CN114182199A - Transition metal doped amorphous carbon film and preparation method thereof - Google Patents
Transition metal doped amorphous carbon film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transition metal doped amorphous carbon film and a preparation method thereof, belonging to the field of manufacturing of space microwave devices, wherein the transition metal doped amorphous carbon film comprises a transition metal buffer layer, a transition metal discontinuously doped amorphous carbon layer and a transition metal continuously doped amorphous carbon layer which are sequentially arranged on the surface of a metal substrate from bottom to top; the transition metal discontinuously doped amorphous carbon layer is formed by alternately overlapping a plurality of transition metal doped amorphous carbon sub-layers and a plurality of undoped amorphous carbon sub-layers. The invention promotes sp in an amorphous carbon network by doping transition metal in the amorphous carbon film, wherein transition metal atoms can be combined with carbon atoms to form corresponding carbides3Hybridized carbon-carbon bond to sp2Hybridization of carbon-carbon bond conversion to increase sp in amorphous carbon film2The content of hybridized carbon-carbon bonds enhances the scattering effect on electrons, thereby reducing the secondary electron emission coefficient of the amorphous carbon film.
Description
Technical Field
The invention belongs to the field of manufacturing of space microwave devices, and relates to a transition metal doped amorphous carbon film and a preparation method thereof.
Background
When an initial electron with certain energy bombards a solid material, an incident electron is subjected to inelastic scattering in the material, so that the electron in the material is excited to form an internal secondary electron with certain energy distribution, a part of the internal secondary electron moves towards the surface direction, interacts with the solid in the moving process, loses part of energy, and when the internal secondary electron reaches the surface, part of the electron escapes from the surface to form a secondary electron by overcoming a surface potential barrier, and the process is called secondary electron emission.
With the rapid development of the aerospace industry, the demand of the space technology on high-power microwave devices is continuously improved, and secondary electron emission is a serious problem in the use process of the space high-power microwave devices. The secondary electron emission reduces the performance of the microwave device to greatly reduce the working capacity of the microwave device, and even causes permanent damage to the microwave device and even the whole system. For example, secondary electron emission on the surface of a multistage depressed collector in a space traveling wave tube can deteriorate current distribution, reduce the efficiency of the collector, increase the risk of electron backflow, increase heat dissipation power and form noise, and cause deterioration of technical performance of the traveling wave tube; the secondary electron emission on the surface of a dielectric window in the high-power microwave device can cause surface breakdown, and the high-power microwave transmission is severely limited; and, the high power microwave switch may face the micro-discharge phenomenon caused by secondary electron emission during use, causing switch damage and failure. Therefore, secondary electron emission becomes one of important factors threatening the safe and reliable use of the space high-power microwave device, and the inhibition of the secondary electron emission has important scientific significance and application value for improving the working efficiency, reliability and stability of the space high-power microwave device including a space traveling wave tube, a dielectric window and a high-power microwave switch and promoting the development of the space high-power microwave technology. Secondary electron emission is a threat spaceOne of the important factors for the safe and reliable use of the power microwave device is that in order to avoid the performance reduction and even damage of the device caused by secondary electron emission and improve the working efficiency, reliability and stability of the space high-power microwave device including a space traveling wave tube, a dielectric window and a high-power microwave switch, the secondary electron emission coefficient of the surface of the material of the high-power microwave device must be reduced. The amorphous carbon film has sp with strong electron scattering ability in the amorphous carbon film2The film has lower secondary electron emission coefficient due to hybridization of carbon-carbon bonds, and has better stability under high radio frequency field, high temperature and long-term work, thus becoming a more common film material for inhibiting secondary electron emission. However, with the development of space technology, the power of the high-power microwave device is increasing continuously, and the requirement for the amorphous carbon film to suppress secondary electron emission is also increasing continuously, so that the secondary electron emission coefficient of the amorphous carbon film needs to be further reduced to avoid the performance reduction and even damage of the device caused by secondary electron emission, and the space where the power of the microwave device can be increased is increased.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a transition metal doped amorphous carbon film and a preparation method thereof, which can effectively reduce the secondary electron emission coefficient of a space high-power microwave device material, avoid the performance reduction and even damage of the device caused by secondary electron emission, and improve the working efficiency, reliability and stability of the device.
In order to achieve the purpose, the invention has the following technical scheme:
in a first aspect, a transition metal doped amorphous carbon film is provided, which comprises a transition metal buffer layer, an amorphous carbon layer discontinuously doped with transition metal and an amorphous carbon layer continuously doped with transition metal, which are sequentially arranged on the surface of a metal substrate from bottom to top; the transition metal discontinuously doped amorphous carbon layer is formed by alternately overlapping a plurality of transition metal doped amorphous carbon sub-layers and a plurality of undoped amorphous carbon sub-layers;
the total film thickness of the transition metal doped amorphous carbon film is 50nm to 300 nm; the amorphous carbon particle size of the amorphous carbon layer discontinuously doped by the transition metal and the amorphous carbon layer continuously doped by the transition metal is 10 nm-30 nm, the doping content of the transition metal is 2% -5%, and sp is2The content of the hybridized carbon-carbon bond is 60 to 80 percent.
Preferably, the thickness of the transition metal buffer layer is 10nm to 50nm, and the transition metal element used in the transition metal buffer layer is zirconium, vanadium or chromium.
Preferably, the doped elements in the transition metal doped amorphous carbon sublayer are the same as the zirconium, vanadium or chromium elements used in the transition metal buffer layer; the mol content of the doping elements is 4 to 10 percent; the thickness of the transition metal doped amorphous carbon sublayer is 5 nm-10 nm, the number of layers is 5-10, the thickness of the undoped amorphous carbon sublayer is 5 nm-10 nm, and the number of layers is 5-10.
Preferably, the thickness of the amorphous carbon layer doped with the transition metal continuously is 10nm to 20nm, the doping element in the amorphous carbon layer doped with the transition metal continuously is the same as the zirconium, vanadium or chromium element used in the transition metal buffer layer, and the molar content of the doping element is 4% to 10%.
In a second aspect, a method for preparing the transition metal doped amorphous carbon thin film is provided, which comprises:
depositing a transition metal buffer layer on the metal substrate by adopting a method of sputtering a transition metal target;
depositing an amorphous carbon layer discontinuously doped with transition metal on the transition metal buffer layer, specifically, depositing an undoped amorphous carbon sublayer by adopting a method of independently sputtering a graphite target in the process of depositing the amorphous carbon layer discontinuously doped with transition metal, and depositing the amorphous carbon sublayer doped with transition metal by adopting a method of co-sputtering the graphite target and the transition metal target;
and depositing the amorphous carbon layer continuously doped with the transition metal on the amorphous carbon layer discontinuously doped with the transition metal by adopting a method of co-sputtering a graphite target and a transition metal target.
Preferably, before depositing the transition metal buffer layer on the metal substrate, the surface of the metal substrate is bombarded by a magnetron sputtering apparatus with argon ions to remove surface contamination.
Preferably, in the argon ion bombardment process, the air pressure of a cavity of a sample preparation chamber of the magnetron sputtering instrument is 0.1 Pa-1 Pa, the sputtering power is 30W-100W, and the bombardment time is 5 minutes-10 minutes.
Preferably, in the step of depositing the transition metal buffer layer on the metal substrate by using the method of sputtering the transition metal target, the temperature of the metal substrate is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering apparatus, the pressure of a cavity is 0.1-1 Pa, the sputtering power of the transition metal target is 50-150W, and the sputtering time is 2-10 minutes.
Preferably, in the step of depositing the amorphous carbon layer discontinuously doped with the transition metal on the transition metal buffer layer, the number of times of alternately depositing the amorphous carbon sub-layer doped with the transition metal and the amorphous carbon sub-layer undoped with the transition metal is 5 to 10;
in the process of depositing the transition metal doped amorphous carbon sublayer, the temperature of a metal substrate is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering instrument, the air pressure of a cavity is 0.1-1 Pa, the sputtering power of a graphite target is 50-150W, the sputtering power of a transition metal target is 10-40W, and the co-sputtering time is 10-20 minutes;
in the process of depositing the undoped amorphous carbon sublayer, the temperature of the metal substrate is 500-700 ℃, the flow of argon gas is 20-40 sccm and the pressure of the cavity is 0.1-1 Pa in a film forming chamber of a magnetron sputtering device, the sputtering power of a graphite target is 50-150W, and the single sputtering time is 10-20 minutes.
Preferably, in the step of depositing the amorphous carbon layer continuously doped with the transition metal on the amorphous carbon layer discontinuously doped with the transition metal by adopting a co-sputtering graphite target and transition metal target method, the temperature of the metal substrate is 500-700 ℃, argon gas flow is introduced into a film forming chamber of a magnetron sputtering apparatus at 20-40 sccm, the cavity pressure is 0.1-1 Pa, the graphite target sputtering power is 50-150W, the transition metal target sputtering power is 10-40W, and the co-sputtering time is 20-40 minutes.
Compared with the prior art, the invention has the following beneficial effects:
the existing secondary electron emission inhibition technology based on the amorphous carbon film generally adopts the mode of directly depositing a pure amorphous carbon film or a titanium element-doped amorphous carbon film on a metal substrate of oxygen-free copper, aluminum alloy, stainless steel and the like so as to reduce the secondary electron emission coefficient of a metal material, and the reduction capability of the mode is limited, so that the requirement of a high-power microwave device cannot be met. On the contrary, the invention dopes transition metal elements including zirconium, vanadium or chromium in the amorphous carbon film, and adopts the technique of discontinuous doping of transition metal to reasonably control the doping content of the transition metal in the film to a lower level (2-5%) and promote sp in the amorphous carbon network to solve the problem that the doping content of the transition metal in the film is easily overhigh even if the lowest glow starting power of a target is adopted when the magnetron sputtering method is continuously doped with the transition metal3Hybridized carbon-carbon bond to sp2Hybridization of carbon-carbon bond conversion to increase sp in amorphous carbon film2The content of hybridized carbon-carbon bonds enhances the scattering effect on electrons, thereby reducing the secondary electron emission coefficient of the amorphous carbon film. Meanwhile, a transition metal buffer layer is arranged between the metal substrate and the amorphous carbon layer intermittently doped with the transition metal, and transition metal atoms and carbon atoms are easily combined to form corresponding carbides, so that the film-substrate binding force between the metal substrate and the amorphous carbon layer intermittently doped with the transition metal can be improved, and sp in an amorphous carbon film can be promoted2The content of hybridized carbon-carbon bond is increased, and the secondary electron emission coefficient of the amorphous carbon film is further reduced. In view of the above, the transition metal doped amorphous carbon thin film of the present invention as a coating can significantly reduce the secondary electron emission coefficient of metal materials such as oxygen-free copper, aluminum alloy, stainless steel, and the like.
Drawings
FIG. 1 is a schematic structural diagram of a transition metal doped amorphous carbon thin film according to an embodiment of the present invention;
wherein, 1-a metal substrate; 2-a transition metal buffer layer; 3-amorphous carbon layer intermittently doped with transition metal; 4-amorphous carbon layer with continuous doping of transition metal; 5-a transition metal doped amorphous carbon sublayer; 6-a layer of undoped amorphous carbon;
FIG. 2 is a graph showing the variation of the secondary electron emission coefficient with incident electron energy for depositing zirconium-doped amorphous carbon thin films on oxygen-free copper under different zirconium buffer layer thicknesses (0nm, 10nm, 20nm, and 30nm) in accordance with the present invention;
FIG. 3 is a graph of the secondary electron emission coefficient as a function of incident electron energy for zirconium-doped amorphous carbon films deposited on oxygen-free copper with different zirconium doping levels (2.8%, 4.5%, 13.1%) in accordance with an embodiment of the present invention;
FIG. 4 is a curve showing the variation of the secondary electron emission coefficient with incident electron energy for the amorphous carbon thin film deposited on the oxygen-free copper substrate, the zirconium continuous doped amorphous carbon thin film deposited on the oxygen-free copper substrate, and the zirconium discontinuous doped amorphous carbon thin film deposited on the oxygen-free copper substrate according to the embodiment of the present invention;
fig. 5 is a graph showing the variation of the secondary electron emission coefficient with incident electron energy for an oxygen-free copper substrate, an amorphous carbon film deposited on an oxygen-free copper substrate, a titanium-doped amorphous carbon film with a titanium buffer layer deposited on an oxygen-free copper substrate, a zirconium-doped amorphous carbon film with a zirconium buffer layer deposited on an oxygen-free copper substrate, a vanadium-doped amorphous carbon film with a vanadium buffer layer deposited on an oxygen-free copper substrate, and a chromium-doped amorphous carbon film with a chromium buffer layer deposited on an oxygen-free copper substrate according to the embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention aims to improve the existing secondary electron emission inhibition technology based on an amorphous carbon film so as to further improve the inhibition capability of the amorphous carbon film on secondary electron emission, and provides the method that argon ions are used for bombarding the surface of a metal substrate 1 to remove surface pollution, then a layer of transition metal buffer layer 2 is deposited on the metal substrate 1, then an amorphous carbon layer 3 with discontinuously doped transition metal is deposited on the transition metal buffer layer 2 by a method of alternately repeating co-sputtering of a graphite target and a transition metal target and independent sputtering of the graphite target, and finally an amorphous carbon layer 4 with continuously doped transition metal is deposited on the amorphous carbon layer 3 with discontinuously doped transition metal by a method of co-sputtering of the graphite target and the transition metal target. The method provided by the invention can improve the amorphous carbonThe film-substrate binding force between the film and the metal substrate is improved, and sp in the amorphous carbon film is increased2The content of hybridized carbon-carbon bonds is reduced, so that the amorphous carbon film prepared based on the method has a lower secondary electron emission coefficient, and can better inhibit the secondary electron emission on the surface of the metal substrate.
Example 1
Taking the zirconium-doped amorphous carbon film as an example, referring to fig. 1, the zirconium-doped amorphous carbon film of the present invention is sequentially provided with a zirconium buffer layer, a zirconium discontinuously-doped amorphous carbon layer and a zirconium continuously-doped amorphous carbon layer from bottom to top, and the preparation method comprises the following steps:
step 1, bombarding the surface of a metal substrate by adopting argon ions, wherein the air pressure of a cavity is 0.18Pa during argon ion bombardment, the sputtering power is 50W, and the bombardment time is 5 minutes.
And 2, depositing a zirconium buffer layer on the metal substrate by adopting a radio-frequency sputtering zirconium target method, wherein the temperature of the metal substrate is controlled to be 500 ℃, the flow of argon gas introduced into a film forming chamber is 30sccm, the air pressure of a cavity is 0.15Pa, the sputtering power of the zirconium target is 100W, the sputtering time is 2 minutes, and the thickness of the zirconium buffer layer is about 10 nm.
3, depositing a zirconium discontinuously-doped amorphous carbon layer on the metal substrate plated with the zirconium buffer layer by adopting an alternative method of co-sputtering a graphite target and a zirconium target and independently sputtering the graphite target, wherein the number of times of the co-sputtering of the graphite target and the zirconium target and the independent sputtering of the graphite target are 5 times, so that the zirconium-doped amorphous carbon sublayer is 5 layers, and the undoped amorphous carbon sublayer is 5 layers; in the process of co-sputtering and depositing a zirconium-doped amorphous carbon sublayer by using a graphite target and a zirconium target, wherein the temperature of a metal substrate is 500 ℃, the flow of argon introduced into a film forming chamber is 30sccm, the air pressure of a cavity is 0.15Pa, the sputtering power of the graphite target is 150W, the sputtering power of the zirconium target is 30W, the co-sputtering time is 10 minutes, and the thickness of each zirconium-doped amorphous carbon sublayer is about 5 nm; in the process of independently sputtering the graphite target to deposit the undoped amorphous carbon sublayer, the temperature of the metal substrate is 500 ℃, the flow of argon gas introduced into the film forming chamber is 30sccm, the pressure of the cavity is 0.15Pa, the sputtering power of the graphite target is 150W, the independent sputtering time is 10 minutes, and the thickness of each undoped amorphous carbon sublayer is about 5 nm.
And 4, depositing a zirconium continuously-doped amorphous carbon layer on the zirconium discontinuously-doped amorphous carbon layer by adopting a graphite target and zirconium target co-sputtering method, wherein the temperature of the metal substrate is 500 ℃, the flow of argon introduced into the film forming chamber is 30sccm, the pressure of the cavity is 0.15Pa, the sputtering power of the graphite target is 150W, the sputtering power of the zirconium target is 30W, the co-sputtering time is 20 minutes, and the thickness of the zirconium continuously-doped amorphous carbon layer is about 10 nm.
The thickness of the zirconium-doped amorphous carbon film prepared by the steps is about 70nm, the particle size of the amorphous carbon is about 15nm, and sp is2The hybridized carbon-carbon bond content is about 71%.
Example 2
Taking the vanadium-doped amorphous carbon film as an example, referring to fig. 1, the vanadium-doped amorphous carbon film of the present invention comprises a vanadium buffer layer, an amorphous carbon layer intermittently doped with vanadium, and an amorphous carbon layer continuously doped with vanadium, which are sequentially disposed from bottom to top. The preparation method comprises the following steps:
step 1, bombarding the surface of a metal substrate by adopting argon ions, wherein the air pressure of a cavity is 0.18Pa during argon ion bombardment, the sputtering power is 100W, and the bombardment time is 5 minutes.
And 2, depositing a vanadium buffer layer on the metal substrate by adopting a radio frequency sputtering vanadium target method, wherein the temperature of the metal substrate is 600 ℃, the flow of argon introduced into the film forming chamber is 20sccm, the air pressure of the cavity is 0.12Pa, the sputtering power of the vanadium target is 100W, the sputtering time is 5 minutes, and the thickness of the vanadium buffer layer is about 25 nm.
3, depositing a vanadium discontinuously-doped amorphous carbon layer on the metal substrate plated with the vanadium buffer layer by adopting a graphite target and vanadium target co-sputtering and graphite target single sputtering alternating method, wherein the graphite target and vanadium target co-sputtering and graphite target single sputtering alternating times are 6 times, so that the vanadium-doped amorphous carbon sublayer is 6 layers, and the undoped amorphous carbon sublayer is 6 layers; in the process of co-sputtering and depositing the vanadium-doped amorphous carbon sublayer by using the graphite target and the vanadium target, the temperature of a metal substrate is 600 ℃, the flow of argon introduced into a film forming chamber is 20sccm, the air pressure of a cavity is 0.12Pa, the sputtering power of the graphite target is 100W, the sputtering power of the vanadium target is 20W, the co-sputtering time is 15 minutes, and the thickness of each vanadium-doped amorphous carbon sublayer is about 5 nm; in the process of independently sputtering the graphite target to deposit the undoped amorphous carbon sublayer, the temperature of the metal substrate is 600 ℃, the flow of argon gas introduced into the film forming chamber is 20sccm, the pressure of the cavity is 0.12Pa, the sputtering power of the graphite target is 100W, the independent sputtering time is 15 minutes, and the thickness of each undoped amorphous carbon sublayer is about 5 nm.
And 4, depositing a vanadium continuously doped amorphous carbon layer on the vanadium discontinuously doped amorphous carbon layer by adopting a graphite target and vanadium target co-sputtering method, wherein the temperature of the metal substrate is 600 ℃, the flow of argon introduced into the film forming chamber is 20sccm, the pressure of the cavity is 0.12Pa, the sputtering power of the graphite target is 100W, the sputtering power of the vanadium target is 20W, the co-sputtering time is 30 minutes, and the thickness of the vanadium continuously doped amorphous carbon layer is about 15 nm.
The thickness of the zirconium-doped amorphous carbon film prepared by the steps is about 100nm, the particle size of the amorphous carbon is about 20nm, sp is2The hybridized carbon-carbon bond content is about 64%.
Example 3
Taking the chromium-doped amorphous carbon film as an example, referring to fig. 1, the chromium-doped amorphous carbon film of the present invention comprises a chromium buffer layer, an amorphous carbon layer intermittently doped with chromium, and an amorphous carbon layer continuously doped with chromium, which are sequentially disposed from bottom to top. The preparation method comprises the following steps:
step 1, bombarding the surface of a metal substrate by adopting argon ions, wherein the pressure of a cavity is 1Pa during the argon ion bombardment, the sputtering power is 100W, and the bombardment time is 10 minutes.
And 2, depositing a chromium buffer layer on the metal substrate by adopting a radio frequency sputtering chromium target method, wherein the temperature of the metal substrate is 700 ℃, the flow of argon introduced into a film forming chamber is 40sccm, the air pressure of a cavity is 1Pa, the sputtering power of the chromium target is 150W, the sputtering time is 10 minutes, and the thickness of the chromium buffer layer is about 50 nm.
Step 3, depositing chromium-discontinuously-doped amorphous carbon layers on the metal substrate plated with the chromium buffer layer by adopting a method of alternating co-sputtering of a graphite target and a chromium target and independent sputtering of the graphite target, wherein the number of times of the co-sputtering of the graphite target and the chromium target and the independent sputtering of the graphite target is 10, so that the chromium-doped amorphous carbon sub-layers are 10, and the undoped amorphous carbon sub-layers are 10; in the process of co-sputtering and depositing a chromium-doped amorphous carbon sublayer by using a graphite target and a chromium target, the temperature of a metal substrate is 700 ℃, the flow of argon introduced into a film forming chamber is 40sccm, the pressure of a cavity is 1Pa, the sputtering power of the graphite target is 120W, the sputtering power of the chromium target is 40W, the co-sputtering time is 20 minutes, and the thickness of each chromium-doped amorphous carbon sublayer is about 10 nm; in the process of independently sputtering the graphite target to deposit the undoped amorphous carbon sublayer, the temperature of the metal substrate is 700 ℃, the flow of argon gas introduced into the film forming chamber is 40sccm, the pressure of the cavity is 1Pa, the sputtering power of the graphite target is 120W, the independent sputtering time is 20 minutes, and the thickness of each undoped amorphous carbon sublayer is about 10 nm.
And 4, depositing a chromium-continuously-doped amorphous carbon layer on the vanadium-discontinuously-doped amorphous carbon layer by adopting a graphite target and chromium target co-sputtering method, wherein the temperature of the metal substrate is 700 ℃, the flow of argon introduced into the film forming chamber is 40sccm, the pressure of the cavity is 1Pa, the sputtering power of the graphite target is 120W, the sputtering power of the chromium target is 40W, the co-sputtering time is 40 minutes, and the thickness of the chromium-continuously-doped amorphous carbon layer is about 20 nm.
The thickness of the zirconium-doped amorphous carbon film prepared by the steps is about 270nm, the particle size of the amorphous carbon is about 30nm, and sp is2The hybrid carbon-carbon bond content is about 74%.
Referring to fig. 2, comparing the curves of the secondary electron emission coefficients of the zirconium-doped amorphous carbon thin films deposited on the oxygen-free copper substrate according to the incident electron energies under the conditions of different thicknesses of the zirconium buffer layer (0nm, 10nm, 20nm and 30nm), it is apparent from the graph that the secondary electron emission coefficients of the three zirconium-doped amorphous carbon thin films with the zirconium buffer layer are significantly lower compared to the sample without the zirconium buffer layer, and the lower the secondary electron emission coefficient of the zirconium-doped amorphous carbon thin film with the increase of the thickness of the zirconium buffer layer, the lower the reduction of the secondary electron emission coefficient of the zirconium-doped amorphous carbon thin film with the increase of the thickness of the zirconium buffer layer is when the thickness of the zirconium buffer layer is increased to 30 nm.
Referring to fig. 3, comparing the curves of the secondary electron emission coefficient of the zirconium-doped amorphous carbon film deposited on oxygen-free copper with different zirconium doping contents (2.8%, 4.5%, 13.1%), it can be seen that the secondary electron emission coefficient of the amorphous carbon film can be significantly reduced by doping the transition metal zirconium at a low concentration, but the secondary electron emission coefficient of the amorphous carbon film cannot be reduced when the zirconium doping content is too high (e.g., 13.1%).
Referring to fig. 4, comparing the curves of the secondary electron emission coefficient of the amorphous carbon film deposited on the oxygen-free copper substrate, the zirconium continuously doped amorphous carbon film deposited on the oxygen-free copper substrate, and the zirconium discontinuously doped amorphous carbon film deposited on the oxygen-free copper substrate with the change of the incident electron energy, it can be seen from the graphs that the secondary electron emission coefficient of the zirconium discontinuously doped amorphous carbon film on the oxygen-free copper substrate is lower than that of the zirconium continuously doped amorphous carbon film deposited on the oxygen-free copper substrate.
Referring to fig. 5, comparing the curves of the secondary electron emission coefficient with the incident electron energy of the oxygen-free copper substrate, the amorphous carbon film deposited on the oxygen-free copper substrate, the titanium doped amorphous carbon film with the titanium buffer layer deposited on the oxygen-free copper substrate, the zirconium doped amorphous carbon film with the zirconium buffer layer deposited on the oxygen-free copper substrate, the vanadium doped amorphous carbon film with the vanadium buffer layer deposited on the oxygen-free copper substrate, and the chromium doped amorphous carbon film with the chromium buffer layer deposited on the oxygen-free copper substrate, the samples are all manufactured by adopting optimized process parameters, and as can be seen from the figure, the secondary electron emission coefficients of the samples of the zirconium-doped amorphous carbon film with the zirconium buffer layer, the vanadium-doped amorphous carbon film with the vanadium buffer layer and the chromium-doped amorphous carbon film with the chromium buffer layer are lower than those of the samples of the oxygen-free copper substrate, the amorphous carbon film and the titanium-doped amorphous carbon film with the titanium buffer layer.
As can be seen from the above specific examples and the related descriptions, compared with the existing amorphous carbon film preparation technology, the amorphous carbon film with corresponding transition metal low-concentration doping (2% -5%) of the transition metal buffer layer containing zirconium, vanadium and chromium, which is prepared by adopting the film structure and the preparation method of the invention, has higher sp2The carbon-carbon bond is hybridized, so that the material has a lower secondary electron emission coefficient, and can play a role in inhibiting the secondary electron emission of the space high-power microwave device material.
Although the present invention has been described in detail with reference to the above embodiments, the present invention is not limited thereto. The invention is not limited to the above scheme, and the amorphous carbon film structure with the transition metal buffer layer and the corresponding film preparation method are adopted to reduce the secondary electron emission coefficient of the amorphous carbon film according to the basic concept of the invention so as to achieve the effect of better inhibiting the secondary electron emission of the material of the space high-power microwave device, and the invention belongs to the protection scope of the invention.
Claims (10)
1. A transition metal doped amorphous carbon film is characterized by comprising a transition metal buffer layer (2), a transition metal discontinuously doped amorphous carbon layer (3) and a transition metal continuously doped amorphous carbon layer (4) which are sequentially arranged on the surface of a metal substrate (1) from bottom to top; the transition metal discontinuously doped amorphous carbon layer (3) is formed by alternately superposing a plurality of transition metal doped amorphous carbon sublayers (5) and a plurality of undoped amorphous carbon sublayers (6);
the total thickness of the transition metal doped amorphous carbon film is 50 nm-300 nm; the amorphous carbon particle sizes of the amorphous carbon layer (3) discontinuously doped with the transition metal and the amorphous carbon layer (4) continuously doped with the transition metal are 10 nm-30 nm, the doping content of the transition metal is 2% -5%, and sp is2The content of the hybridized carbon-carbon bond is 60 to 80 percent.
2. The transition metal doped amorphous carbon film of claim 1, wherein: the thickness of the transition metal buffer layer (2) is 10 nm-50 nm, and the transition metal element used by the transition metal buffer layer (2) is zirconium, vanadium or chromium.
3. The transition metal doped amorphous carbon film of claim 2, wherein: the doped elements in the transition metal doped amorphous carbon sublayer (5) are the same as the zirconium, vanadium or chromium elements used in the transition metal buffer layer (2); the mol content of the doping elements is 4 to 10 percent; the thickness of the transition metal doped amorphous carbon sublayer (5) is 5 nm-10 nm, the number of layers is 5-10, the thickness of the undoped amorphous carbon sublayer (6) is 5 nm-10 nm, and the number of layers is 5-10.
4. The transition metal doped amorphous carbon film of claim 1, wherein: the thickness of the amorphous carbon layer (4) continuously doped with the transition metal is 10-20 nm, the doped elements in the amorphous carbon layer (4) continuously doped with the transition metal are the same as the zirconium, vanadium or chromium elements used in the transition metal buffer layer (2), and the molar content of the doped elements is 4-10%.
5. A method for preparing the transition metal doped amorphous carbon thin film according to any one of claims 1 to 4, comprising:
depositing a transition metal buffer layer (2) on a metal substrate (1) by adopting a method of sputtering a transition metal target;
depositing a transition metal discontinuously-doped amorphous carbon layer (3) on the transition metal buffer layer (2), specifically, in the process of depositing the transition metal discontinuously-doped amorphous carbon layer (3), depositing an undoped amorphous carbon sublayer (6) by adopting a method of sputtering a graphite target alone, and depositing a transition metal doped amorphous carbon sublayer (5) by adopting a method of co-sputtering the graphite target and the transition metal target;
and depositing the amorphous carbon layer (4) continuously doped with the transition metal on the amorphous carbon layer (3) discontinuously doped with the transition metal by adopting a method of co-sputtering a graphite target and a transition metal target.
6. The method of claim 5, wherein: before the transition metal buffer layer (2) is deposited on the metal substrate (1), the surface of the metal substrate (1) is bombarded by argon ions through a magnetron sputtering instrument to remove surface contamination.
7. The method of claim 6, wherein: in the argon ion bombardment process, the air pressure of a cavity of a sample preparation chamber of the magnetron sputtering instrument is 0.1 Pa-1 Pa, the sputtering power is 30W-100W, and the bombardment time is 5 minutes-10 minutes.
8. The method of claim 5, wherein: in the step of depositing the transition metal buffer layer (2) on the metal substrate (1) by adopting the method of sputtering the transition metal target, the temperature of the metal substrate (1) is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering instrument, the air pressure of a cavity is 0.1-1 Pa, the sputtering power of the transition metal target is 50-150W, and the sputtering time is 2-10 minutes.
9. The method of claim 5, wherein: in the step of depositing the amorphous carbon layer (3) discontinuously doped with the transition metal on the transition metal buffer layer (2), the number of times of alternately depositing the amorphous carbon sub-layer (5) doped with the transition metal and the amorphous carbon sub-layer (6) undoped with the transition metal is 5 to 10;
in the process of depositing the transition metal doped amorphous carbon sublayer (5), the temperature of the metal substrate (1) is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering instrument, the air pressure of a cavity is 0.1-1 Pa, the sputtering power of a graphite target is 50-150W, the sputtering power of a transition metal target is 10-40W, and the co-sputtering time is 10-20 minutes;
in the process of depositing the undoped amorphous carbon sublayer (6), the temperature of the metal substrate (1) is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering instrument, the pressure of a cavity is 0.1-1 Pa, the sputtering power of a graphite target is 50-150W, and the single sputtering time is 10-20 minutes.
10. The method of claim 5, wherein: in the step of depositing the amorphous carbon layer (4) continuously doped with the transition metal on the amorphous carbon layer (3) discontinuously doped with the transition metal by adopting a co-sputtering graphite target and transition metal target method, the temperature of the metal substrate (1) is 500-700 ℃, argon gas flow of 20-40 sccm is introduced into a film forming chamber of a magnetron sputtering instrument, the cavity air pressure is 0.1-1 Pa, the graphite target sputtering power is 50-150W, the transition metal target sputtering power is 10-40W, and the co-sputtering time is 20-40 minutes.
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