, direct current aluminium cathode arc power supply；3, pulse graphite cathode arc power supply；4, direct current aluminium cathode
Target；5, magnetic filter is deflected；6, specimen rotating holder；7, pulse graphite cathode target；8, grid bias power supply；9, pulse graphite anode
Target；10, bleed-off passage；11, vacuum extractor；12, argon inlet hole；13, argon flow amount meter, 14, ion source；15, nitrogen into
Stomata；16, nitrogen stream gauge.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Embodiment 1：
There is provided the coating apparatus used in a kind of matrix surface modifying process first, i.e. the direct current and pulse bidifly rises the moon
Pole electrical arc coating apparatus, as shown in Figure 1, the device includes vacuum chamber 1, direct current aluminium cathode target 4, pulse graphite cathode target 7；Vacuum
Room 1 rear wall installation direct current aluminium cathode arc power supply 2 and pulse graphite cathode arc power supply 3,4 outside of direct current aluminium cathode target are equipped with upper
The next group of deflection magnetic filter 5 being combined, 1 bottom of vacuum chamber are equipped with circular rotating sample stage 6, and sample stage lower end is in vacuum
Outdoor connects grid bias power supply 8；7 lower section of pulse graphite cathode target is equipped with pulse graphite anode target 9, is set below direct current aluminium cathode target
There is plasma sputter source 14；It is equipped with bleed-off passage 10 below vacuum chamber 1 rear wall, outside connects vacuum extractor 11, on vacuum chamber 1
Portion；Bleed-off passage is equipped with below vacuum chamber rear wall, outside connects vacuum extractor, and argon gas is respectively set in vacuum chamber top and side
Air admission hole 12 and nitrogen air admission hole 15, air admission hole 12 are externally connected to argon flow amount meter 13 and nitrogen stream gauge 16.
This gives the aluminium nitrogen using above-mentioned apparatus in workpiece surface preparation high rigidity, high tenacity to be co-doped with diamond-like
The method of stone laminated film.Workpiece is tested, operating procedure is as follows：
(1) workpiece surface is handled：Workpiece is sequentially placed into acetone soln, ethanol solution and deionized water and is respectively cleaned by ultrasonic 10
Min, removes the grease and other pollutants on surface, and it is for use that matrix is then placed in oven drying；
(2) specimen rotating holder 6 being fixed on pretreated workpiece in the vacuum chamber 1 of cathode arc device as shown in Figure 1
On, direct current aluminium cathode target 4 and pulse graphite cathode target 7 are separately mounted to direct current aluminium cathode arc power supply 2 and pulsed cathode electric arc
On the evaporator of power supply 3；
(3) vacuum chamber 1 is vacuumized with vacuum extractor 11, vacuum degree is made to reach 6 × 10−4Pa；It is passed through by air admission hole 12
In argon gas to vacuum chamber 1, the flow of argon gas is controlled by gas flowmeter 13, and adjusting argon inlet flow is 35 sccm, makes vacuum
Room stable gas pressure is 5 × 10−2Pa；Open specimen rotating holder 6, using ion source 14 to workpiece surface carry out sputter clean, argon from
The energy and beam current density of son are respectively 3 keV and ~ 25 A/m2, 15 min of scavenging period then cools to room temperature；
(4) argon inlet mouth 12 is closed, nitrogen inlet 15 is opened, it is 35 sccm to adjust 16 charge flow rate of nitrogen stream gauge,
Gas pressure in vacuum is 5 × 10−2.Nitrogen (N is ionized using ion source 142) generate nitrogen ion beam (N+).Open DC cathode simultaneously
Arc evaporation power supply 2 and pulsed cathode arc evaporation source 3, adjusting DC cathode voltage are 80 V, and DC cathode electric current is 60A；
Adjusting pulsed cathode voltage is 350 V, and pulse frequency is 6 Hz, and it is compound to be co-doped with diamond-like for obtained aluminium nitrogen on the workpiece of rotation
Film.
Embodiment 2：
Present embodiments provide it is a kind of using 1 described device of embodiment prepare high rigidity, high tenacity aluminium nitrogen be co-doped with diamond-like
The method of laminated film, includes the following steps：
(1) workpiece surface is handled：Workpiece is sequentially placed into acetone soln, ethanol solution and deionized water and is respectively cleaned by ultrasonic 10
Min, removes the grease and other pollutants on surface, and it is for use that matrix is then placed in oven drying；
(2) specimen rotating holder 6 being fixed on pretreated workpiece in the vacuum chamber 1 of cathode arc device as shown in Figure 1
On, direct current aluminium cathode target 4 and pulse graphite cathode target 7 are separately mounted to direct current aluminium cathode arc power supply 2 and pulsed cathode electric arc
On the evaporator of power supply 3；
(3) vacuum chamber 1 is vacuumized with vacuum extractor 11, vacuum degree is made to reach 6 × 10−4Pa；It is passed through by air admission hole 12
In argon gas to vacuum chamber 1, the flow of argon gas is controlled by gas flowmeter 13, and adjusting argon inlet flow is 50 sccm, makes vacuum
Room stable gas pressure is 8 × 10−2Pa；Open specimen rotating holder 6, using ion source 14 to workpiece surface carry out sputter clean, argon from
The energy and beam current density of son are respectively 2 keV and ~ 20 A/m2, 15 min of scavenging period then cools to room temperature；
(4) argon inlet mouth 12 is closed, nitrogen inlet 15 is opened, it is 50 sccm to adjust 16 charge flow rate of nitrogen stream gauge,
Gas pressure in vacuum is 8 × 10−2.Nitrogen (N is ionized using ion source 142) generate nitrogen ion beam (N+).Open DC cathode simultaneously
Arc evaporation power supply 2 and pulsed cathode arc evaporation source 3, adjusting DC cathode voltage are 80 V, and DC cathode electric current is 80A；
Adjusting pulsed cathode voltage is 350 V, and pulse frequency is 10 Hz, and it is multiple to be co-doped with diamond-like for obtained aluminium nitrogen on the workpiece of rotation
Close film.
Comparative example：
This example gives the method for preparing non-impurity-doped diamond-film-like in workpiece surface using the prior art, tries workpiece
It tests, operating procedure is as follows：
(1) workpiece substrate surface treatment：It is clear that workpiece is sequentially placed into each ultrasound in acetone soln, ethanol solution and deionized water
10 min are washed, the grease and other pollutants on surface are removed, it is for use that matrix is then placed in oven drying；
(2) pretreated workpiece is fixed on the indoor specimen rotating holder of vacuum, graphite target is mounted on pulsed cathode electric arc
Evaporator on；
(3) vacuum degree is made to reach 6 × 10 vacuum chamber with vacuum extractor−4Pa；It is passed through argon gas by air inlet
Into vacuum chamber, the flow of argon gas is controlled by flowmeter, and gas pressure in vacuum is made to stablize 5 × 10−2Pa；Specimen rotating holder is opened,
Sputter clean is carried out to silicon chip using ion source, the energy and beam current density of argon ion are respectively 3 keV and ~ 25 A/m2, clearly
15 min of time is washed, is then cooled to room temperature；
(4) argon inlet mouth is closed, unbalanced pulse cathode arc power supply adjusts cathode voltage in 300 V, pulse frequency 3
Hz, the depositing diamond-like monofilm on the workpiece surface of rotation, umber of pulse 1500,2 r/min of sample stage rotating speed.
Product obtained is tested for the property below：
As shown in Figures 2 and 3, the aluminium nitrogen under the different technical parameters prepared using the method for the present invention is co-doped with diamond-like THIN COMPOSITE
Film shows the surface topography of nanostructure, and film surface particle size and roughness are closely related with technological parameter.
Al 2p XPS spectrum shown in Fig. 4 and Fig. 5 show aluminium nitrogen be co-doped in diamond-like carbon composite film comprising Al-N,
Al-O and Al metallic bonds, film form hard aluminium nitride ceramics phase and the pure aluminum with high ductibility.
Aluminium nitrogen shown in Fig. 6 and Fig. 7 is co-doped with the cut microscope photo of diamond-like carbon composite film, and different process is shown in figure
There is film surface cut different gash depths, film toughness to improve under parameter, and groove periphery does not have apparent crackle, resistance to split
Line extended capability is strong.
Aluminium nitrogen prepared by the present invention is co-doped with the pure DLC film prepared in diamond-like carbon composite film and comparative example
Mechanical property compares：By Si Tuoni stress tests and nano-indenter test thin film mechanical performance, test result shows embodiment
1 and embodiment 2 in aluminium nitrogen to be co-doped with the residual stress of diamond-like carbon composite film be respectively 0.83 GPa and 1.81 GPa, nanometer is hard
Degree（H）Respectively 23.5 GPa and 30 GPa, plasticity_resistant deformation index（H/E）Respectively 0.092 and 0.080；And pure diamond-like
Residual stress, nano hardness and the plasticity_resistant deformation index of stone film are respectively 3.51GPa, 19.2GPa and 0.061..Therefore,
The residual stress of diamond-like based coextruded film is significantly reduced by the method for the invention, and improves its hardness, abrasion resistance
Energy and toughness.
Claims (8)
1. a kind of method for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：Using ion source auxiliary cathode electricity
The bidifly of arc deposition technique, two different characteristics of configuration rises cathode arc coating apparatus, one of them is DC arc-plasma evaporation
Cathode source, for installing aluminium target, another is pulsed arc evaporation cathode source, for installing graphite target；Before film deposition,
First it is passed through Ar and N2Mixed gas carries out sputter clean using ion source to workpiece surface；In film deposition process, made with nitrogen
For reaction gas, it is ionic nitrogen to be ionized nitrogen using ion source, by rotational workpieces, makes to be mounted on DC arc-plasma evaporation cathode
The aluminium target and graphite target in source and pulsed arc evaporation cathode source realize the sputtering sedimentation in workpiece surface, and it is controllable to obtain ingredient
Comprising AlN reinforced by nanoparticles phase, simple substance Al nano particle toughening phases aluminium nitrogen be co-doped with diamond-like carbon composite film.
2. the method according to claim 1 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：Including with
Lower step：
(1) workpiece surface is handled：Workpiece is sequentially placed into acetone soln, ethanol solution and deionized water and carries out ultrasound respectively
10 min are cleaned, the grease and other pollutants on surface are removed, it is for use that matrix is then placed in oven drying；
(2) by processed workpiece be fixed on bidifly rise cathode arc coating apparatus vacuum chamber on specimen rotating holder, it is high
Pure aluminum target and graphite target are separately mounted on the evaporator of DC cathode electric arc and pulsed cathode electric arc；
(3) vacuum degree is made to reach 4 × 10 vacuum chamber with vacuum extractor−4~6×10−4Pa；It is logical by air inlet
Enter in argon gas to vacuum chamber, argon flow amount is controlled by flowmeter, adjusts argon flow amount meter charge flow rate, gas pressure in vacuum is made to stablize
3 × 10−2~6×10−2Pa；Specimen rotating holder is opened, sputter clean is carried out to workpiece surface using ion source, is then cooled down
To room temperature；
(4) argon inlet mouth is closed, nitrogen inlet is opened, nitrogen stream gauge charge flow rate is adjusted, gas pressure in vacuum is made to stablize
3 × 10−2~6×10−2Pa；Nitrogen ion beam is generated using ion source ionization nitrogen；DC cathode arc evaporation electricity is opened simultaneously
Source and pulsed cathode arc evaporation source, adjusting DC cathode voltage are 60 ~ 90 V, and DC cathode electric current is 60 ~ 70A；Adjust arteries and veins
It is 300 ~ 350 V to rush cathode voltage, and pulse frequency is 3 ~ 10 Hz, and it is multiple to be co-doped with diamond-like for deposition of aluminum nitrogen on the workpiece of rotation
Close film.
3. the method according to claim 2 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：The step
Suddenly（3）In, the ion source of sputter clean is argon ion, and argon flow amount is 30 ~ 60sccm, and the time of sputter clean is 10 ~ 15
Min, the energy and beam current density of argon ion are respectively 2 ~ 4 keV and 15 ~ 25 A/m2。
4. the method according to claim 2 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：The step
Suddenly（4）In, it is 30 ~ 60sccm to be passed through nitrogen flow, and the energy of Nitrogen ion is 120 ~ 150 eV.
5. the method according to claim 2 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：The step
Suddenly when pulse cathode arc prepares diamond-film-like in (4), umber of pulse 370-3000.
6. the method according to claim 2 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：The step
Suddenly the sputter clean and rotating speed of sample stage is 1-3 r/min when deposition film in (3), (4).
7. the method according to claim 2 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：Gained is multiple
The film thickness for closing film is 1.0 μm ~ 1.2 μm.
8. the method according to claim 1 for preparing aluminium nitrogen and being co-doped with diamond-like carbon composite film, it is characterised in that：Described
Bidifly rises cathode arc coating apparatus, which includes vacuum chamber, direct current aluminium cathode target, pulse graphite cathode target；Vacuum chamber
Rear wall installs direct current aluminium cathode arc power supply and pulse graphite cathode arc power supply, is mutually tied equipped with upper next group outside aluminium cathode target
The deflection magnetic filter of conjunction, vacuum chamber bottom are equipped with circular rotating sample stage, and sample stage lower end is inclined in vacuum chamber external connection
Voltage source；Pulse graphite anode target is equipped with below pulse graphite cathode target；Plasma sputter source is equipped with below DC cathode target；Vacuum
Bleed-off passage is equipped with below the rear wall of room, outside connects vacuum extractor, and argon gas and nitrogen is respectively set in vacuum chamber top and side
Air admission hole, air admission hole are externally connected to gas flowmeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556974.6A CN108677144B (en) | 2018-06-01 | 2018-06-01 | Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810556974.6A CN108677144B (en) | 2018-06-01 | 2018-06-01 | Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108677144A true CN108677144A (en) | 2018-10-19 |
| CN108677144B CN108677144B (en) | 2020-02-28 |
Family
ID=63809483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810556974.6A Expired - Fee Related CN108677144B (en) | 2018-06-01 | 2018-06-01 | Method for preparing aluminum-nitrogen co-doped diamond-like carbon composite film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108677144B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686521A (en) * | 2018-12-23 | 2019-04-26 | 苏州晶鼎鑫光电科技有限公司 | Method for manufacturing thin film resistive film based on ceramic |
| CN110205589A (en) * | 2019-07-12 | 2019-09-06 | 江苏徐工工程机械研究院有限公司 | Pulse carbon ion excitation source device |
| CN111850484A (en) * | 2020-07-24 | 2020-10-30 | 太原理工大学 | Device and method for preparing tough amorphous carbon-based multiphase hybrid film |
| CN111906144A (en) * | 2020-07-17 | 2020-11-10 | 太原理工大学 | Method for improving interface bonding strength of titanium/aluminum composite board |
| CN112038481A (en) * | 2020-09-01 | 2020-12-04 | 武汉大学 | Heavy rare earth doped ZnO columnar crystal preferred orientation piezoelectric film material and preparation method thereof |
| US20220025538A1 (en) * | 2021-07-14 | 2022-01-27 | Jomoo Kitchen & Bath Co., Ltd. | Method for metallizing plastic by pre-plating for electroplating |
| CN116219391A (en) * | 2023-05-09 | 2023-06-06 | 艾瑞森表面技术（苏州）股份有限公司 | AlN doped diamond-like coating process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798679A (en) * | 2010-03-31 | 2010-08-11 | 北京科技大学 | Preparation method of composite coating used for gas bearing |
| US20120244281A1 (en) * | 2010-11-25 | 2012-09-27 | The University Of Bristol | Low work function diamond surface and radiation energy converters using same |
| CN105132878A (en) * | 2015-09-11 | 2015-12-09 | 太原理工大学 | Method for preparing titanium/diamond-like nanometer multilayer film on silicon surface |
| CN106011745A (en) * | 2016-06-15 | 2016-10-12 | 太原理工大学 | Device and method for preparing amorphous carbon and nitrogen thin films on surface of silicon |
| CN106684387A (en) * | 2016-12-20 | 2017-05-17 | 深圳先进技术研究院 | Lithium ion battery negative electrode comprising diamond-like thin film layer, preparation method for negative electrode, and lithium ion battery |
-
2018
- 2018-06-01 CN CN201810556974.6A patent/CN108677144B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798679A (en) * | 2010-03-31 | 2010-08-11 | 北京科技大学 | Preparation method of composite coating used for gas bearing |
| US20120244281A1 (en) * | 2010-11-25 | 2012-09-27 | The University Of Bristol | Low work function diamond surface and radiation energy converters using same |
| CN105132878A (en) * | 2015-09-11 | 2015-12-09 | 太原理工大学 | Method for preparing titanium/diamond-like nanometer multilayer film on silicon surface |
| CN106011745A (en) * | 2016-06-15 | 2016-10-12 | 太原理工大学 | Device and method for preparing amorphous carbon and nitrogen thin films on surface of silicon |
| CN106684387A (en) * | 2016-12-20 | 2017-05-17 | 深圳先进技术研究院 | Lithium ion battery negative electrode comprising diamond-like thin film layer, preparation method for negative electrode, and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| BING ZHOU等: "Synthesis and characterization of Ti and N binary-doped ɑ-C films deposited by pulse cathode arc with ionic source assistant", 《SURFACE AND INTERFACE ANALYSIS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109686521A (en) * | 2018-12-23 | 2019-04-26 | 苏州晶鼎鑫光电科技有限公司 | Method for manufacturing thin film resistive film based on ceramic |
| CN110205589A (en) * | 2019-07-12 | 2019-09-06 | 江苏徐工工程机械研究院有限公司 | Pulse carbon ion excitation source device |
| CN110205589B (en) * | 2019-07-12 | 2023-12-08 | 江苏徐工工程机械研究院有限公司 | Pulse carbon ion excitation source device |
| CN111906144A (en) * | 2020-07-17 | 2020-11-10 | 太原理工大学 | Method for improving interface bonding strength of titanium/aluminum composite board |
| CN111906144B (en) * | 2020-07-17 | 2022-02-22 | 太原理工大学 | Method for improving interface bonding strength of titanium/aluminum composite board |
| CN111850484A (en) * | 2020-07-24 | 2020-10-30 | 太原理工大学 | Device and method for preparing tough amorphous carbon-based multiphase hybrid film |
| CN112038481A (en) * | 2020-09-01 | 2020-12-04 | 武汉大学 | Heavy rare earth doped ZnO columnar crystal preferred orientation piezoelectric film material and preparation method thereof |
| CN112038481B (en) * | 2020-09-01 | 2023-09-22 | 武汉大学 | Heavy rare earth doped ZnO columnar crystal preferred orientation piezoelectric film material and preparation method thereof |
| US20220025538A1 (en) * | 2021-07-14 | 2022-01-27 | Jomoo Kitchen & Bath Co., Ltd. | Method for metallizing plastic by pre-plating for electroplating |
| CN116219391A (en) * | 2023-05-09 | 2023-06-06 | 艾瑞森表面技术（苏州）股份有限公司 | AlN doped diamond-like coating process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108677144B (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108677144A (en) | A method of it preparing aluminium nitrogen and is co-doped with diamond-like carbon composite film | |
| US8173278B2 (en) | Coated body | |
| CN109338300B (en) | high-hardness material of high-entropy alloy nitride coating and preparation method thereof | |
| CN107130222A (en) | High-power impulse magnetron sputtering CrAlSiN nano-composite coatings and preparation method thereof | |
| JP2004501793A (en) | DLC layer system with improved sliding properties and process for producing such a layer system | |
| CN105887012B (en) | A kind of Zr-B-N nano-composite coatings preparation process | |
| CN104141109B (en) | Method for in-situ synthesis of composite TiC-DLC coating on surface of titanium | |
| CN109338319A (en) | A method of improving carbide surface titanium aluminium nitrogen coating obdurability | |
| CN114000115B (en) | Ti-B-N nano composite coating and preparation method thereof | |
| CN111155064A (en) | Method for preparing TiAlSiN composite coating by high-power pulse magnetron sputtering | |
| Liu et al. | Effects of nitrogen-argon flow ratio on the microstructural and mechanical properties of TiAlSiN/CrN multilayer coatings prepared using high power impulse magnetron sputtering | |
| CN111647851A (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
| CN111850484B (en) | Device and method for preparing tough amorphous carbon-based multiphase hybrid film | |
| CN105463391B (en) | A kind of nanocrystalline ZrB2Superhard coating and preparation method | |
| CN114703452B (en) | CoCrFeNi high-entropy alloy doped amorphous carbon film and preparation method thereof | |
| JP2011194519A (en) | Surface-coated cutting tool for turning work superior in wear resistance and method of manufacturing the same | |
| CN110468381A (en) | A kind of higher-order of oscillation pulsed magnetron sputtering method | |
| CN112501553B (en) | Mo-doped AlCrSiN/Mo self-lubricating film and preparation method thereof | |
| CN108130518A (en) | A kind of AlB with high high-temp stability2Type WB2(N) ganoine thin film and preparation method thereof | |
| JP2013248674A (en) | Surface-coated cutting tool having hard coated layer maintaining heat resistance and wear resistance | |
| JP5035979B2 (en) | Surface-coated cutting tool that exhibits high wear resistance with a hard coating layer in high-speed milling and a method for producing the same | |
| CN111500990B (en) | Zr-Ti-B-N nano composite coating and preparation method thereof | |
| CN114672779A (en) | TiB2Preparation method of/Ti composite coating | |
| CN111647859B (en) | Preparation process of Zr-Ti-B-N nano composite coating in reducing atmosphere | |
| CN108411266A (en) | A kind of method of metal surface growth metal carbides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200730 Address after: 3-713, 7th floor, building 25, No.9 yard, anningzhuang West Road, Haidian District, Beijing 100085 Patentee after: Beijing Wuke Guohua Technology Co.,Ltd. Address before: 030024 Yingze, Shanxi Province, Berlin District, West Street, No. 79, No. Patentee before: Taiyuan University of Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200228 |