CN114990476A - Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof - Google Patents
Nitrogen-doped tetrahedral amorphous carbon film and preparation method and application thereof Download PDFInfo
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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) depositing a diamond-like transition layer on the Ti transition layer by using a graphite target and controlling the negative bias to be-1300V to-1100V through a magnetic filtration cathode arc technology under the condition of vacuum pumping; 3) in nitrogen atmosphere, a ta-C layer is deposited on the diamond-like transition layer by utilizing a graphite target and controlling the negative bias to be-400V to-120V through a magnetic filtration cathode arc technology, and the nitrogen-doped tetrahedral amorphous carbon film is obtained. The nitrogen-doped tetrahedral amorphous carbon film disclosed by the invention has low resistivity, high hardness and large thickness, can be applied to a bipolar plate of a fuel cell, 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 formed of diamond-structured sp 3 Sp of carbon and graphite structures 2 An amorphous carbon film formed by mixing carbon. Sp in ta-C film 3 High content of carbon, high sp 3 The carbon content makes the mechanical property and physical property (such as high hardness, high wear resistance, high thermal conductivity, high corrosion resistance and the like) of the diamond approach, but the sp is high 3 The carbon content and the highly distorted structure also result in high resistivity of the ta-C film, which greatly limits its application in the field of conductive films.
After nitrogen is doped into the ta-C film, C-N bonds and C-N bonds are formed with carbon, so that 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 the material to have excellent electrical conductivity, and simultaneously has good heat conducting property, mechanical property and corrosion resistance, and the corrosion resistance of the metal bipolar plate can be effectively improved and an oxide layer is prevented from being formed on the surface of the metal bipolar plate by depositing the nitrogen-doped ta-C film on the surface of the metal bipolar plate. However, although the resistivity of the ta-C thin film can be reduced by the conventional method for doping nitrogen into the ta-C thin film, the hardness of the ta-C thin film is reduced, the mechanical property of the ta-C thin film is influenced, and the ta-C thin film is difficult to completely meet the actual application requirements.
Therefore, it is very important to develop a nitrogen-doped ta-C thin film with low resistivity and high hardness.
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:
a preparation method of a 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) depositing a diamond-like transition layer on the Ti transition layer by using a graphite target and controlling the negative bias to be-1300V to-1100V through a magnetic filtration cathode arc technology under the condition of vacuum pumping;
3) in nitrogen atmosphere, a ta-C layer is deposited on the diamond-like transition layer by utilizing a graphite target and controlling the negative bias to be-400V to-120V through a magnetic filtration cathode arc technology, and the nitrogen-doped tetrahedral amorphous carbon film is obtained.
Preferably, the protective atmosphere in the step 1) is argon atmosphere, and the flow rate of argon is 200sccm to 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 600 s.
Preferably, the step 2) of vacuumizing is to vacuumize to a pressure of less than 5 × 10 -3 Pa。
Preferably, the operating parameters of the magnetic filtration cathodic arc in the step 2) are as follows: the target current is 40-60A, and the deposition time is 1800-2200 s.
Preferably, the flow rate of the nitrogen in the step 3) is 1sccm to 50 sccm.
Preferably, the operating parameters of the magnetic filtration cathodic arc in the step 3) are as follows: the target current is 40-60A, and the deposition time is 7500-8500 s.
A nitrogen-doped tetrahedral amorphous carbon film is prepared by the preparation method.
A bipolar plate having the above nitrogen-doped tetrahedral amorphous carbon film deposited on the surface thereof.
A fuel cell comprises the bipolar plate.
The invention has the beneficial effects that: the nitrogen-doped tetrahedral amorphous carbon film disclosed by the invention has low resistivity, high hardness and large thickness, can be applied to a bipolar plate of a fuel cell, and is suitable for large-scale popularization and application.
Specifically, the method comprises the following steps:
1) resistivity of nitrogen-doped tetrahedral amorphous carbon film of the inventionLow, only 3.3 × 10 -4 Ω·cm～4.0×10 -4 Omega cm, conductivity is superior to 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 even if the N concentration reaches 3.4 at%, the hardness is still maintained at 42.1 GPa;
3) the thickness of the nitrogen-doped tetrahedral amorphous carbon film is large and is in the range of 1.15-1.50 microns.
Drawings
FIG. 1 is an XPS spectrum of a nitrogen-doped tetrahedral amorphous carbon thin film of example 1.
Fig. 2 is an XPS spectrum of the tetrahedral amorphous carbon thin film of comparative example 1.
Fig. 3 is a graph showing the ratio of C-C bonds, C ═ C bonds, C-N bonds, and C ═ N bonds as a function of nitrogen doping concentration.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with alcohol, placing in sample chamber, closing furnace door, and vacuumizing to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting a graphite target to deposit the diamond-like transition layer, setting the negative bias of a substrate to-1200V and the target current to 50A, and depositing 2000s, namely depositing the diamond-like transition layer (low sp) on the Ti transition layer 3 Carbon content);
3) introducing nitrogen gas with flow rate of 4sccm, adjusting substrate negative bias to-120V, depositing 8000s, and depositing ta-C layer (high sp) on the diamond-like carbon transition layer 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:
a preparation method of a nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with ethanol, placing in sample chamber, closing furnace door, and vacuumizing to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting a graphite target to deposit the diamond-like transition layer, setting the negative bias of a substrate to-1200V and the target current to 50A, and depositing 2000s, namely depositing the diamond-like transition layer (low sp) on the Ti transition layer 3 Carbon content);
3) introducing nitrogen gas with flow rate of 10sccm, adjusting the substrate negative bias to-120V, depositing 8000s, and depositing a ta-C layer (high sp) on the diamond-like transition layer 3 Carbon content), closing the vacuum pump, introducing air, opening the sample chamber and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Example 3:
a preparation method of a nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with ethanol, and placing in sampleIn the product chamber, the furnace door is closed and vacuum is pumped to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting a graphite target to deposit the diamond-like transition layer, setting the negative bias of a substrate to-1200V and the target current to 50A, and depositing 2000s, namely depositing the diamond-like transition layer (low sp) on the Ti transition layer 3 Carbon content);
3) introducing nitrogen gas with flow rate of 20sccm, negatively biasing the substrate to-120V, depositing 8000s, and depositing ta-C layer (high sp) on the diamond-like transition layer 3 Carbon content), closing the vacuum pump, introducing air, opening the sample chamber and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Example 4:
a preparation method of a nitrogen-doped tetrahedral amorphous carbon film comprises the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with alcohol, placing in sample chamber, closing furnace door, and vacuumizing to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting graphite target to deposit diamond-like transition layer, negative bias of-1200V, target current of 50A, and depositing for 2000s in Ti transitionDepositing a diamond-like transition layer (low sp) 3 Carbon content);
3) introducing nitrogen gas with flow rate of 50sccm, adjusting the substrate negative bias to-120V, depositing 8000s, and depositing a ta-C layer (high sp) on the diamond-like transition layer 3 Carbon content), closing the vacuum pump, introducing air, opening the sample chamber and taking out the sample to obtain the nitrogen-doped tetrahedral amorphous carbon film.
Comparative example 1:
a tetrahedral amorphous carbon film is prepared by the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with ethanol, placing in sample chamber, closing furnace door, and vacuumizing to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting a graphite target to deposit the diamond-like transition layer, setting the negative bias of a substrate to-1200V and the target current to 50A, and depositing 2000s, namely depositing the diamond-like transition layer (low sp) on the Ti transition layer 3 Carbon content);
3) adjusting the substrate to-120V with negative bias, depositing 8000s, and depositing a ta-C layer (high sp) on the diamond-like transition layer 3 Carbon content), closing the vacuum pump, introducing air, opening the sample cavity and taking out the sample to obtain the tetrahedral amorphous carbon film.
Comparative example 2:
a tetrahedral amorphous carbon film is prepared by the following steps:
1) cleaning silicon single crystal wafer (100) in ultrasonic cleaning machine containing ethanol and deionized water for 10min, oven drying, wiping with alcohol, and placing in sampleIn the chamber, the furnace door is closed and vacuum is pumped to 5 × 10 -3 Pa, introducing argon (purity 99.999%) with flow rate of 250sccm under-200V bias, and Ar-treating 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 (with the purity of 99.99%) to 150 ℃, depositing for 500s, and then closing the power supply and an argon valve, namely depositing a Ti transition layer on the surface of the silicon single crystal wafer;
2) opening the vacuum pump to vacuumize to 5X 10 -3 Below Pa, starting a graphite target to deposit the diamond-like transition layer, setting the negative bias of a substrate to-1200V and the target current to 50A, and depositing 2000s, namely depositing the diamond-like transition layer (low sp) on the Ti transition layer 3 Carbon content);
3) adjusting the substrate to-400V with negative bias, depositing 8000s, and depositing a ta-C layer (high sp) on the diamond-like transition layer 3 Carbon content), closing the vacuum pump, introducing air, opening the sample cavity and taking out the sample to obtain the tetrahedral amorphous carbon film.
And (3) performance testing:
1) an X-ray photoelectron spectroscopy (XPS) graph of the nitrogen-doped tetrahedral amorphous carbon thin film of example 1 is shown in fig. 1 (the solid line is a fitted curve, and the dotted line is a raw data curve).
As can be seen from fig. 1: the coincidence degree of the fitting curve and the original data curve is good, which shows that the fitting result is reliable; using a Gaussian-Lorentzian fit of 30% Lorentzian, the binding energies were as follows: C-C (285.1eV ± 0.1eV), C ═ C (284.4eV ± 0.1eV), C ═ N (285.9eV ± 0.1eV), C — N (287.2eV ± 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 the fitted curve, dashed line is the raw data curve).
As can be seen from fig. 2: small amounts of C-O and C ═ O bonds occur due to small amounts of air left in the chamber or surface adsorbed oxygen left in the atmosphere.
3) Curves of the C-C bond, C ═ C bond, C-N bond, and C ═ N bond occupancy ratios as a function of nitrogen doping concentration (obtained from the nitrogen-doped tetrahedral amorphous carbon thin films according to examples 1 to 4 and the tetrahedral amorphous carbon thin film of comparative example 1) are shown in fig. 3.
As can be seen from fig. 3: as the nitrogen doping concentration increases, sp 3 The carbon content gradually decreases, the contents of C-N bonds and C ═ N bonds gradually increase, and the content of C ═ N bonds increases more rapidly than that of C — N bonds, indicating that C ═ N bonds are mainly formed after nitrogen incorporation.
4) The nitrogen-doped tetrahedral amorphous carbon thin films of examples 1 to 4 and the tetrahedral amorphous carbon thin films of comparative examples 1 to 2 were subjected to performance tests, and the test results are shown in the following table:
TABLE 1 Performance test results for Nitrogen-doped ta-C films of examples 1-4 and ta-C films of comparative examples 1-2
Note:
nitrogen doping concentration: testing by Electron Probe (EPMA);
sp 3 carbon content: testing by X-ray photoelectron spectroscopy, wherein the target material is Al target, the energy is 1486.6eV, and 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: testing the hardness of the film through a nano indentation experiment, wherein the load is 5mN, the indentation depth is about 100nm, six points are printed on each sample, and the arithmetic average value is taken;
resistivity: the sheet resistance of the film is obtained through a four-probe test, and the resistivity of the film is calculated through the following formula: rho ═ R S X ω, where ρ represents the resistivity in Ω · cm, R s The sheet resistance is expressed in units of Ω/□, ω is the film thickness in units of cm, and three points are measured for each sample, and the arithmetic mean is taken as the result.
As can be seen from Table 1:
a) the resistivity of the ta-C film after doping with 1.8 at% of nitrogen is from more than 1.7X 10 2 Omega cm rapidly decreases to 3.3X 10 -4 Omega cm (graphite resistivity 8X 10) -4 Ω·cm～13×10 -4 Ω · cm) and subsequently the resistivity remains substantially stable with increasing nitrogen doping concentration, but sp 3 The carbon content is gradually reduced, and the hardness and the thickness of the film are also gradually reduced;
b) comparing the nitrogen-doped ta-C film of example 1 with the ta-C films of comparative examples 1-2, the ta-C film had the highest sp under a negative bias of 120V 3 Carbon content and hardness, the resistivity of the nitrogen-doped ta-C film of example 1 was 3.3X 10 under a negative bias of 120V -4 Omega cm, reach the good conductor level, the hardness is only lower than ta-C film of comparative example 1 under the same bias by 1.6 GPa;
c) in the nitrogen-doped ta-C films of comparative examples 1-4, the resistivity of the ta-C film after increasing the nitrogen doping concentration was maintained at the same level as that of the nitrogen-doped ta-C film of example 1, but sp thereof 3 The carbon content, hardness and thickness all continue to decrease.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped tetrahedral amorphous carbon film is characterized by comprising 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 condition of vacuum pumping, depositing a diamond-like transition layer on the Ti transition layer by using a graphite target and controlling the negative bias voltage to be-1300V-1100V through a magnetic filtration cathodic arc technology;
3) in nitrogen atmosphere, a ta-C layer is deposited on the diamond-like transition layer by utilizing a graphite target and controlling the negative bias to be-400V to-120V through a magnetic filtration cathode arc technology, and the nitrogen-doped tetrahedral amorphous carbon film is obtained.
2. The method of preparing a 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 argon is 200-300 sccm.
3. The method for preparing a nitrogen-doped tetrahedral amorphous carbon film according to claim 1 or 2, wherein: 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 600 s.
4. The method of preparing a nitrogen-doped tetrahedral amorphous carbon film according to claim 1, wherein: step 2) the vacuum pumping is vacuum pumping until the pressure is less than 5 multiplied by 10 -3 Pa。
5. The method for preparing a nitrogen-doped tetrahedral amorphous carbon film according to claim 1 or 4, wherein: the operation parameters of the magnetic filtration cathode arc in the step 2) are as follows: the target current is 40-60A, and the deposition time is 1800-2200 s.
6. The method of preparing a nitrogen-doped tetrahedral amorphous carbon film according to claim 1, wherein: the flow rate of the nitrogen in the step 3) is 1 sccm-50 sccm.
7. The method for preparing a nitrogen-doped tetrahedral amorphous carbon film according to claim 1 or 6, wherein: and 3) the operating parameters of the magnetic filtration cathode arc are as follows: the target current is 40-60A, and the deposition time is 7500-8500 s.
8. A nitrogen-doped tetrahedral amorphous carbon film, which is prepared by the preparation method of any one of claims 1 to 7.
9. A bipolar plate having a surface deposited with the nitrogen-doped tetrahedral amorphous carbon thin film of claim 8.
10. A fuel cell comprising the bipolar plate of claim 9.
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