CN108118305A - A kind of tough integrated fullerene carbon nitrogen multi-layer compound film and preparation method thereof - Google Patents
A kind of tough integrated fullerene carbon nitrogen multi-layer compound film and preparation method thereof Download PDFInfo
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- CN108118305A CN108118305A CN201711408160.XA CN201711408160A CN108118305A CN 108118305 A CN108118305 A CN 108118305A CN 201711408160 A CN201711408160 A CN 201711408160A CN 108118305 A CN108118305 A CN 108118305A
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- 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
- C23C14/0036—Reactive sputtering
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- 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
- C23C14/0641—Nitrides
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- 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
- C23C14/0641—Nitrides
- C23C14/0658—Carbon nitride
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- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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
Abstract
The present invention relates to a kind of tough integrated fullerene carbon nitrogen multi-layer compound films and preparation method thereof, belong to field of surface engineering technique.The membrane structure is followed successively by metallic matrix, soft or hard alternately transition zone and fullerene carbonitride layer, wherein, the soft or hard alternately transition zone repeats to replace using one layer of Ti film and one layer of TiN film as a cycle, is one layer of Ti film on metallic matrix, is one layer of TiN film under fullerene carbonitride layer.The film has high rigidity, high tenacity, high-bond, film and the good and excellent abrasion resistance properties of matrix deformability, so as to improve the service life of the abrasion resistance properties of film-substrate cohesion and matrix, extension matrix.The present invention is prepared for having soft or hard alternately transition zone using DC pulse magnetically controlled sputter method, reduces internal stress, prevents crack propagation, the method is simple and easy to control.
Description
Technical field
The present invention relates to a kind of tough integrated fullerene carbon nitrogen multi-layer compound films and preparation method thereof, belong to surface
Field of engineering technology.
Background technology
Fullerene carbon nitrogen (FL-CNx) film has high rigidity, high resiliency recovery coefficient, excellent toughness and excellent
Tribological property has wide practical use in space operation parts.However, high rigidity and the class fowler of high elastic modulus
Alkene film preparation be easy to cause the spalling failure of film on the relatively low metallic matrix of hardness and elastic modulus.It is big both at home and abroad
Quantifier elimination the result shows that, the major reason of diaphragm failure is that big residual stress, film and basal body binding force are poor, so as to cause film with
Matrix peels off.Therefore prepare film it is good with basal body binding force and have excellent toughness film be a problem to be solved.Soft or hard friendship
For the multilayer film of structure, internal layer structure makes crackle generate deflection in interface, and crack tip is wrapped up by soft formation, soft
The internal part that generates of layer is plastically deformed, energy when alleviating interfacial stress, and can be deposited by shear strain with absorbing membrane
Amount reduces residual stress, so as to improve toughness.The hardness and elastic modulus of mantle Ti films respectively may be about 3.5GPa and 140GPa,
The hardness and elastic modulus of dura mater TiN respectively reaches 27GPa and 310GPa.Can multilayer be made by modulation ratio and modulation period
The hardness and elastic modulus of film fluctuates between mantle and dura mater.How should by this characteristic of the multilayer film of soft or hard alternating structure
Use fullerene carbon nitrogen film kind, the tough one of research and preparation with high rigidity, high tenacity and good combination power
Change multilayer film to be of great significance to adapt to engine request.
The content of the invention
In view of this, it is an object of the invention to provide a kind of tough integrated fullerene carbon nitrogen multi-layer compound film and
Its preparation method, the film have high rigidity, high tenacity and good film-substrate cohesion；The method is simple and easy to control.
To achieve the above object, technical scheme is as follows：
A kind of tough integrated fullerene carbon nitrogen multi-layer compound film, the membrane structure are followed successively by metallic matrix, soft
Hard alternately transition zone and fullerene carbonitride layer, wherein, the soft or hard alternately transition zone is using one layer of Ti film and one layer of TiN film as one
A cycle repeats to replace, and is one layer of Ti film on metallic matrix, is one layer of TiN film under fullerene carbonitride layer.
Preferably, the thickness of a cycle is 20nm~50nm；Soft or hard alternately transition region thickness is in 200nm~400nm.
Preferably, the atomic percentage content of N atoms is 8%~12% in the fullerene carbonitride layer.
Preferably, the thickness of the fullerene carbonitride layer is 1000nm~2000nm.
Preferably, the metallic matrix is stainless steel, hard alloy steel or high-speed steel.
A kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film of the present invention, the method
Step is as follows：
It is passed through argon gas in step (1) plated film vacuum chamber, air pressure is 0.3Pa~1Pa, application -800V~-1200V on matrix
Pulsed bias, using anode layer ion beam source ionize argon ion to metal base surface 20~30min of etch cleaner, anode layer
Ion beam source voltage is 1000V~1200V；
Step (2) adjustment ar pressure is 0.5Pa~1.0Pa, and the Dc bias of matrix application -50V~-100V uses
Magnetron sputtering method prepares Ti layers, and Ti target currents are 1.5A~2A；
Step (3) is passed through nitrogen, nitrogen flow 10SCCM, argon flow amount 40SCCM, and air pressure is 0.5Pa~1.0Pa,
The Dc bias of matrix application -50V~-100V prepares TiN layer using reactive magnetron sputtering method, and Ti target currents are 1.5A~2A；
Step (4) is repeated in step 2 and step 3, until soft or hard alternately transition region thickness is 200nm~400nm；
Step (5) adjustment argon flow amount is 20SCCM, and nitrogen flow is 20~30SCCM, and air pressure is 0.5Pa~1.0Pa,
Cavity inner temperature is 300 DEG C~450 DEG C, and the Dc bias of matrix application -50V~-100V is prepared using reactive magnetron sputtering method
Fullerene carbonitride layer, graphite target sputtering current are 1.5A~2A；
After step (6) film layer reaches actual demand thickness, stop plated film, plated film indoor temperature is reduced to less than 80 DEG C, obtains
To a kind of tough integrated, multi-level fullerene carbon nitrogen film.
Preferably, the pulse voltage of magnetron sputtering is 500V~700V, and frequency is 20kHz~80kHz.
Preferably, the purity of Ti targets is 99.99%.
Preferably, the purity of graphite target is 99.99%.
Advantageous effect
One kind of the present invention is tough integrated fullerene carbon nitrogen multi-layer compound film is first prepare it is soft or hard alternate
(Ti/TiN/Ti/TiN ...) transition zone, then prepares fullerene carbonitride layer on transition zone, makes the two preferable film layers of class toughness
Combination of materials together, not only has remarkable result to improving film overall flexibility, but also can overcome fullerene carbon-base film
The shortcomings that combining force difference is deposited directly on matrix.The thickness control of Ti/TiN in each cycle in soft or hard alternately transition zone is existed
20nm~50nm can reduce point defect and dislocation, and the toughness of film is improved since transition zone.Nitrogen is to inducing individual layer in the present invention
Graphite, which curls into fullerene micro-structure, to play an important roll, therefore the content of N element in fullerene carbonitride layer is controlled
In 8at%~12at%.Tough integration (Ti/TiN/Ti/TiN ...)/(FL-CNx) multi-layer compound films of the present invention
With high rigidity, high tenacity, high-bond, film and the good and excellent abrasion resistance properties of matrix deformability, so as to improve film
Base junction is made a concerted effort and the abrasion resistance properties of matrix, the service life for extending matrix.
The present invention is prepared for the mistake with soft or hard alternating (Ti/TiN/Ti/TiN ...) using DC pulse magnetically controlled sputter method
Layer is crossed, internal stress is reduced, prevents crack propagation.The hardness and elastic modulus of transition zone can be adjusted according to basis material, is made
The elasticity modulus of transition zone and hardness from the hardness that fullerene film is gradually transitted to close to matrix hardness and elasticity modulus and
The characteristics of elasticity modulus, this is not available for monofilm.Be prepared have both high rigidity and high tenacity fullerene carbon nitrogen it is more
Layer laminated film；Conventional rigid film is overcome to be difficult to have both and high pass through firmly with high-ductility in integral shortcoming, the method
It adjusts nitrogen flow, depositing temperature and substrate bias and can reach the purpose for effectively controlling tough integrated film microstructure content.
The method is simple and easy to control.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film described in the present embodiment：
(1) using 9Cr18 stainless steel materials as matrix, basis material grinds and mechanically polishes through sand paper before experiment, is placed on
Ultrasonic cleaning 5min in acetone soln, then cleans 5min in alcoholic solution again, and vacuum chamber is packed into after being dried up with hair-dryer,
Vacuumizing makes vacuum degree be less than 3 × 10-3Pa。
(2) it is passed through the argon gas of 0.5Pa in plated film vacuum chamber, the pulsed bias of application -1200V on matrix, using anode layer
Ion beam source ionizes argon ion to matrix surface etch cleaner 20min, and anode layer ion beam source voltage is arranged to 1000V.
(3) 50SCCM argon gas is passed through in coating chamber, ar pressure is in 0.5Pa~1.0Pa, the direct current of matrix application -100V
Bias prepares Ti layers using magnetron sputtering technique, and the purity of Ti targets is that 99.99%, Ti target currents are 1.5A, the Ti film thickness of deposition
It spends for 10nm；
(4) nitrogen and argon gas, nitrogen flow 10SCCM, argon flow amount 40SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, the Dc bias of matrix application -100V.TiN layer, Ti target currents are prepared using reaction magnetocontrol sputtering technology
For 1.5A；The TiN film thickness of deposition is 10nm；
(5) (4) 10 cycles of step (3) and step are repeated in, prepare the soft or hard alternately transition that thickness is 200nm
Layer；
(6) argon gas and nitrogen, argon flow amount 20SCCM, nitrogen flow 30SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, cavity inner temperature is 400 DEG C, the Dc bias of matrix application -100V.It is prepared using reaction magnetocontrol sputtering
Fullerene carbon-base film, the purity of graphite target are 99.99%, and graphite target sputtering current is 1.5A, the fullerene carbon of deposition
Nitrogen film thickness is 1000nm；
(7) stop plated film, until plated film indoor temperature is reduced to less than 80 DEG C, takes out matrix, obtain a kind of tough one
Change multilayer fullerene carbon nitrogen film.
The section of the film is carried out using the scanning electron microscope of the model QUANTA-200 of FEI Co.'s production
Electron spectrometer (EDS) line scanning, analysis result show the actual (real) thickness of soft or hard alternately transition zone as 208nm, class fowler
The actual (real) thickness of olefinic carbon nitrogen layer is 1065nm.
Using the Technai F30 type Flied emission transmission electron microscopes that FEI Co. produces to the micro- knot of the film
Structure is observed, the results showed that the film is coiled structure.
The membrane structure is characterized using Jobin Yvon LabRam HR800 Raman spectrometers, described in display
Five-membered ring and heptatomic ring are formd in film, further demonstrates that and fullerene micro-structure is formd in the film.
The X-ray photoelectron spectroscopic analysis instrument produced using Thermofisher Scienticfic Comp-any companies
(XPS) N content in fullerene carbonitride layer is characterized, the results showed that N element content is 8.6at%.
Hardness using the nano-hardness tester testing film of CSM instrument companies of Switzerland is more than 20GPa, and elastic restitution coefficient is big
In 85%；Combination power using the nano impress instrument testing film of CSM instrument companies of Switzerland is more than 200mN.
Embodiment 2
A kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film described in the present embodiment：
(1) using hard alloy as basis material, basis material grinds and mechanically polishes through sand paper before experiment, is placed on acetone
Ultrasonic cleaning 5min in solution, then cleans 5min in alcoholic solution again, and vacuum chamber is packed into after being dried up with hair-dryer, takes out true
Sky makes vacuum degree be less than 3 × 10-3Pa。
(2) it is passed through the argon gas of 0.5Pa in plated film vacuum chamber, the pulsed bias of application -1200V on matrix, using anode layer
Ion beam source ionizes argon ion to matrix surface etch cleaner 25min, and anode layer ion beam source voltage is arranged to 1100V.
(3) 50SCCM argon gas is passed through in coating chamber, ar pressure is in 0.5Pa~1.0Pa, the direct current of matrix application -100V
Bias prepares Ti layer using magnetron sputtering technique, and the purity of Ti targets is that 99.99%, Ti target currents are about 1.8A, the Ti films of deposition
Thickness is 35nm；
(4) nitrogen and argon gas, nitrogen flow 10SCCM, argon flow amount 40SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, the Dc bias of matrix application -100V.TiN layer, Ti target currents are prepared using reaction magnetocontrol sputtering technology
About 1.8A；The TiN film thickness of deposition is 5nm；
(5) (4) 7 cycles of step (3) and step are repeated in, wherein, the thickness of Ti films reduce successively 5nm (by 35nm,
30nm, 25nm, 20nm, 15nm, 10nm, 5nm) variation, the thickness of TiN film successively increase 5nm (by 5nm, 10nm, 15nm,
20nm, 25nm, 30nm, 35nm) variation, prepare the soft or hard alternately transition zone that thickness is about 280nm；
(6) argon gas and nitrogen, argon flow amount 20SCCM, nitrogen flow 30SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, cavity inner temperature is 400 DEG C, the Dc bias of matrix application -100V.It is prepared using reaction magnetocontrol sputtering
Fullerene carbon-base film, the purity of graphite target are 99.99%, and graphite target sputtering current is 1.8A, the fullerene carbon of deposition
Nitrogen film thickness is 1500nm；
(7) stop plated film, until plated film indoor temperature is reduced to less than 80 DEG C, takes out matrix, obtain a kind of tough one
Change multilayer fullerene carbon nitrogen film.
The section of the film is carried out using the scanning electron microscope of the model QUANTA-200 of FEI Co.'s production
Electron spectrometer (EDS) line scanning, analysis result show the actual (real) thickness of soft or hard alternately transition zone as 271nm, class fowler
The actual (real) thickness of olefinic carbon nitrogen layer is 1561nm.
Using the Technai F30 type Flied emission transmission electron microscopes that FEI Co. produces to the micro- knot of the film
Structure is observed, the results showed that the film is coiled structure.
The membrane structure is characterized using Jobin Yvon LabRam HR800 Raman spectrometers, described in display
Five-membered ring and heptatomic ring are formd in film, further demonstrates that and fullerene micro-structure is formd in the film.
The X-ray photoelectron spectroscopic analysis instrument produced using Thermofisher Scienticfic Comp-any companies
(XPS) N content in fullerene carbonitride layer is characterized, the results showed that N element content is 10.3at%.
Hardness using the nano-hardness tester testing film of CSM instrument companies of Switzerland is more than 20GPa, and elastic restitution coefficient is big
In 85%；Combination power using the nano impress instrument testing film of CSM instrument companies of Switzerland is more than 200mN.
Embodiment 3
A kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film described in the present embodiment：
(1) using high speed steel material as matrix, basis material grinds and mechanically polishes through sand paper before experiment, and it is molten to be placed on acetone
Ultrasonic cleaning 5min in liquid, then cleans 5min in alcoholic solution again, is packed into vacuum chamber after being dried up with hair-dryer, vacuumizes
Vacuum degree is made to be less than 3 × 10-3Pa。
(2) it is passed through the argon gas of 0.5Pa in plated film vacuum chamber, the pulsed bias of application -1200V on matrix, using anode layer
Ion beam source ionizes argon ion to matrix surface etch cleaner 30min, and anode layer ion beam source voltage is arranged to 1200V.
(3) 50SCCM argon gas is passed through in coating chamber, ar pressure is in 0.5Pa~1.0Pa, the direct current of matrix application -100V
Bias prepares Ti layer using magnetron sputtering technique, and the purity of Ti targets is that 99.99%, Ti target currents are about 2A, the Ti film thickness of deposition
It spends for 20nm；
(4) nitrogen and argon gas, nitrogen flow 10SCCM, argon flow amount 40SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, the Dc bias of matrix application -100V.TiN layer, Ti target currents are prepared using reaction magnetocontrol sputtering technology
About 1.5A；The TiN film thickness of deposition is 20nm；
(5) (4) 10 cycles of step (3) and step are repeated in, prepare the soft or hard alternately transition that thickness is about 400nm
Layer；
(6) argon gas and nitrogen, argon flow amount 20SCCM, nitrogen flow 30SCCM are passed through in coating chamber, air pressure is kept
In 0.5Pa~1.0Pa, cavity inner temperature is 400 DEG C, the Dc bias of matrix application -100V.It is prepared using reaction magnetocontrol sputtering
Fullerene carbon-base film, the purity of graphite target are 99.99%, and graphite target sputtering current is 2A, the fullerene carbon nitrogen of deposition
Film thickness is 2000nm；
(7) stop plated film, until plated film indoor temperature is reduced to less than 80 DEG C, takes out matrix, obtain a kind of tough one
Change multilayer fullerene carbon nitrogen film.
The section of the film is carried out using the scanning electron microscope of the model QUANTA-200 of FEI Co.'s production
Electron spectrometer (EDS) line scanning, analysis result show the actual (real) thickness of soft or hard alternately transition zone as 406nm, class fowler
The actual (real) thickness of olefinic carbon nitrogen layer is 1987nm.
Using the Technai F30 type Flied emission transmission electron microscopes that FEI Co. produces to the micro- knot of the film
Structure is observed, the results showed that the film is coiled structure.
The membrane structure is characterized using Jobin Yvon LabRam HR800 Raman spectrometers, described in display
Five-membered ring and heptatomic ring are formd in film, further demonstrates that and fullerene micro-structure is formd in the film.
The X-ray photoelectron spectroscopic analysis instrument produced using Thermofisher Scienticfic Comp-any companies
(XPS) N content in fullerene carbonitride layer is characterized, the results showed that N element content is 11.2at%.Using Switzerland CSM
The hardness of the nano-hardness tester testing film of instrument company is more than 20GPa, and elastic restitution coefficient is more than 85%；Using Switzerland CSM
The combination power of the nano impress instrument testing film of instrument company is more than 200mN.
Invention include but not limited to above example, it is every carried out under the spirit and principles in the present invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (9)
1. a kind of tough integrated fullerene carbon nitrogen multi-layer compound film, it is characterised in that：The membrane structure is followed successively by gold
Belong to matrix, soft or hard alternately transition zone and fullerene carbonitride layer, wherein, the soft or hard alternately transition zone is with one layer of Ti film and one layer
TiN film repeats to replace for a cycle, is one layer of Ti film on metallic matrix, is one layer of TiN film under fullerene carbonitride layer.
2. a kind of tough integrated fullerene carbon nitrogen multi-layer compound film as described in claim 1, it is characterised in that：One
The thickness in cycle is 20nm~50nm；Soft or hard alternately transition region thickness is in 200nm~400nm.
3. a kind of tough integrated fullerene carbon nitrogen multi-layer compound film as described in claim 1, it is characterised in that：It is described
The atomic percentage content of N atoms is 8%~12% in fullerene carbonitride layer.
4. a kind of tough integrated fullerene carbon nitrogen multi-layer compound film as described in claim 1, it is characterised in that：It is described
The thickness of fullerene carbonitride layer is 1000nm~2000nm.
5. a kind of tough integrated fullerene carbon nitrogen multi-layer compound film as described in claim 1, it is characterised in that：It is described
Metallic matrix is stainless steel, hard alloy steel or high-speed steel.
6. a kind of system of integrated fullerene carbon nitrogen multi-layer compound film tough as claimed in any one of claims 1 to 5, wherein
Preparation Method, it is characterised in that：The method step is as follows：
It is passed through argon gas in step (1) plated film vacuum chamber, air pressure is 0.3Pa~1Pa, the arteries and veins of application -800V~-1200V on matrix
Punching bias ionizes argon ion to metal base surface 20~30min of etch cleaner, anode layer ion using anode layer ion beam source
Electron gun voltage is 1000V~1200V；
Step (2) adjusts ar pressure as 0.5Pa~1.0Pa, the Dc bias of matrix application -50V~-100V, using magnetic control
Sputtering method prepares Ti layers, and Ti target currents are 1.5A~2A；
Step (3) is passed through nitrogen, nitrogen flow 10SCCM, argon flow amount 40SCCM, and air pressure is 0.5Pa~1.0Pa, matrix
The Dc bias of application -50V~-100V prepares TiN layer using reactive magnetron sputtering method, and Ti target currents are 1.5A~2A；
Step (4) is repeated in step (2) and step (3), until soft or hard alternately transition region thickness is 200nm~400nm；
Step (5) adjustment argon flow amount be 20SCCM, nitrogen flow be 20~30SCCM, air pressure be 0.5Pa~1.0Pa, cavity
Interior temperature is 300 DEG C~450 DEG C, the Dc bias of matrix application -50V~-100V, and it is rich to prepare class using reactive magnetron sputtering method
Olefinic carbon nitrogen layer is strangled, graphite target sputtering current is 1.5A~2A；
After step (6) film layer reaches actual demand thickness, stop plated film, plated film indoor temperature is reduced to less than 80 DEG C, obtains one
Plant tough integrated, multi-level fullerene carbon nitrogen film.
7. a kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film as claimed in claim 6, special
Sign is：The pulse voltage of magnetron sputtering is 500V~700V, and frequency is 20kHz~80kHz.
8. a kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film as claimed in claim 6, special
Sign is：The purity of Ti targets is 99.99%.
9. a kind of preparation method of tough integrated fullerene carbon nitrogen multi-layer compound film as claimed in claim 6, special
Sign is：The purity of graphite target is 99.99%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711408160.XA CN108118305B (en) | 2017-12-22 | 2017-12-22 | Tough integrated fullerene-like carbon nitrogen multilayer composite film and preparation method thereof |
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| CN201711408160.XA CN108118305B (en) | 2017-12-22 | 2017-12-22 | Tough integrated fullerene-like carbon nitrogen multilayer composite film and preparation method thereof |
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| CN108754425A (en) * | 2018-06-06 | 2018-11-06 | 西安交通大学 | A kind of new waterproof erosion composite coating structure |
| CN111455315A (en) * | 2020-05-14 | 2020-07-28 | 中国科学院兰州化学物理研究所 | Preparation of fullerene/amorphous hydrocarbon composite film and application of fullerene/amorphous hydrocarbon composite film in vacuum low-temperature environment |
| CN112795882A (en) * | 2020-12-11 | 2021-05-14 | 兰州空间技术物理研究所 | High-hardness wear-resistant fullerene-like carbon film and preparation method thereof |
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| US20090304321A1 (en) * | 2005-08-01 | 2009-12-10 | Aktiebolaget Skf | Cage for a roller bearing and method of producing the same |
| CN101469402A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Preparation of fullerene-like carbon film |
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| CN111455315A (en) * | 2020-05-14 | 2020-07-28 | 中国科学院兰州化学物理研究所 | Preparation of fullerene/amorphous hydrocarbon composite film and application of fullerene/amorphous hydrocarbon composite film in vacuum low-temperature environment |
| CN112795882A (en) * | 2020-12-11 | 2021-05-14 | 兰州空间技术物理研究所 | High-hardness wear-resistant fullerene-like carbon film and preparation method thereof |
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