CN108118305B - Tough integrated fullerene-like carbon nitrogen multilayer composite film and preparation method thereof - Google Patents
Tough integrated fullerene-like carbon nitrogen multilayer composite film and preparation method thereof Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
The invention relates to a tough integrated fullerene-like carbon nitrogen multilayer composite film and a preparation method thereof, belonging to the technical field of surface engineering. The film structure sequentially comprises a metal substrate, a soft-hard alternating transition layer and a fullerene-like carbon nitrogen layer, wherein the soft-hard alternating transition layer uses a Ti film and a TiN film as a period to repeatedly alternate, the Ti film is arranged on the metal substrate, and the TiN film is arranged below the fullerene-like carbon nitrogen layer. The film has high hardness, high toughness, high bonding force, good deformability of the film and the substrate and excellent wear resistance, thereby improving the bonding force of the film substrate and the wear resistance of the substrate and prolonging the service life of the substrate. The invention adopts the direct current pulse magnetron sputtering method to prepare the soft-hard alternating transition layer, reduces the internal stress and prevents the crack from expanding, and the method is simple and easy to control.
Description
Technical Field
The invention relates to a tough integrated fullerene-like carbon nitrogen multilayer composite film and a preparation method thereof, belonging to the technical field of surface engineering.
background
The fullerene-like carbon nitrogen (FL-CNx) film has high hardness, high elastic recovery coefficient, good toughness and excellent tribological performance, and has wide application prospect in space moving parts. However, the preparation of fullerene-like films having high hardness and high elastic modulus is susceptible to exfoliation failure of the film on a metal substrate having relatively low hardness and elastic modulus. A large number of research results at home and abroad show that the important reasons for the failure of the film are large residual stress and poor binding force between the film and a substrate, so that the film and the substrate are peeled off. Therefore, the preparation of a film with good bonding force with a substrate and good toughness is a problem to be solved urgently. The multilayer film with the soft-hard alternating structure has the advantages that the internal layered structure enables the cracks to deflect at the interface, the tips of the cracks are wrapped by the soft layer, partial plastic deformation is generated in the soft layer, the interface stress is relieved, the energy generated when the film is deposited can be absorbed through shear strain, the residual stress is reduced, and therefore the toughness is improved. The hardness and elastic modulus of the soft film Ti film are respectively about 3.5GPa and 140GPa, and the hardness and elastic modulus of the hard film TiN can respectively reach 27GPa and 310 GPa. The hardness and elastic modulus of the multilayer film can be fluctuated between the soft film and the hard film by the modulation ratio and the modulation period. How to apply the characteristic of the multilayer film with the soft-hard alternating structure to the fullerene-like carbon nitride film, and the research and preparation of the tough integrated multilayer film with high hardness, high toughness and good bonding force to adapt to engineering requirements have important significance.
disclosure of Invention
in view of the above, the present invention aims to provide a tough integrated fullerene-like carbon nitrogen multilayer composite film and a preparation method thereof, wherein the film has high hardness, high toughness and good film-substrate bonding force; the method is simple and easy to control.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the film structure sequentially comprises a metal substrate, a soft and hard alternating transition layer and a fullerene-like carbon nitrogen layer, wherein the soft and hard alternating transition layer uses a Ti film and a TiN film as a period to repeatedly alternate, the Ti film is arranged on the metal substrate, and the TiN film is arranged below the fullerene-like carbon nitrogen layer.
Preferably, the thickness of one period is 20nm to 50 nm; the thickness of the soft-hard alternating transition layer is 200 nm-400 nm.
preferably, the atomic percentage of the N atoms in the fullerene-like carbon nitrogen layer is 8 to 12 percent.
Preferably, the thickness of the fullerene-like carbon nitrogen layer is 1000nm to 2000 nm.
Preferably, the metal matrix is stainless steel, hard alloy steel or high speed steel.
The invention relates to a preparation method of a tough integrated fullerene-like carbon nitrogen multilayer composite film, which comprises the following steps:
Introducing argon into a film-coating vacuum chamber in the step (1), wherein the air pressure is 0.3 Pa-1 Pa, applying a pulse bias voltage of-800V to-1200V on a substrate, and etching and cleaning the surface of the metal substrate for 20-30 min by adopting an anode layer ion beam source to ionize argon ions, wherein the anode layer ion beam source voltage is 1000V-1200V;
adjusting the argon pressure to 0.5-1.0 Pa, applying a direct current bias voltage of-50V to-100V to the substrate, and preparing a Ti layer by adopting a magnetron sputtering method, wherein the current of a Ti target is 1.5-2A;
Introducing nitrogen with the flow of 10SCCM, the flow of 40SCCM and the air pressure of 0.5-1.0 Pa, applying a direct current bias of-50V to-100V on the substrate, and preparing a TiN layer by adopting a reactive magnetron sputtering method, wherein the current of the Ti target is 1.5-2A;
Step (4) repeating the step (2) and the step (3) in sequence until the thickness of the soft-hard alternating transition layer is 200 nm-400 nm;
Adjusting the flow of argon gas to be 20SCCM, the flow of nitrogen gas to be 20-30 SCCM, the air pressure to be 0.5-1.0 Pa, the temperature in the cavity to be 300-450 ℃, applying a direct current bias voltage of-50V to-100V on the substrate, preparing a fullerene-like carbon nitrogen layer by adopting a reactive magnetron sputtering method, wherein the sputtering current of a graphite target is 1.5-2A;
And (6) stopping coating after the film layer reaches the actual required thickness, and reducing the temperature in the coating chamber to be below 80 ℃ to obtain the toughness integrated multilayer fullerene-like carbon nitrogen film.
Preferably, the pulse voltage of magnetron sputtering is 500V-700V, and the frequency is 20 kHz-80 kHz.
Preferably, the purity of the Ti target is 99.99%.
Preferably, the graphite target has a purity of 99.99%.
Advantageous effects
The invention discloses a tough integrated fullerene-like carbon nitrogen multilayer composite film, which is prepared by preparing a soft-hard alternating (Ti/TiN/Ti/TiN …) transition layer and then preparing a fullerene-like carbon nitrogen layer on the transition layer, so that two film layer materials with better toughness are combined together, thereby not only having a remarkable effect on improving the overall toughness of the film, but also overcoming the defect of poor bonding force when the fullerene-like carbon-based film is directly deposited on a substrate. The thickness of Ti/TiN in each period of the soft and hard alternating transition layer is controlled to be 20 nm-50 nm, so that point defects and dislocation can be reduced, and the toughness of the film is improved from the transition layer. The nitrogen plays an important role in inducing the single-layer graphite to curl to form a fullerene-like microstructure, so that the content of the N element in the fullerene-like carbon nitrogen layer is controlled to be 8 at% -12 at%. The toughness integrated (Ti/TiN/Ti/TiN …)/(FL-CNx) multilayer composite film has high hardness, high toughness, high binding force, good deformation capacity of the film and the matrix and excellent wear resistance, so that the binding force of the film and the matrix is improved, and the service life of the matrix is prolonged.
the invention adopts a direct current pulse magnetron sputtering method to prepare a transition layer with alternating hardness and softness (Ti/TiN/Ti/TiN …), reduces the internal stress and prevents the crack from expanding. The hardness and elastic modulus of the transition layer can be adjusted according to the base material, so that the elastic modulus and hardness of the transition layer are gradually transited to the hardness and elastic modulus of the fullerene-like thin film from the hardness and elastic modulus which are close to the base material, which is a characteristic that a single-layer film does not have. Preparing a fullerene-like carbon nitrogen multilayer composite film with high hardness and high toughness; the method overcomes the defect that the traditional hard film is difficult to integrate high hardness and high toughness, and can achieve the purpose of effectively controlling the microstructure content of the toughness integrated film by adjusting the nitrogen flow, the deposition temperature and the substrate bias voltage. The method is simple and easy to control.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
the preparation method of the tough integrated fullerene-like carbon nitrogen multilayer composite film in the embodiment comprises the following steps:
(1) The method comprises the steps of taking a 9Cr18 stainless steel material as a substrate, grinding and mechanically polishing the substrate material before experiment, placing the substrate material in an acetone solution for ultrasonic cleaning for 5min, then cleaning in an alcohol solution for 5min, drying by a blower, putting the substrate material into a vacuum chamber, and vacuumizing to ensure that the vacuum degree is lower than 3 x 10 -3 Pa.
(2) Introducing argon gas of 0.5Pa into the vacuum chamber, applying-1200V pulse bias voltage on the substrate, etching and cleaning the substrate surface for 20min by using anode layer ion beam source to ionize argon ions, and setting the anode layer ion beam source voltage to be 1000V.
(3) Introducing 50SCCM argon into the coating chamber, wherein the pressure of the argon is 0.5-1.0 Pa, applying-100V direct current bias on the substrate, and preparing a Ti layer by adopting a magnetron sputtering technology, wherein the purity of a Ti target is 99.99%, the current of the Ti target is 1.5A, and the thickness of the deposited Ti film is 10 nm;
(4) Introducing nitrogen and argon into the coating chamber, wherein the flow of the nitrogen is 10SCCM, the flow of the argon is 40SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, and the substrate is applied with a direct current bias of-100V. Preparing a TiN layer by adopting a reactive magnetron sputtering technology, wherein the current of a Ti target is 1.5A; the thickness of the deposited TiN film is 10 nm;
(5) Sequentially repeating the step (3) and the step (4) for 10 periods to prepare a soft-hard alternating transition layer with the thickness of 200 nm;
(6) Introducing argon and nitrogen into the coating chamber, wherein the flow of the argon is 20SCCM, the flow of the nitrogen is 30SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, the temperature in the cavity is 400 ℃, and the substrate applies a direct current bias of 100V below zero. Preparing a fullerene-like carbon-based film by adopting reactive magnetron sputtering, wherein the purity of a graphite target is 99.99 percent, the sputtering current of the graphite target is 1.5A, and the thickness of the deposited fullerene-like carbon nitride film is 1000 nm;
(7) stopping coating until the temperature in the coating chamber is reduced to be below 80 ℃, and taking out the substrate to obtain the tough integrated multilayer fullerene-like carbon nitrogen film.
An electron energy spectrometer (EDS) line scanning analysis is carried out on the section of the film by adopting a scanning electron microscope with the model number QUANTA-200 produced by FEI company, and the analysis result shows that the actual thickness of the soft and hard alternating transition layer is 208nm, and the actual thickness of the fullerene-like carbon nitrogen layer is 1065 nm.
the microstructure of the film was observed using a field emission transmission electron microscope model Technai F30, manufactured by FEI corporation, and the film was found to have a coiled structure.
the structure of the film is characterized by a Jobin Yvon LabRam HR800 Raman spectrometer, and the five-membered ring and the seven-membered ring are formed in the film, so that the fullerene-like microstructure is further formed in the film.
The N content in the fullerene-like carbon nitrogen layer was characterized by an X-ray photoelectron spectroscopy analyzer (XPS) manufactured by Thermofisher scientific company-any, and the result showed that the N element content was 8.6 at%.
The hardness of the film is tested by adopting a nano indenter of Swiss CSM instrument company to be more than 20GPa, and the elastic recovery coefficient is more than 85 percent; the film was tested to have a binding force of greater than 200mN using a nano scratch tester from swiss CSM instruments.
Example 2
The preparation method of the tough integrated fullerene-like carbon nitrogen multilayer composite film in the embodiment comprises the following steps:
(1) taking hard alloy as a base material, grinding and mechanically polishing the base material by using sand paper before an experiment, placing the base material in an acetone solution for ultrasonic cleaning for 5min, then cleaning the base material in an alcohol solution for 5min, drying the base material by using a blower, putting the base material into a vacuum chamber, and vacuumizing to ensure that the vacuum degree is lower than 3 multiplied by 10 -3 Pa.
(2) Introducing argon gas of 0.5Pa into the vacuum chamber, applying-1200V pulse bias voltage on the substrate, etching and cleaning the substrate surface for 25min by using anode layer ion beam source to ionize argon ions, and setting the anode layer ion beam source voltage to be 1100V.
(3) Introducing 50SCCM argon into the coating chamber, wherein the pressure of the argon is 0.5 Pa-1.0 Pa, applying-100V direct current bias on the substrate, preparing a Ti layer by adopting a magnetron sputtering technology, wherein the purity of a Ti target is 99.99%, the current of the Ti target is about 1.8A, and the thickness of the deposited Ti film is 35 nm;
(4) Introducing nitrogen and argon into the coating chamber, wherein the flow of the nitrogen is 10SCCM, the flow of the argon is 40SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, and the substrate is applied with a direct current bias of-100V. Preparing a TiN layer by adopting a reactive magnetron sputtering technology, wherein the current of a Ti target is about 1.8A; the thickness of the deposited TiN film is 5 nm;
(5) Repeating the step (3) and the step (4) for 7 periods in sequence, wherein the thickness of the Ti film is reduced by 5nm (according to 35nm, 30nm, 25nm, 20nm, 15nm, 10nm and 5nm) in sequence, the thickness of the TiN film is increased by 5nm (according to 5nm, 10nm, 15nm, 20nm, 25nm, 30nm and 35nm) in sequence, and a soft-hard alternating transition layer with the thickness of about 280nm is prepared;
(6) Introducing argon and nitrogen into the coating chamber, wherein the flow of the argon is 20SCCM, the flow of the nitrogen is 30SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, the temperature in the cavity is 400 ℃, and the substrate applies a direct current bias of 100V below zero. Preparing a fullerene-like carbon-based film by adopting reactive magnetron sputtering, wherein the purity of a graphite target is 99.99 percent, the sputtering current of the graphite target is 1.8A, and the thickness of the deposited fullerene-like carbon nitride film is 1500 nm;
(7) Stopping coating until the temperature in the coating chamber is reduced to be below 80 ℃, and taking out the substrate to obtain the tough integrated multilayer fullerene-like carbon nitrogen film.
An electron energy spectrometer (EDS) line scanning analysis is carried out on the section of the film by adopting a scanning electron microscope with the model number QUANTA-200 produced by FEI company, and the analysis result shows that the actual thickness of the soft and hard alternating transition layer is 271nm, and the actual thickness of the fullerene-like carbon nitrogen layer is 1561 nm.
the microstructure of the film was observed using a field emission transmission electron microscope model Technai F30, manufactured by FEI corporation, and the film was found to have a coiled structure.
the structure of the film is characterized by a Jobin Yvon LabRam HR800 Raman spectrometer, and the five-membered ring and the seven-membered ring are formed in the film, so that the fullerene-like microstructure is further formed in the film.
the N content in the fullerene-like carbon nitrogen layer was characterized by an X-ray photoelectron spectroscopy analyzer (XPS) manufactured by Thermofisher scientific company-any, and the result showed that the N element content was 10.3 at%.
The hardness of the film is tested by adopting a nano indenter of Swiss CSM instrument company to be more than 20GPa, and the elastic recovery coefficient is more than 85 percent; the film was tested to have a binding force of greater than 200mN using a nano scratch tester from swiss CSM instruments.
Example 3
The preparation method of the tough integrated fullerene-like carbon nitrogen multilayer composite film in the embodiment comprises the following steps:
(1) Taking a high-speed steel material as a substrate, grinding and mechanically polishing the substrate material by using sand paper before an experiment, placing the substrate material in an acetone solution for ultrasonic cleaning for 5min, then cleaning the substrate material in an alcohol solution for 5min, drying the substrate material by using a blower, putting the substrate material into a vacuum chamber, and vacuumizing the vacuum chamber until the vacuum degree is lower than 3 x 10 -3 Pa.
(2) Introducing argon gas of 0.5Pa into the vacuum chamber, applying-1200V pulse bias voltage on the substrate, etching and cleaning the substrate surface for 30min by using anode layer ion beam source to ionize argon ions, and setting the anode layer ion beam source voltage to 1200V.
(3) Introducing 50SCCM argon into the coating chamber, wherein the pressure of the argon is 0.5-1.0 Pa, applying-100V direct current bias on the substrate, preparing a Ti layer by adopting a magnetron sputtering technology, wherein the purity of a Ti target is 99.99%, the current of the Ti target is about 2A, and the thickness of the deposited Ti film is 20 nm;
(4) Introducing nitrogen and argon into the coating chamber, wherein the flow of the nitrogen is 10SCCM, the flow of the argon is 40SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, and the substrate is applied with a direct current bias of-100V. Preparing a TiN layer by adopting a reactive magnetron sputtering technology, wherein the current of a Ti target is about 1.5A; the thickness of the deposited TiN film is 20 nm;
(5) Sequentially repeating the step (3) and the step (4) for 10 periods to prepare a soft-hard alternating transition layer with the thickness of about 400 nm;
(6) Introducing argon and nitrogen into the coating chamber, wherein the flow of the argon is 20SCCM, the flow of the nitrogen is 30SCCM, the air pressure is kept between 0.5Pa and 1.0Pa, the temperature in the cavity is 400 ℃, and the substrate applies a direct current bias of 100V below zero. Preparing a fullerene-like carbon-based film by adopting reactive magnetron sputtering, wherein the purity of a graphite target is 99.99 percent, the sputtering current of the graphite target is 2A, and the thickness of the deposited fullerene-like carbon nitride film is 2000 nm;
(7) Stopping coating until the temperature in the coating chamber is reduced to be below 80 ℃, and taking out the substrate to obtain the tough integrated multilayer fullerene-like carbon nitrogen film.
An electron energy spectrometer (EDS) line scanning analysis was performed on the cross section of the thin film using a scanning electron microscope model QUANTA-200 manufactured by FEI corporation, and the analysis result showed that the actual thickness of the soft-hard alternating transition layer was 406nm and the actual thickness of the fullerene-like carbon nitrogen layer was 1987 nm.
the microstructure of the film was observed using a field emission transmission electron microscope model Technai F30, manufactured by FEI corporation, and the film was found to have a coiled structure.
The structure of the film is characterized by a Jobin Yvon LabRam HR800 Raman spectrometer, and the five-membered ring and the seven-membered ring are formed in the film, so that the fullerene-like microstructure is further formed in the film.
the N content in the fullerene-like carbon nitrogen layer was characterized by an X-ray photoelectron spectroscopy analyzer (XPS) manufactured by Thermofisher scientific company-any, and the result showed that the N element content was 11.2 at%. The hardness of the film is tested by adopting a nano indenter of Swiss CSM instrument company to be more than 20GPa, and the elastic recovery coefficient is more than 85 percent; the film was tested to have a binding force of greater than 200mN using a nano scratch tester from swiss CSM instruments.
The invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the spirit and principle of the invention are deemed to be within the scope of the invention.
Claims (7)
1. A preparation method of a tough integrated fullerene-like carbon nitrogen multilayer composite film is characterized by comprising the following steps: the film structure sequentially comprises a metal substrate, a soft-hard alternating transition layer and a fullerene-like carbon nitrogen layer, wherein the soft-hard alternating transition layer repeatedly alternates in a period of a Ti film and a TiN film, the Ti film is arranged on the metal substrate, the TiN film is arranged below the fullerene-like carbon nitrogen layer, and the thickness of the period is 20 nm-50 nm; the thickness of the soft and hard alternating transition layer is 200 nm-400 nm; the method comprises the following steps:
Introducing argon into a film-coating vacuum chamber in the step (1), wherein the air pressure is 0.3 Pa-1 Pa, applying a pulse bias voltage of-800V to-1200V on a substrate, and etching and cleaning the surface of the metal substrate for 20-30 min by adopting an anode layer ion beam source to ionize argon ions, wherein the anode layer ion beam source voltage is 1000V-1200V;
adjusting the argon pressure to 0.5-1.0 Pa, applying a direct current bias voltage of-50V to-100V to the substrate, and preparing a Ti layer by adopting a magnetron sputtering method, wherein the current of a Ti target is 1.5-2A;
Introducing nitrogen with the flow of 10SCCM, the flow of 40SCCM and the air pressure of 0.5-1.0 Pa, applying a direct current bias of-50V to-100V on the substrate, and preparing a TiN layer by adopting a reactive magnetron sputtering method, wherein the current of the Ti target is 1.5-2A;
Step (4) repeating the step (2) and the step (3) in sequence until the thickness of the soft-hard alternating transition layer is 200 nm-400 nm;
Adjusting the flow of argon gas to be 20SCCM, the flow of nitrogen gas to be 20-30 SCCM, the air pressure to be 0.5-1.0 Pa, the temperature in the cavity to be 300-450 ℃, applying a direct current bias voltage of-50V to-100V on the substrate, preparing a fullerene-like carbon nitrogen layer by adopting a reactive magnetron sputtering method, wherein the sputtering current of a graphite target is 1.5-2A;
and (6) stopping coating after the film layer reaches the actual required thickness, and reducing the temperature in the coating chamber to be below 80 ℃ to obtain the toughness integrated multilayer fullerene-like carbon nitrogen film.
2. The method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the atomic percentage of N atoms in the fullerene-like carbon nitrogen layer is 8-12%.
3. The method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the thickness of the fullerene-like carbon nitrogen layer is 1000 nm-2000 nm.
4. The method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the metal matrix is stainless steel, hard alloy steel or high-speed steel.
5. the method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the pulse voltage of the magnetron sputtering is 500V-700V, and the frequency is 20 kHz-80 kHz.
6. the method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the purity of the Ti target was 99.99%.
7. the method for preparing the tough integrated fullerene-like carbon nitrogen multilayer composite film as claimed in claim 1, wherein the method comprises the following steps: the purity of the graphite target was 99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| CN111455315B (en) * | 2020-05-14 | 2021-12-31 | 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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| CN101469402B (en) * | 2007-12-25 | 2010-11-24 | 中国科学院兰州化学物理研究所 | Preparation of fullerene-like carbon film |
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