A crystal-amorphous thin film with super-smooth surface and a preparation method and application thereof

Abstract

The application discloses a crystal-amorphous thin film with an ultrasmooth surface and a preparation method and application thereof, and the method comprises the following steps: S1, preparing an AlCrZrMoV high-entropy alloy target material and a TiBC composite target material; S2, preparing a crystal-amorphous thin film by adopting a magnetron sputtering method. The application comprises the application of the crystal-amorphous thin film with the ultrasmooth surface in the preparation of a mechanical part protective coating. The crystal-amorphous thin film obtained by the method has high purity, good compactness and good film forming uniformity; the crystal-amorphous thin film is well combined with a substrate and is easy to realize industrialization; and the hardness and the elastic modulus of the crystal-amorphous thin film are higher than those of common high-entropy alloy materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite film materials, in particular to a crystal-amorphous film with super-smooth surface and a preparation method and application thereof. BACKGROUND

[0002] Although traditional transition metal nitride hard protective coatings such as TiN and NbN can improve the service life of mechanical parts to a certain extent, the high residual stress of the film and the brittleness of the ceramic film itself will lead to the failure of the film in extreme environments. The research on multi-component ceramics has attracted widespread interest for decades, and after the introduction of the concept of high-entropy stabilization, high-entropy ceramics containing 5 or more than 5 cations have attracted great attention due to their excellent performance in various structures and functions. One of the four effects of high-entropy alloys-cocktail effect in properties can obtain the integration of various properties through the addition of multiple elements, which helps to make up for the limitations of traditional ceramic performance. Compared with traditional nitride ceramics, they have higher strength, hardness, corrosion resistance, wear resistance and high-temperature stability, etc. Therefore, high-entropy ceramic films have potential application prospects in the protection field of important mechanical parts in extreme harsh environments.

[0003] In recent years, high-entropy nitride thin films / coatings prepared by physical vapor deposition have become a research hotspot, which not only shows similar excellent performance to bulk high-entropy alloys, but also is even better than them in some properties. High-entropy alloys and metallic glasses are two types of materials based on the mixing of multiple main elements. It is proposed that the addition of weak nitride-forming elements (Cr, Mo, etc.) will disturb the crystal structure and lead to the formation of amorphous phase. Metallic glasses (MG) have no grain boundaries and dislocations, and usually have better corrosion resistance and higher strength than crystals. In addition, the formation of nanocomposite structure is an effective way to improve the strength of the material without losing toughness. The toughening mechanism of nanocomposite thin films is the blunting effect of the metal phase to the crack tip and the inhibition effect of the phase interface to the crack propagation. Therefore, the design of crystal-amorphous nanocomposite structure may improve the strength, toughness and wear resistance of high-entropy alloy thin films. SUMMARY

[0004] In view of the above technical deficiencies, the purpose of the present application is to provide a crystal-amorphous film with super-smooth surface and a preparation method and application thereof, in particular to the introduction of glass-forming element TiBC composite component, the preparation of nanocomposite material with crystal-amorphous dual-phase structure by magnetron sputtering technology and the adjustment of the process parameters of sputtering AlCrZrMoV and TiBC two composite targets.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is as follows:

[0006] The application provides a preparation method of a crystal-amorphous thin film with an ultra-smooth surface.

[0007] S1, preparing a high-entropy composite target material:

[0008] Al, Cr, Zr, Mo and V powders with high purity (≥99.9%) are melted and cast into ingots according to the equal-molar proportion of alloy raw materials by adopting a powder metallurgy method.

[0009] The ingots are crushed and ball milled into powders, and then sieved.

[0010] The alloy powders are loaded into a mold by adopting isostatic pressing, and then high-temperature sintering is performed, and the parameters are 650 DEG C / 45 min, 850 DEG C / 45 min and 1400 DEG C / 3 h respectively, finally, the formed alloy sample is cooled to room temperature and demolded, and finally, the AlCrZrMoV high-entropy alloy target material is formed.

[0011] The TiBC composite target material with TiB2:TiC=0.8:0.2 is prepared by adopting the same method.

[0012] S2, preparing a crystal-amorphous thin film by adopting a magnetron sputtering method:

[0013] S2.1, cleaning: the silicon wafer substrate is cleaned in petroleum ether and ethanol by using ultrasonic waves successively for 15-20 min.

[0014] S2.2, removing oxides: the sample is subjected to low-energy Ar + ion bombardment for 10 min to eliminate oxide impurities before depositing the thin film.

[0015] S2.3, sputtering film deposition: the AlCrZrMoV high-entropy alloy target material and the TiBC composite target material are placed at a position 15 cm below the substrate, and when the pressure in the vacuum chamber is lower than 2.0 mPa, sputtering film deposition can be started; the sputtering gas pressure is 0.3-0.6 Pa; the total sum of Ar gas flow and N2 flow is kept at 60 sccm, and the N2 flow is 3 sccm, 10 sccm, 20 sccm and 30 sccm respectively; a bias voltage of-80 V is applied to the substrate, and the duty cycle is 70%; the sputtering power of the two target materials is 100 W and 60 W respectively, and the crystal-amorphous thin film is prepared.

[0016] As preferred, the molar proportion of high-purity Al, Cr, Zr, Mo and V in step S1 is 1:1:1:1:1, and the proportion of TiB2:TiC is 0.8:0.2.

[0017] As preferred, the parameters of high-temperature sintering in step S1 are 650 DEG C / 45 min, 850 DEG C / 45 min and 1400 DEG C / 3 h respectively. ​

[0018] As preferably, the N2 flow rate in step S2 is 3sccm / 10sccm / 20sccm / 30sccm.

[0019] As preferably, the sputtering power of the two target materials in step S2 is 100W and 60W respectively.

[0020] As preferably, the film deposition time in step S2 is 3h.

[0021] As preferably, the sputtering process in step S2 adopts a mode of 50min deposition per cycle, followed by 10min cooling.

[0022] The application also provides a crystal-amorphous thin film with super-smooth surface prepared by the above method.

[0023] The application also provides an application of the crystal-amorphous thin film with super-smooth surface, which includes the application of the crystal-amorphous thin film with super-smooth surface in preparing mechanical part protective coating.

[0024] The application has the following advantages:

[0025] 1. The application provides a method for preparing a crystal-amorphous thin film with super-smooth surface, the coordinated flow behavior of the MG phase and dislocation flow in the crystal makes the uniform plastic co-deformation of the two regions possible; the design concept of the crystal-amorphous high-entropy nanocomposite material provides a new method for developing advanced materials with super-smooth surface and high hardness, low friction coefficient.

[0026] 2. The composite thin film obtained by the method has high purity, good density and good film uniformity; the thin film is well combined with the substrate and is easy to realize industrialization.

[0027] 3. The hardness and elastic modulus of the composite thin film prepared by the application are higher than those of ordinary high-entropy alloy materials. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiment or prior art description. Obviously, the drawings in the following description only constitute some embodiments of the application, and for those skilled in the art, other drawings can also be obtained without creative labor based on these drawings.

[0029] Figure 1 It is a schematic diagram of the positional relationship between the two target materials and the substrate in the embodiment of the application.

[0030] Figure 2 It is an XRD diagram of the thin film in the embodiment.

[0031] Figure 3 This is a cross-sectional topography diagram of the thin film in the embodiment;

[0032] Figure 4 The AFM surface morphology and roughness diagrams of the thin film in the examples are shown.

[0033] Explanation of reference numerals in the attached figures: Figure 3 , Figure 4 In the diagram, (a) represents N0; (b) represents N3; (c) represents N10; (d) represents N20; and (e) represents N30. Detailed Implementation

[0034] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0035] A method for preparing a crystalline-amorphous thin film with an ultra-smooth surface includes the following steps:

[0036] S1. Preparation of high-entropy composite target material:

[0037] High-purity Al, Cr, Zr, Mo, and V powders are melted and synthesized into alloy raw materials in equimolar proportions and then cast into ingots using powder metallurgy.

[0038] The ingot is then crushed, ball-milled into powder, and then sieved.

[0039] The alloy powder was loaded into the mold by isostatic pressing and then sintered at high temperature with parameters of 650℃ / 45min, 850℃ / 45min, and 1400℃ / 3h. Finally, the formed alloy sample was cooled to room temperature and demolded to form AlCrZrMoV high-entropy alloy target.

[0040] TiBC composite targets with a TiB2:TiC ratio of 0.8:0.2 were prepared using the same method.

[0041] S2. Preparation of crystalline-amorphous thin films using magnetron sputtering:

[0042] S2.1 Cleaning: The silicon wafer substrate is continuously ultrasonically cleaned in petroleum ether and ethanol for 15-20 minutes;

[0043] S2.2, Deoxide Removal: Before depositing the thin film, the sample is subjected to low-energy Ar oxidation. + Ion bombardment for 10 minutes to eliminate oxide impurities;

[0044] S2.3, sputtering film: AlCrZrMoV high-entropy alloy target and TiBC composite target are placed 15 cm below the substrate (as shown in Figure 1 When the pressure in the vacuum chamber is lower than Mpa, sputtering film can be started; the sputtering gas pressure is 0.3-0.6 Pa; the total Ar gas flow and N2 flow is kept at 60 sccm, and the N2 flow is 3 sccm, 10 sccm, 20 sccm, and 30 sccm respectively; a bias voltage of -80 V is applied to the substrate, and the duty cycle is 70%; the sputtering power of the two kinds of target materials is 100 W and 60 W respectively, and a crystal-amorphous thin film is prepared.

[0045] Further, in step S1, the molar ratio of high-purity Al, Cr, Zr, Mo, and V is 1:1:1:1:1; the ratio of TiB2:TiC is 0.8:0.2.

[0046] Further, in step S1, the parameters of high-temperature sintering are 650℃ / 45min, 850℃ / 45min, and 1400℃ / 3h respectively.

[0047] Further, in step S2, the N2 flow is 3 sccm / 10 sccm / 20 sccm / 30 sccm.

[0048] Further, in step S2, the sputtering power of the two kinds of target materials is 100 W and 60 W respectively.

[0049] Further, in step S2, the film deposition time is 3h.

[0050] Further, in step S2, the sputtering process adopts a mode of 50min deposition per cycle, followed by 10min cooling. Example 1

[0051] A crystal-amorphous thin film with super-smooth surface is prepared by the following method:

[0052] S1, preparation of high-entropy composite target:

[0053] High-purity Al, Cr, Zr, Mo, and V powders are melted and alloyed according to the equal molar ratio of alloy raw materials, and then cast into ingots by powder metallurgy method;

[0054] The ingots are crushed and ball milled into powders, which are then sieved;

[0055] The alloy powders are loaded into a mold by isostatic pressing, and then high-temperature sintering is performed with parameters of 650℃ / 45min, 850℃ / 45min, and 1400℃ / 3h respectively. Finally, the formed alloy sample is cooled to room temperature and demolded, and an AlCrZrMoV high-entropy alloy target is finally formed.

[0056] TiBC composite targets with a TiB2:TiC ratio of 0.8:0.2 were prepared using the same method.

[0057] S2. Preparation of crystalline-amorphous thin films using magnetron sputtering:

[0058] S2.1 Cleaning: The silicon wafer substrate is continuously ultrasonically cleaned in petroleum ether and ethanol for 15-20 minutes.

[0059] S2.2, Deoxide Removal: Before depositing the thin film, the sample is subjected to low-energy Ar oxidation. + Ion bombardment for 10 minutes to eliminate oxide impurities;

[0060] S2.3 Sputtering Coating: AlCrZrMoV high-entropy alloy target and TiBC composite target are placed 15cm below the substrate. When the vacuum chamber pressure is lower than... Sputtering can begin at MPa; sputtering pressure is 0.3-0.6 Pa; the total flow rate of Ar gas and N2 gas is kept constant at 60 sccm, and the flow rate of N2 gas is 3 sccm; a bias voltage of -80V is applied to the substrate, with a duty cycle of 70%; the sputtering power of the two targets is 100W and 60W respectively, to obtain a crystalline-amorphous thin film, denoted as N3. Example 2

[0061] The difference between this embodiment and the previous embodiment is that the N2 gas flow rate in step S2 is 10 sccm, while the other steps are the same as in embodiment 1, and the resulting film is denoted as N10. Example 3

[0062] The difference between this embodiment and the previous embodiment is that the N2 gas flow rate in step S2 is 20 sccm, while the other steps are the same as in embodiment 1, and the resulting film is denoted as N20. Example 4

[0063] The difference between this embodiment and the previous embodiment is that the N2 gas flow rate in step S2 is 30 sccm, while the other steps are the same as in embodiment 1, and the resulting film is denoted as N30.

[0064] Comparative Example 1

[0065] The difference between this embodiment and Embodiment 1 is as follows:

[0066] 1. In step S2, the flow rates of Ar and N2 gases are 30 sccm and 0 sccm, respectively;

[0067] 2. In step S2, the sputtering target only uses the AlCrZrMoV high-entropy alloy target prepared by the method in step S1, and does not use the TiBC composite target. The resulting film is denoted as N0.

[0068] The performance parameters, surface morphology and roughness, and phase of the thin film materials obtained in Examples 1-4 and Comparative Example 1 were detected, and the detection results are as follows:

[0069] The hardness and elastic modulus of the nanocomposite thin film were measured by using a nanoindentation tester using a continuous stiffness mode, and in order to avoid the adverse effects of the substrate on the measurement data, the indentation depth was not more than one tenth of the overall depth of the thin film, and the measurement results are shown in Table 1.

[0070] Table 1. Basic parameters, hardness, and elastic modulus of the nanocomposite thin film coating.

[0071] As can be seen from Table 1, the crystal-amorphous thin film prepared by the method of the present application has better hardness and elastic modulus than the thin film obtained by sputtering only using the AlCrZrMoV high-entropy alloy target.

[0072] Figure 2 The X-ray diffraction patterns of the thin films obtained in Examples 1-4 and Comparative Example 1 show that the crystal-amorphous thin film prepared by the method of the present application has a dual-phase structure of amorphous phase and FCC phase compared with the thin film obtained by sputtering only using the AlCrZrMoV high-entropy alloy target. And as the N2 gas flow increases, the preferred orientation of the prepared composite thin film material changes. When the nitrogen flow increases to 30 SCCM, the thin film structure is mainly amorphous, with a small amount of crystal structure.

[0073] Figure 3 The cross-sectional morphology of the thin films obtained in Examples 1-4 and Comparative Example 1 shows that the thickness of the crystal-amorphous thin film prepared by the method of the present application is 1-1.74 microns, and as the N2 gas flow increases, the thickness of the prepared thin film gradually decreases. The Si sheet substrate of the thin film is not separated, indicating that they are well combined, and the thin film is vertically distributed perpendicular to the substrate surface.

[0074] Figure 4 The atomic force microscope (AFM) measurement result graph (the scanning area is 5*5 microns) shows the surface morphology and roughness of the thin films obtained in Examples 1-4 and Comparative Example 1, and the size difference of the particle structure can be observed. With the introduction of nitrogen, the roughness of the thin film first increases and then decreases. The crystal-amorphous thin film (N30) prepared by the method of the present application has smaller roughness and is more dense than the thin film obtained by sputtering only using the AlCrZrMoV high-entropy alloy target.

[0075] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalent technologies, the present application also intends to include these modifications and variations.

Claims

1. A method for preparing a crystalline-amorphous thin film having an ultra-smooth surface, characterized in that, The method comprises the following steps: S1, preparing a high-entropy composite target material: Al, Cr, Zr, Mo, and V powders with high purity are melted and cast into ingots by powder metallurgy; The ingots are crushed and ball-milled into powders, which are then sieved; The alloy powders are loaded into a mold by isostatic pressing, and then high-temperature sintering is performed, and finally the formed alloy sample is cooled to room temperature and demolded, and the AlCrZrMoV high-entropy alloy target material is obtained; A TiBC composite target material is prepared by the same method using TiB2 and TiC as raw materials; S2, preparing a crystal-amorphous thin film by a magnetron sputtering method: S2.1, cleaning: the silicon substrate is cleaned in petroleum ether and ethanol for 15-20 min by ultrasonic cleaning; S2.2, De-oxidation: The sample was subjected to low-energy Ar + Ion bombardment for 10 min to eliminate oxide impurities; S2.3, sputtering film: AlCrZrMoV high-entropy alloy target and TiBC composite target are placed 15 cm below the substrate, and when the pressure in the vacuum chamber is lower than 4-6x10 −5 Mpa, sputtering film can be started; The sputtering pressure is 0.3-0.6 Pa; the total Ar gas flow and N2 flow are kept at 60 sccm, and the N2 flow is 3 sccm, 10 sccm, 20 sccm, and 30 sccm, respectively; a bias voltage of-80 V is applied to the substrate, and the duty cycle is 70%, and a crystal-amorphous thin film is prepared.

2. The method for preparing a crystal-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S1, the molar ratio of high-purity Al, Cr, Zr, Mo, and V is 1:1:1:1:1; the ratio of TiB2 to TiC is 0.8:0.

2.

3. The method for preparing a crystalline-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S1, the high-temperature sintering parameters are 650 ℃ / 45 min, 850 ℃ / 45 min, and 1400 ℃ / 3 h, respectively.

4. The method for preparing a crystal-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S2, the sputtering power of the two target materials is 100 W and 60 W, respectively.

5. The method for preparing a crystalline-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S2, the film plating time is 3 h.

6. The method for preparing a crystalline-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S2, the sputtering process adopts a mode of depositing for 50 min per cycle, and then cooling for 10 min.

7. The method for preparing a crystal-amorphous thin film with an ultra-smooth surface as described in claim 1, characterized in that, In step S2, the thickness of the crystal-amorphous thin film is between 1-1.74 μm.

8. A crystalline-amorphous thin film having an ultra-smooth surface, characterized in that, Prepared by the preparation method of any one of claims 1-7.

9. Use of a crystalline-amorphous thin film having an ultra-smooth surface according to claim 8, characterized in that, The application includes the application of the crystal-amorphous thin film with an ultra-smooth surface in the preparation of mechanical part protective coatings.

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