A co-sputtering method for preparing a molybdenum carbide composite phase film
By combining co-sputtering of Mo2C and Mo targets with annealing, α-MoC/β-Mo2C composite phase thin films were prepared, solving the problems of large-area preparation and process complexity of molybdenum carbide catalysts in the prior art. This method enabled the preparation of large-area, uniform molybdenum carbide thin films, improving hydrogen evolution performance and reducing costs.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-08
- Publication Date
- 2026-03-31
AI Technical Summary
Existing technologies make it difficult to prepare efficient molybdenum carbide hydrogen evolution catalysts on a large scale and stably. Furthermore, nanoparticles are prone to agglomeration, the preparation process is complex and costly, and it is difficult to meet the needs of commercial applications.
Molybdenum carbide thin films were deposited on a substrate using a co-sputtering method with Mo2C and Mo targets, and then annealed with a mixture of Ar and H2 gas to obtain α-MoC/β-Mo2C composite phase thin films.
Large-area, uniform molybdenum carbide thin films were successfully prepared, exhibiting superior hydrogen evolution performance. The preparation process was simplified, costs were reduced, and the films are suitable for binderless hydrogen evolution anode electrode materials.
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Figure CN117926183B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of material preparation, in particular to a co-sputtering preparation method of molybdenum carbide composite phase film. BACKGROUND
[0002] Pt / C electrode is a commercial hydrogen evolution cathode material, which has excellent hydrogen evolution performance. However, the price of noble metal is high, and for hydrogen evolution application, a catalyst with low cost, high efficiency, acid and alkali resistance and good stability has better commercial application prospect. Molybdenum carbide has a similar orbital structure to Pt, and theoretically has good hydrogen evolution performance, and is expected to replace Pt and become a commercial hydrogen evolution catalyst. The hydrogen evolution performance of molybdenum carbide is affected by the too high electron density of d orbital, although the hydrogen adsorption capacity is strong, but the hydrogen desorption capacity is weak, and it needs to be modified to improve its hydrogen evolution performance.
[0003] In recent years, with the development of research methods and manufacturing technology, the hydrogen evolution performance of molybdenum carbide has been continuously improved by using methods such as doping, morphology control, structure engineering and heterostructure. Although the hydrogen evolution performance of molybdenum carbide has been greatly improved in theoretical research and laboratory sample preparation, commercial application requires large-area, stable preparation and simple preparation method. There are still some problems in the preparation of hydrogen evolution electrode by using nano powder, such as easy agglomeration of nano powder, which needs complex means to resist agglomeration when used in large area; the adhesive used in the preparation of electrode has high price and increases the preparation process; and the process is difficult to control when a large amount of nano powder is synthesized. The sputtering method for preparing large-area thin film has stable process, uniform particle dispersion, strong adhesion to the substrate, and does not need adhesive. It has good commercial application prospect.
[0004] Molybdenum carbide has four common phases, of which the hydrogen evolution performance of α-MoC and β-Mo2C is concerned. Through theoretical calculation of the two phases, it is considered that β-Mo2C has lower hydrogen binding energy than α-MoC, but a large number of studies have confirmed that α-MoC also has excellent hydrogen evolution performance. In recent years, the study of α-MoC / β-Mo2C composite phase has increased, and both theoretical calculation and experiment have confirmed that α-MoC / β-Mo2C composite phase has better hydrogen evolution performance than single α-MoC and β-Mo2C. When molybdenum carbide film is prepared by sputtering method, the Mo / C ratio has a great influence on the phase transition. When molybdenum carbide target is sputtered, it is difficult to obtain β-Mo2C phase film.
[0005] Therefore, in view of the deficiencies of the prior art, it is very necessary to provide a co-sputtering preparation method of molybdenum carbide composite phase film to solve the deficiencies of the prior art. SUMMARY
[0006] The present application aims at avoiding the defects of the prior art and providing a co-sputtering preparation method of a molybdenum carbide composite phase film.
[0007] The above-mentioned object of the present application is achieved by the following technical measures:
[0008] The present application provides a co-sputtering preparation method of a molybdenum carbide composite phase film, which simultaneously deposits Mo2C and Mo on a substrate through co-sputtering of a Mo2C target and a Mo target, and obtains an α-MoC / β-Mo2C composite phase film after annealing treatment.
[0009] The co-sputtering preparation method of a molybdenum carbide composite phase film of the present application comprises the following steps:
[0010] S1, placing a substrate on a rotatable substrate support of a vacuum magnetron sputtering device;
[0011] S2, placing a Mo2C target in a first target gun and a Mo target in a second target gun, and simultaneously depositing a molybdenum carbide film;
[0012] S3, annealing the molybdenum carbide film obtained in S2 under Ar and H2 mixed gas, the annealing temperature being 600-700℃, to obtain an α-MoC / β-Mo2C composite phase film.
[0013] Preferably, S3 is specifically: the molybdenum carbide film obtained in S2 is annealed under Ar and H2 mixed gas, the temperature is raised to an annealing temperature of 600-700℃ at a rate of 8-12℃ / min, then the temperature is kept for 50-70min, and finally the temperature is naturally lowered to obtain an α-MoC / β-Mo2C composite phase film.
[0014] Preferably, S2 is specifically: the Mo2C target is placed in the first target gun and the Mo target is placed in the second target gun, the sputtering pressure is controlled to be 0.5-1.0Pa, the sputtering power of the first target gun is controlled to be 150-220W, the sputtering power of the second target gun is controlled to be 20-50W, and the sputtering is performed for 25-45min to simultaneously deposit a molybdenum carbide film.
[0015] Preferably, S3 is specifically: the molybdenum carbide film obtained in S2 is annealed under Ar and H2 mixed gas, the temperature is raised to an annealing temperature of 650℃ at a rate of 10℃ / min, then the temperature is kept for 60min, and finally the temperature is naturally lowered to obtain an α-MoC / β-Mo2C composite phase film.
[0016] Preferably, in the S2, the Mo2C target is arranged in the first target gun, the Mo target is arranged in the second target gun, the sputtering pressure is controlled to be 0.8 Pa, the sputtering power of the first target gun is controlled to be 160-200 W, the sputtering power of the second target gun is controlled to be 30 W, and the sputtering is performed for 30 min, so as to simultaneously deposit the molybdenum carbide film.
[0017] Preferably, the Mo2C target in the S2 is provided with a radio frequency power source.
[0018] Preferably, the Mo target gun in the S2 is provided with a direct current power source.
[0019] In the S3, the mixed gas is 90% Ar and 10% H2 by volume.
[0020] In the S2, the substrate holder rotates at a speed of 90 rpm.
[0021] In the S2, the first target gun and the second target gun are both 45° with the substrate and are both 8 cm away from the substrate.
[0022] The present application discloses a method for preparing a molybdenum carbide composite phase film by co-sputtering. The method comprises the following steps: arranging a Mo2C target and a Mo target on a substrate, and co-sputtering the Mo2C target and the Mo target to simultaneously deposit Mo2C and Mo, and then annealing to obtain an α-MoC / β-Mo2C composite phase film. The method can obtain the α-MoC / β-Mo2C composite phase film by co-sputtering the Mo2C target and the Mo target, and the α-MoC / β-Mo2C composite phase film has better hydrogen evolution performance than a single-phase MoC. The method for preparing the molybdenum carbide composite phase film is simple and stable, and thus can be applied to the preparation of a large-area, binder-free hydrogen evolution negative electrode material. BRIEF DESCRIPTION OF DRAWINGS
[0023] The present application is further described with reference to the accompanying drawings, but the content in the drawings does not constitute any limitation to the present application.
[0024] Figure 1 FIG. 1 is a schematic structural diagram of a magnetron sputtering film coating device.
[0025] Figure 2 FIG. 4 is an XRD pattern of the film before and after annealing in Example 1.
[0026] Figure 3 FIG. 5 is a TEM photo of the α-MoC / β-Mo2C composite phase film in Example 1.
[0027] Figure 4 FIG. 6 is a SAED diffraction pattern of the α-MoC / β-Mo2C composite phase film in Example 1.
[0028] Figure 5This is a SEM image of the α-MoC / β-Mo2C composite phase thin film of Example 2.
[0029] Figure 6 The linear sweep voltammetric curve of the α-MoC / β-Mo2C composite phase thin film obtained in Example 2 in 0.5M H2SO4 electrolyte is shown.
[0030] Figure 7 The linear sweep voltammetry curve of the α-MoC / β-Mo2C composite phase thin film obtained in Example 2 in 1M KOH electrolyte is shown. Detailed Implementation
[0031] The technical solution of the present invention will be further described in conjunction with the following embodiments.
[0032] Example 1
[0033] A method for co-sputtering molybdenum carbide composite phase thin films involves simultaneously depositing Mo2C and Mo on a substrate via co-sputtering with a Mo2C target and a Mo target, followed by annealing to obtain an α-MoC / β-Mo2C composite phase thin film.
[0034] The co-sputtering preparation method of the molybdenum carbide composite phase thin film of the present invention includes the following steps:
[0035] S1. Place the single-sided polished monocrystalline silicon substrate as the substrate onto the rotatable substrate support of the vacuum magnetron sputtering instrument, and then place the substrate into the vacuum magnetron sputtering equipment (e.g., Figure 1 A rotatable substrate support; the single-sided polished monocrystalline silicon substrate is ultrasonicated with acetone, alcohol and deionized water for 15 minutes before being placed in, and then dried with an N2 air gun.
[0036] S2. Place the Mo2C target in the first target gun and the Mo target in the second target gun. The purity of both targets is 99.99%. The angle between the first and second target guns and the substrate is 45°, and the distance between them is 8cm. Then, evacuate the vacuum chamber of the vacuum magnetron sputtering equipment to 8*10. -4 Ar gas at 70 sccm was introduced to control the sputtering pressure in the vacuum chamber at 0.8 Pa. The substrate support was rotated at 90 rpm to ensure uniform composition of the deposited film. The sputtering power of the first target gun was controlled at 200 W, and the sputtering power of the second target gun was controlled at 30 W. Finally, the sample baffle was opened to allow sputtered particles from both the Mo2C and Mo targets to be deposited simultaneously on the substrate. After sputtering for 30 min, the sample baffle and the target guns were closed, resulting in a molybdenum carbide film with a thickness of 700 nm to 1 μm. The Mo2C target used an RF power supply, while the Mo target gun used a DC power supply.
[0037] S3. The molybdenum carbide thin film obtained in S2 is placed in a tube furnace, and a mixture of Ar and H2 gas is introduced. Under the Ar and H2 gas mixture, with a volume ratio of 90% Ar + 10% H2, the temperature is raised to an annealing temperature of 650°C at a controlled heating rate of 10°C / min, and then held at that temperature for 60 min. After the holding period, the temperature is allowed to cool naturally, finally obtaining an α-MoC / β-Mo2C composite phase thin film. The Mo / C atomic ratio in the α-MoC / β-Mo2C composite phase thin film obtained in this invention is 1.8–2.2.
[0038] Example 2
[0039] A method for co-sputtering molybdenum carbide composite phase thin films involves simultaneously depositing Mo2C and Mo on a substrate via co-sputtering with a Mo2C target and a Mo target, followed by annealing to obtain an α-MoC / β-Mo2C composite phase thin film.
[0040] The co-sputtering preparation method of the molybdenum carbide composite phase thin film of the present invention includes the following steps:
[0041] S1. Place the hydrophobic carbon paper as a substrate on the rotatable substrate support of the vacuum magnetron sputtering instrument.
[0042] S2. Place the Mo2C target in the first target gun and the Mo target in the second target gun. The purity of both targets is 99.99%. The angle between the first and second target guns and the substrate is 45°, and the distance between them is 8cm. Then, evacuate the vacuum chamber of the vacuum magnetron sputtering equipment to 8*10. -4 Ar gas at 70 sccm was introduced to control the sputtering pressure in the vacuum chamber at 0.8 Pa. The substrate support was rotated at 90 rpm to ensure uniform composition of the deposited film. The sputtering power of the first target gun was controlled at 180 W, and the sputtering power of the second target gun was controlled at 30 W. Finally, the sample baffle was opened to allow sputtered particles from both the Mo2C and Mo targets to be deposited simultaneously on the substrate. After sputtering for 30 minutes, the sample baffle and the target guns were closed, yielding a molybdenum carbide film. The Mo2C target used an RF power supply, while the Mo target gun used a DC power supply.
[0043] S3. The molybdenum carbide film obtained in S2 is placed in a tube furnace, and a mixture of Ar and H2 gas is introduced. Under the mixed Ar and H2 gas with a volume ratio of 90% Ar + 10% H2, the heating rate is controlled to raise the temperature to 650℃ at 10℃ / min, and then the temperature is held for 60min. After the holding time is completed, the temperature is allowed to drop naturally to finally obtain the α-MoC / β-Mo2C composite phase film.
[0044] Example 3
[0045] A method for co-sputtering molybdenum carbide composite phase thin films involves simultaneously depositing Mo2C and Mo on a substrate via co-sputtering with a Mo2C target and a Mo target, followed by annealing to obtain an α-MoC / β-Mo2C composite phase thin film.
[0046] The co-sputtering preparation method of the molybdenum carbide composite phase thin film of the present invention includes the following steps:
[0047] S1. Place the single-sided polished monocrystalline silicon substrate as the substrate onto the rotatable substrate support of the vacuum magnetron sputtering instrument. Place the substrate on the rotatable substrate support of the vacuum magnetron sputtering equipment. Before placing the single-sided polished monocrystalline silicon substrate, sonicate it with acetone, alcohol, and deionized water for 15 minutes respectively, and then dry it with an N2 air gun.
[0048] S2. Place the Mo2C target in the first target gun and the Mo target in the second target gun. The purity of both targets is 99.99%. The angle between the first and second target guns and the substrate is 45°, and the distance between them is 8cm. Then, evacuate the vacuum chamber of the vacuum magnetron sputtering equipment to 8*10. -4 Ar gas at 70 sccm was introduced to control the sputtering pressure in the vacuum chamber at 0.5 Pa. The substrate support was rotated at 90 rpm to ensure uniform composition of the deposited film. The sputtering power of the first target gun was controlled at 150 W, and the sputtering power of the second target gun was controlled at 20 W. Finally, the sample baffle was opened to allow sputtered particles from both the Mo2C and Mo targets to be deposited simultaneously on the substrate. After sputtering for 30 minutes, the sample baffle and the target guns were closed, yielding a molybdenum carbide film. The Mo2C target used an RF power supply, while the Mo target gun used a DC power supply.
[0049] S3. The molybdenum carbide film obtained in S2 is placed in a tube furnace, and a mixture of Ar and H2 gas is introduced. Under the mixed Ar and H2 gas with a volume ratio of 90% Ar + 10% H2, the heating rate is controlled to raise the temperature to 600℃ at 8℃ / min, and then the temperature is held for 50 min. After the holding time is completed, the temperature is allowed to drop naturally to finally obtain the α-MoC / β-Mo2C composite phase film.
[0050] Example 4
[0051] A method for co-sputtering molybdenum carbide composite phase thin films involves simultaneously depositing Mo2C and Mo on a substrate via co-sputtering with a Mo2C target and a Mo target, followed by annealing to obtain an α-MoC / β-Mo2C composite phase thin film.
[0052] The co-sputtering preparation method of the molybdenum carbide composite phase thin film of the present invention includes the following steps:
[0053] S1. Place the single-sided polished monocrystalline silicon substrate as the substrate onto the rotatable substrate support of the vacuum magnetron sputtering instrument. Place the substrate on the rotatable substrate support of the vacuum magnetron sputtering equipment. Before placing the single-sided polished monocrystalline silicon substrate, sonicate it with acetone, alcohol, and deionized water for 15 minutes respectively, and then dry it with an N2 air gun.
[0054] S2. Place the Mo2C target in the first target gun and the Mo target in the second target gun. The purity of both targets is 99.99%. The angle between the first and second target guns and the substrate is 45°, and the distance between them is 8cm. Then, evacuate the vacuum chamber of the vacuum magnetron sputtering equipment to 8*10. -4 Ar gas at 70 sccm was introduced to control the sputtering pressure in the vacuum chamber at 1.0 Pa. The substrate support was rotated at 90 rpm to ensure uniform composition of the deposited film. The sputtering power of the first target gun was controlled at 220 W, and the sputtering power of the second target gun was controlled at 50 W, allowing sputtered particles from both the Mo2C and Mo targets to be deposited simultaneously on the substrate. After sputtering for 45 min, the sample baffle and the target guns were turned off, resulting in a molybdenum carbide film. The Mo2C target used an RF power supply, while the Mo target gun used a DC power supply.
[0055] S3. The molybdenum carbide film obtained in S2 is placed in a tube furnace, and a mixture of Ar and H2 gas is introduced. Under the mixed Ar and H2 gas with a volume ratio of 90% Ar + 10% H2, the heating rate is controlled to raise the temperature to 700℃ at 12℃ / min, and then the temperature is held for 70 min. After the holding time is completed, the temperature is allowed to drop naturally to finally obtain the α-MoC / β-Mo2C composite phase film.
[0056] Experiments and Testing
[0057] 1. XRD test
[0058] The molybdenum carbide thin film, also known as the pre-annealed film, and the α-MoC / β-Mo2C composite phase thin film, also known as the post-annealed film, were compared with the pre-annealed and post-annealed films of Example 1 by XRD analysis. Figure 2 .
[0059] Depend on Figure 2 It can be seen that the XRD pattern of the film after sputtering shows the (111) and (200) diffraction peaks of α-MoC. After annealing at 650℃, the XRD pattern of the α-MoC / β-Mo2C composite film shows the (100), (002) and (101) diffraction peaks of β-Mo2C in addition to the (111) and (200) diffraction peaks of α-MoC, indicating that the film is an α-MoC / β-Mo2C composite phase.
[0060] 2. TEM test
[0061] The α-MoC / β-Mo2C composite thin film prepared in Example 1 was photographed using TEM. Figure 3 .
[0062] exist Figure 3 The uniform distribution of two different crystal lattices was observed. After measuring the interplanar spacing, it corresponds to the (111) crystal plane of α-MoC and the (102) crystal plane of β-Mo2C.
[0063] The SAED diffraction pattern of the α-MoC / β-Mo2C composite thin film prepared in Example 1 is shown below. Figure 4 .
[0064] from Figure 4 As can be seen, and with typical polycrystalline diffraction rings, multiple crystal planes belonging to α-MoC and β-Mo2C can be identified, confirming that the obtained film is an α-MoC / β-Mo2C composite phase.
[0065] 3. SEM testing
[0066] Obtain SEM images of the α-MoC / β-Mo2C composite phase thin film obtained in Example 2, such as... Figure 5 As shown. By Figure 5 As can be seen, the sputtered molybdenum carbide particles uniformly cover the surface of the carbon paper fiber to form a dense film with a particle size of 10nm to 25nm.
[0067] 4. Hydrogen evolution performance test
[0068] The α-MoC / β-Mo2C composite phase film obtained in Example 2 was used as the negative electrode for hydrogen evolution testing.
[0069] Hydrogen evolution tests were performed using a standard three-electrode system in 0.5 M H₂SO₄ and 1 M KOH electrolytes. Prior to the test, the electrolytes were purged with N₂ for 5 minutes to remove oxygen. A saturated calomel reference electrode was used for the 0.5 M H₂SO₄ electrolyte, and a mercury / mercury oxide reference electrode was used for the 1 M KOH electrolyte. The tests were then conducted using an electrochemical workstation.
[0070] Key evaluation parameters for hydrogen evolution catalysts include: 1. Overpotential: A lower overpotential, achieving the same current density, indicates that less energy is required to achieve the same amount of hydrogen evolution; 2. Tafel slope: The Tafel slope is an important indicator of the kinetics of the hydrogen evolution reaction, reflecting the charge transfer capability. A smaller Tafel slope indicates that a smaller overpotential is required to increase the same current density, implying faster charge transfer kinetics; 3. Stability: The long-term operational stability of the catalyst.
[0071] 4.1. The linear sweep voltammetric curve of the α-MoC / β-Mo2C composite phase thin film obtained in Example 2 in 0.5M H2SO4 electrolyte was obtained. Figure 6 .
[0072] from Figure 6 The 10mA cm can be calculated from the curve. -2 The overpotential at the current density is 119 mV, and the Tafel slope is 73 mVdec. -1 .
[0073] 4.2. The linear sweep voltammetric curve of the α-MoC / β-Mo2C composite phase thin film obtained in Example 2 in 1 MkOH electrolyte was obtained. Figure 7 .
[0074] from Figure 7 From the curve, 10mA cm can be calculated. -2 The overpotential at a current density of 116 mV has a Tafel slope of 80.9 mV dec. -1 .
[0075] It should be noted that for non-precious metal thin-film catalysts, achieving an overpotential below 200mV and a decay rate of 100mV is crucial. -1 The following Tafel slope, therefore Figure 6 and Figure 7 The α-MoC / β-Mo2C composite phase film exhibits excellent hydrogen evolution performance.
[0076] In summary, the co-sputtering preparation method for molybdenum carbide composite phase thin films of the present invention can prepare α-MoC / β-Mo2C molybdenum carbide composite phase thin films, which exhibit better hydrogen evolution performance compared with single α-MoC or β-Mo2C phase thin films. Furthermore, this co-sputtering preparation method utilizes co-sputtering deposition with a Mo2C target and a Mo target, and can be achieved through controlled annealing. Therefore, the preparation method of the present invention has the advantages of simplicity and good stability, and is thus suitable for preparing large-area, binder-free hydrogen evolution anode electrode materials.
[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A co-sputtering method for preparing a MoC composite phase thin film, characterized in that: Mo2C and Mo are simultaneously deposited on a substrate by co-sputtering of Mo2C target and Mo target, and after annealing treatment, an α-MoC / β-Mo2C composite phase thin film is obtained; The method comprises the following steps: S1, placing a substrate on a rotatable substrate support of a vacuum magnetron sputtering device; S2, placing a Mo2C target in a first target gun and a Mo target in a second target gun to simultaneously deposit a molybdenum carbide thin film; S3, annealing the molybdenum carbide thin film obtained in S2 under Ar and H2 mixed gas, with an annealing temperature of 600-700 ℃, to obtain an α-MoC / β-Mo2C composite phase thin film; S3 is specifically that the molybdenum carbide thin film obtained in S2 is heated to an annealing temperature of 600-700 ℃ at a heating rate of 8-12 ℃ / min under Ar and H2 mixed gas, then kept for 50-70 min, and finally naturally cooled to obtain an α-MoC / β-Mo2C composite phase thin film; S2 is specifically that the Mo2C target is placed in the first target gun and the Mo target is placed in the second target gun, the sputtering pressure is controlled to be 0.5-1.0 Pa, the sputtering power of the first target gun is controlled to be 150-220 W, the sputtering power of the second target gun is controlled to be 20-50 W, and the molybdenum carbide thin film is simultaneously deposited by sputtering for 25-45 min.
2. The co-sputtering method of claim 1, wherein the MoC composite phase thin film is formed by co-sputtering of a Mo target and a C target. S3 is specifically that the molybdenum carbide thin film obtained in S2 is heated to an annealing temperature of 650 ℃ at a heating rate of 10 ℃ / min under Ar and H2 mixed gas, then kept for 60 min, and finally naturally cooled to obtain an α-MoC / β-Mo2C composite phase thin film.
3. The co-sputtering method of claim 1, wherein the MoC composite phase thin film is formed by co-sputtering of a Mo target and a C target. S2 is specifically that the Mo2C target is placed in the first target gun and the Mo target is placed in the second target gun, the sputtering pressure is controlled to be 0.8 Pa, the sputtering power of the first target gun is controlled to be 160-200 W, the sputtering power of the second target gun is controlled to be 30 W, and the molybdenum carbide thin film is simultaneously deposited by sputtering for 30 min.
4. The co-sputtering method for preparing a MoCx composite phase thin film according to any one of claims 1 to 3, characterized in that: The Mo2C target adopts a radio frequency power supply; The Mo target gun adopts a direct current power supply.
5. The co-sputter deposition method of claim 1, wherein: In S3, the mixed gas is 90% Ar and 10% H2 by volume.
6. The co-sputtering method of claim 1-3, wherein: In S2, the substrate support rotates at a speed of 90 rpm.
7. The co-sputtering method for preparing a MoCx composite phase thin film according to any one of claims 1 to 3, characterized in that: In S2, the included angle between the first target gun, the second target gun and the substrate is 45°, and the distance between them is 8 cm.