CN114990476B - Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a nitrogen-doped tetrahedral amorphous carbon film, and a preparation method and application thereof. The preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps: 1) In a protective atmosphere, depositing a Ti transition layer on the surface of the monocrystalline silicon substrate by utilizing a Ti target through a magnetron sputtering technology; 2) Under the vacuumizing condition, depositing a diamond-like carbon transition layer on the Ti transition layer by utilizing a graphite target through a magnetic filtration cathodic arc technology and controlling the negative bias voltage to be-1300V to-1100V; 3) And in nitrogen atmosphere, depositing a ta-C layer on the diamond-like transition layer by utilizing a graphite target and controlling negative bias voltage to be-400V to-120V through a magnetic filtration cathodic arc technology, thus obtaining the nitrogen doped tetrahedral amorphous carbon film. The nitrogen-doped tetrahedral amorphous carbon film has low resistivity and high hardness, is large in thickness, can be applied to bipolar plates of fuel cells, and is suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of conductive films, in particular to a nitrogen-doped tetrahedral amorphous carbon film, and a preparation method and application thereof.
Background
The tetrahedral amorphous carbon film (ta-C film) is composed of sp of diamond structure 3 Sp of carbon and graphite structure 2 An amorphous carbon film formed by mixing carbon. Sp in ta-C film 3 High carbon content and high sp 3 The carbon content is such that it has mechanical properties and physical properties (such as high hardness, high wear resistance, high thermal conductivity, high corrosion resistance, etc.) close to those of diamond, but high sp 3 The carbon content and highly distorted structure also lead to high resistivity of the ta-C film, which greatly limits its application in the field of conductive films.
After being doped with the ta-C film, the nitrogen can form a C=N bond and a C-N bond with carbon, so that the internal defects of the ta-C film can be reduced, the resistance of the ta-C film can be effectively reduced, and the prepared nitrogen-doped ta-C film can be applied to fuel cells. The bipolar plate of the fuel cell requires that the material has excellent conductivity and also has good heat conduction performance, mechanical performance and corrosion resistance, and the corrosion resistance of the metal bipolar plate can be effectively improved by depositing a nitrogen-doped ta-C film on the surface of the metal bipolar plate, so that an oxide layer is prevented from being formed on the surface of the metal bipolar plate. However, the existing method for realizing nitrogen doping on the ta-C film can reduce the resistivity of the ta-C film, but can also lead to the reduction of the hardness of the ta-C film, influence the mechanical properties of the ta-C film, and hardly completely meet the actual application requirements.
Therefore, developing a nitrogen doped ta-C film with both low resistivity and high hardness is of great importance.
Disclosure of Invention
The invention aims to provide a nitrogen-doped tetrahedral amorphous carbon film, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) In a protective atmosphere, depositing a Ti transition layer on the surface of the monocrystalline silicon substrate by utilizing a Ti target through a magnetron sputtering technology;
2) Under the vacuumizing condition, depositing a diamond-like carbon transition layer on the Ti transition layer by utilizing a graphite target through a magnetic filtration cathodic arc technology and controlling the negative bias voltage to be-1300V to-1100V;
3) And in nitrogen atmosphere, depositing a ta-C layer on the diamond-like transition layer by utilizing a graphite target and controlling negative bias voltage to be-400V to-120V through a magnetic filtration cathodic arc technology, thus obtaining the nitrogen doped tetrahedral amorphous carbon film.
Preferably, the protective atmosphere in the step 1) is an argon atmosphere, and the flow rate of the argon is 200 sccm-300 sccm.
Preferably, the operation parameters of the magnetron sputtering in the step 1) are as follows: the power supply is a direct current power supply with the power of 2kW to 4kW, the temperature of the Ti target is 140 ℃ to 160 ℃, and the deposition time is 400s to 600s.
Preferably, the vacuumizing in the step 2) is vacuumizing to a pressure of less than 5×10 -3 Pa。
Preferably, the operating parameters of the magnetically filtered cathodic arc of step 2) are: the target current is 40A-60A, and the deposition time is 1800 s-2200 s.
Preferably, the flow rate of the nitrogen gas in the step 3) is 1sccm to 50sccm.
Preferably, the operating parameters of the magnetically filtered cathodic arc of step 3) are: the target current is 40A-60A, and the deposition time is 7500 s-8500 s.
A nitrogen-doped tetrahedral amorphous carbon film is prepared by the preparation method.
A bipolar plate is provided, wherein the surface of the bipolar plate is deposited with the nitrogen-doped tetrahedral amorphous carbon film.
A fuel cell comprising the bipolar plate.
The beneficial effects of the invention are as follows: the nitrogen-doped tetrahedral amorphous carbon film has low resistivity and high hardness, is large in thickness, can be applied to bipolar plates of fuel cells, and is suitable for large-scale popularization and application.
Specifically:
1) The nitrogen-doped tetrahedral amorphous carbon film has low resistivity of only 3.3 multiplied by 10 -4 Ω·cm～4.0×10 -4 Omega cm, conductivity is better than that of the traditional graphite material (8 multiplied by 10 -4 Ω·cm～13×10 -4 Ω·cm)；
2) The nitrogen-doped tetrahedral amorphous carbon film has high hardness, and the hardness of the nitrogen-doped tetrahedral amorphous carbon film is kept at 42.1GPa even when the concentration of N reaches 3.4 at%;
3) The thickness of the nitrogen-doped tetrahedral amorphous carbon film is large and is in the range of 1.15-1.50 mu m.
Drawings
Fig. 1 is an XPS spectrum of a nitrogen-doped tetrahedral amorphous carbon film of example 1.
Fig. 2 is an XPS spectrum of the tetrahedral amorphous carbon film of comparative example 1.
Fig. 3 is a plot of C-C, c=c, C-N, and c=n bond duty cycle as a function of nitrogen doping concentration.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
the preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) Placing silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, closing a furnace door, and vacuumizing to 5×10 -3 Pa, introducing argon gas (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating silicon single crystal wafer with hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon content);
3) Introducing nitrogen gas with flow rate of 4sccm, adjusting negative bias of matrix to-120V, depositing 8000s, and depositing ta-C layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Example 2:
the preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) Placing silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, closing a furnace door, and vacuumizing to 5×10 -3 Pa，Then argon with the flow rate of 250sccm (purity 99.999%) is introduced under the bias of-200V, and Ar is carried out on the silicon single crystal wafer by using a hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon content);
3) Introducing nitrogen gas with flow rate of 10sccm, adjusting negative bias of matrix to-120V, depositing 8000s, and depositing ta-C layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Example 3:
the preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) Placing silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, closing a furnace door, and vacuumizing to 5×10 -3 Pa, introducing argon gas (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating silicon single crystal wafer with hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon contentAn amount of;
3) Introducing nitrogen gas with flow rate of 20sccm, adjusting negative bias of matrix to-120V, depositing 8000s, and depositing ta-C layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Example 4:
the preparation method of the nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) Placing silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, closing a furnace door, and vacuumizing to 5×10 -3 Pa, introducing argon gas (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating silicon single crystal wafer with hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon content);
3) Introducing nitrogen gas with flow rate of 50sccm, adjusting negative bias of matrix to-120V, depositing 8000s, and depositing ta-C layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Comparative example 1:
the preparation method of the tetrahedral amorphous carbon film comprises the following steps:
1) Placing the silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, and closingClosing the furnace door, and vacuumizing to 5×10 -3 Pa, introducing argon gas (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating silicon single crystal wafer with hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon content);
3) The substrate was negatively biased to-120V, 8000s was deposited, and a ta-C layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the tetrahedral amorphous carbon film.
Comparative example 2:
the preparation method of the tetrahedral amorphous carbon film comprises the following steps:
1) Placing silicon single crystal wafer (100) into an ultrasonic cleaner filled with ethanol and deionized water for cleaning for 10min, drying in an oven, wiping with ethanol, placing into a sample chamber, closing a furnace door, and vacuumizing to 5×10 -3 Pa, introducing argon gas (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating silicon single crystal wafer with hot filament ion source + Etching for 90min, using argon as working gas, using a direct current power supply with the power of 3kW as a magnetron sputtering power supply, heating a Ti target (purity is 99.99%) to 150 ℃, depositing for 500s, and closing a power supply and an argon valve to form a Ti transition layer on the surface of the silicon single crystal wafer;
2) The vacuum pump is turned on to vacuum to 5X 10 -3 Under Pa, starting graphite target to deposit diamond-like transition layer, wherein the negative bias voltage of matrix is-1200V, the target current is 50A, and depositing for 2000s, namely depositing diamond-like transition layer (low sp 3 Carbon content)；
3) The substrate was negatively biased to-400V, 8000s was deposited, and a ta-C layer was deposited on the diamond-like transition layer (high sp 3 Carbon content), closing the vacuum pump, introducing the atmosphere, opening the sample chamber, and taking out the sample to obtain the tetrahedral amorphous carbon film.
Performance test:
1) An X-ray photoelectron spectroscopy (XPS) chart of the nitrogen-doped tetrahedral amorphous carbon film of example 1 is shown in fig. 1 (solid line is a fitted curve, and broken line is an original data curve).
As can be seen from fig. 1: the coincidence degree of the fitting curve and the original data curve is good, which indicates that the fitting result is reliable; using a Gaussian-Lorentzian fit of 30% Lorentzian, the binding energy is as follows: C-C (285.1 eV.+ -. 0.1 eV), C=C (284.4 eV.+ -. 0.1 eV), C=N (285.9 eV.+ -. 0.1 eV), C-N (287.2 eV.+ -. 0.2 eV).
2) The XPS spectrum of the tetrahedral amorphous carbon film of comparative example 1 is shown in fig. 2 (solid line is a fitted curve, and broken line is an original data curve).
As can be seen from fig. 2: a small amount of C-O bonds and c=o bonds occur, which results from a small amount of air remaining in the chamber or a small amount of oxygen adsorbed on the surface placed in the atmospheric environment.
3) The ratio of C-C bonds, c=c bonds, C-N bonds, and c=n bonds as a function of nitrogen doping concentration (obtained from the nitrogen doped tetrahedral amorphous carbon films of examples 1 to 4 and the tetrahedral amorphous carbon film of comparative example 1) is shown in fig. 3.
As can be seen from fig. 3: sp as the nitrogen doping concentration increases 3 The carbon content gradually decreased, the C-N bond and the c=n bond content gradually increased, and the c=n bond content increased faster than the C-N bond, indicating that the c=n bond was mainly formed after nitrogen incorporation.
4) The nitrogen-doped tetrahedral amorphous carbon films of examples 1 to 4 and the tetrahedral amorphous carbon films of comparative examples 1 to 2 were subjected to performance tests, the test results are shown in the following table:
TABLE 1 Performance test results of Nitrogen-doped ta-C films of examples 1 to 4 and ta-C films of comparative examples 1 to 2
Note that:
nitrogen doping concentration: testing by Electronic Probe (EPMA);
sp 3 carbon content: the test is carried out by X-ray photoelectron spectroscopy, the target material is an Al target, the energy is 1486.6eV, ar is used before each test + Etching for 3min to remove atoms or molecules adsorbed on the surface;
thickness: observing the section through a scanning electron microscope to obtain the thickness of the film;
hardness: the hardness of the film is tested by a nano indentation experiment, the load is 5mN, the indentation depth is about 100nm, six points are punched on each sample, and the arithmetic average value is taken;
resistivity: the sheet resistance of the film is obtained through four-probe test, and the resistivity of the film is calculated through the following formula: ρ=r S Wherein ρ represents resistivity in Ω·cm, R s The square resistance is expressed in omega/≡omega is film thickness in cm, three points are measured for each sample, and the arithmetic average is taken as the result.
As can be seen from table 1:
a) The resistivity of the ta-C film after incorporating 1.8at% of nitrogen is from more than 1.7X10 2 The omega cm is rapidly reduced to 3.3X10 -4 Omega cm (graphite resistivity of 8X 10) -4 Ω·cm～13×10 -4 Ω cm), then the resistivity remains substantially stable with increasing nitrogen doping concentration, but sp 3 The carbon content is gradually reduced, and the film hardness and thickness are also gradually reduced;
b) The nitrogen-doped ta-C film of comparative example 1 and the ta-C films of comparative examples 1-2 have the highest sp under 120V negative bias 3 Carbon content and hardness at 120V negative bias, the resistivity of the nitrogen-doped ta-C film of example 1 was 3.3X10 -4 Omega cm, achieving good conductor levels while hardness is only 1.6GPa lower than the ta-C film of comparative example 1 under the same bias;
c) The nitrogen-doped ta-C films of comparative examples 1 to 4 maintained the resistivity of the ta-C film after the nitrogen doping concentration was increased to be the same as that of the nitrogen-doped ta-C film of example 1At the same level, but its sp 3 The carbon content, hardness and thickness continue to decrease.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the nitrogen-doped tetrahedral amorphous carbon film is characterized by comprising the following steps of:
1) In a protective atmosphere, depositing a Ti transition layer on the surface of the monocrystalline silicon substrate by utilizing a Ti target through a magnetron sputtering technology;
2) Under the vacuumizing condition, depositing a diamond-like carbon transition layer on the Ti transition layer by utilizing a graphite target through a magnetic filtration cathodic arc technology and controlling the negative bias voltage to be-1300V to-1100V;
3) In nitrogen atmosphere, depositing a ta-C layer on the diamond-like transition layer by utilizing a graphite target and controlling negative bias voltage to be-400V to-120V through a magnetic filtration cathodic arc technology, so as to obtain the nitrogen-doped tetrahedral amorphous carbon film;
the operation parameters of the magnetron sputtering in the step 1) are as follows: the power supply is a direct current power supply with the power of 2kW to 4kW, the temperature of the Ti target is 140 ℃ to 160 ℃, and the deposition time is 400s to 600s;
the operation parameters of the magnetic filter cathode arc in the step 2) are as follows: the target current is 40A-60A, and the deposition time is 1800 s-2200 s;
the flow rate of the nitrogen is 1 sccm-50 sccm in the step 3);
the operating parameters of the magnetically filtered cathodic arc of step 3) are: the target current is 40A-60A, and the deposition time is 7500 s-8500 s.
2. The method for preparing the nitrogen-doped tetrahedral amorphous carbon film according to claim 1, wherein: the protective atmosphere in the step 1) is argon atmosphere, and the flow rate of the argon is 200 sccm-300 sccm.
3. The method for preparing the nitrogen-doped tetrahedral amorphous carbon film according to claim 1, wherein: the step 2) of vacuumizing is vacuumizing until the pressure is less than 5 multiplied by 10 -3 Pa。
4. A nitrogen-doped tetrahedral amorphous carbon film, characterized by being produced by the production method according to any one of claims 1 to 3.
5. A bipolar plate having a surface deposited with the nitrogen-doped tetrahedral amorphous carbon film of claim 4.
6. A fuel cell comprising the bipolar plate of claim 5.
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| CN113991134B (en) * | 2021-10-22 | 2023-09-26 | 北京格睿能源科技有限公司 | Amorphous carbon coating for fuel cell metal bipolar plate and preparation method thereof |
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