A zirconium-titanium-silver amorphous / silver nanocrystal multilayer film and a preparation method thereof

Abstract

The application relates to a zirconium-titanium-silver amorphous / silver nanocrystal multilayer film and a preparation method thereof, the multilayer film comprising a zirconium-titanium-silver amorphous film and a silver nanocrystal film with a periodic modulation structure which are sequentially deposited on the surface of a substrate, the total thickness of the multilayer film is 70-100 nm when one period is adopted, and the period number of the multilayer film is 5-15. Compared with the prior art, the application further reduces the elastic modulus while maintaining high hardness.

Description

Technical Field

[0001] This invention belongs to the field of multilayer thin film technology, and relates to a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film and its preparation method. Background Technology

[0002] Currently, traditional multilayer thin films, such as metal multilayer and silicon-based multilayer thin films, have relatively poor corrosion resistance and are prone to problems such as peeling, oxidation, and deterioration during long-term use or in harsh environments, which reduces the reliability and stability of the film.

[0003] The main methods for preparing amorphous alloys include vapor deposition, liquid phase quenching, and reaction methods. Liquid phase quenching is mainly used for preparing bulk amorphous materials, while the preparation of amorphous alloy thin films mainly employs reaction methods (electroplating, electroless plating, and vapor deposition) and vapor deposition methods (pulsed laser deposition and magnetron sputtering). However, in actual production, electroplating causes significant environmental pollution, electroless plating requires special treatment of the substrate surface and has poor film adhesion, and vapor deposition is difficult to control in terms of composition ratio and film formation is challenging. While pulsed laser deposition also has significant advantages, the expensive equipment makes it difficult to use on a large scale. Therefore, in comparison, magnetron sputtering offers advantages such as high efficiency, low temperature, good film formation with dense surface, low roughness, and controllable thickness.

[0004] Compared to other methods for preparing amorphous alloys, which are prone to producing crystalline phases, pores, or cracks, magnetron sputtering offers extremely fast cooling rates, making it an ideal method for preparing amorphous alloy thin film materials. It boasts advantages such as uniform film formation, low substrate temperature rise, high film density, good film-substrate bonding, and excellent controllability and repeatability of the deposition process, and is widely used in microelectronics, semiconductors, and aerospace fields.

[0005] Patent CN117127149A discloses an amorphous alloy thin film, its preparation method, and its application. The thin film is a zirconium-based amorphous alloy thin film co-doped with titanium and silver. The target materials used to prepare the thin film are a zirconium-titanium alloy target and a pure silver target. The thin film is obtained by DC co-sputtering of the zirconium-titanium alloy target and the pure silver target using magnetron sputtering. However, this patent does not significantly improve the brittleness of amorphous materials.

[0006] Patent CN108468032A discloses a method for preparing nanocrystalline thin films with improved plasticity, including: using magnetron sputtering to introduce an amorphous layer into nanocrystals to form a multilayer structure of alternating nanocrystalline / amorphous layers, thereby obtaining a nanocrystalline thin film with improved plasticity. However, this patent only improves hardness and does not provide clear performance guidance regarding elastic modulus. Summary of the Invention

[0007] The purpose of this invention is to overcome at least one defect of the prior art and provide a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film and its preparation method. This invention maintains high hardness while further reducing the elastic modulus.

[0008] The objective of this invention can be achieved through the following technical solutions:

[0009] One of the technical solutions of the present invention is to provide a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film, the multilayer film comprising a zirconium-titanium-silver (Zr-Ti-Ag) amorphous film and a silver (Ag) nanocrystalline film having a periodic modulation structure sequentially deposited on the surface of a substrate, wherein the total thickness of the multilayer film is 70-100 nm when using one cycle, and the number of cycles of the multilayer film is 5-15.

[0010] Furthermore, the thickness of the zirconium-titanium-silver amorphous thin film is 10-20 nm.

[0011] Furthermore, the thickness of the silver nanocrystal film is 60-80 nm.

[0012] One of the technical solutions of the present invention is to provide a method for preparing zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin films. This method involves layer-depositing zirconium-titanium-silver amorphous thin films and silver nanocrystalline thin films on the surface of a substrate by DC magnetron sputtering. The method includes the following steps:

[0013] S1. Preparation of amorphous thin films: Zirconium-titanium-silver amorphous thin films are deposited on the surface of the substrate using a zirconium-titanium alloy target and a pure silver elemental target;

[0014] S2. Preparation of nanocrystalline thin films: Silver nanocrystalline thin films are deposited on the surface of zirconium-titanium-silver amorphous thin films using a pure silver target.

[0015] S3. Multilayer film preparation: The zirconium-titanium-silver amorphous film in step S1 and the silver nanocrystalline film in step S2 are deposited alternately multiple times on the surface of the silver nanocrystalline film to obtain a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film.

[0016] As a preferred technical solution, the substrate includes a glass sheet, a silicon (Si) sheet, or a titanium alloy (Ti6Al4V) sheet.

[0017] As a preferred technical solution, the atomic content ratio of zirconium to titanium in the zirconium-titanium alloy target is (90-70):(10-30).

[0018] Furthermore, the following steps are taken before step S1:

[0019] Surface cleaning: Clean the surface of the substrate and dry it after cleaning for later use;

[0020] Vacuum pre-evacuation: The equipment is roughly evacuated to a vacuum, and then a high vacuum is evacuated;

[0021] Gas introduction: Inert gas is introduced into the equipment to maintain a vacuum;

[0022] Glow Glow Cleaning: Glow Glow Cleaning is performed on zirconium-titanium alloy targets and pure silver targets.

[0023] As a preferred technical solution, the reagent for cleaning the substrate is selected from one or more of acetone and ethanol.

[0024] Furthermore, the vacuum degree of the rough vacuum pumping is 5-10 Pa, and the vacuum degree of the high vacuum pumping is 1×10 Pa. -4 -1×10 -3 Pa.

[0025] As a preferred technical solution, the inert gas is argon (Ar).

[0026] Furthermore, the flow rate of the inert gas is 80-100 sccm, and the vacuum degree for maintaining the vacuum is 1-5 Pa.

[0027] Furthermore, the power of the zirconium-titanium alloy target is 120-200W, the power of the pure silver target is 25-40W, and the glow discharge cleaning time is 3-7 minutes.

[0028] As a preferred technical solution, the rotational speed of the substrate in steps S1 and S2 is 80-100 r / min.

[0029] Furthermore, in step S1, the power of the zirconium-titanium alloy target is 120-200W, the power of the pure silver target is 25-40W, and the deposition time is 90-110min.

[0030] Furthermore, in step S2, the power of the pure silver target is 25-40W, and the deposition time is 130-150min.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] (1) The zirconium-titanium-silver amorphous thin film of the present invention has a large zirconium content, which can reduce the elastic modulus of the amorphous thin film;

[0033] (2) The addition of titanium to the zirconium-titanium-silver amorphous thin film of the present invention not only improves the corrosion resistance of the amorphous thin film, but also improves the biocompatibility of the amorphous thin film.

[0034] (3) The addition of silver to the zirconium-titanium-silver amorphous thin film of the present invention gives the amorphous thin film antibacterial properties and also optimizes the toughness of the amorphous thin film.

[0035] (4) The zirconium-titanium-silver amorphous thin film of the present invention has the characteristics of short-range ordered and long-range disordered arrangement of its atoms, which gives the amorphous thin film the advantages of uniformity, high elasticity and amorphous shape. Compared with traditional thin films, the synergistic effect of zirconium, titanium and silver can make the amorphous thin film not only have high toughness, but also exhibit high hardness, low elastic modulus, good corrosion resistance, electrical conductivity and antibacterial properties. Because the amorphous thin film has high glass forming ability, high hardness and excellent corrosion resistance, it is suitable for applications in various fields, such as medical devices, food packaging, optical coatings, sensors, electronic devices, anti-corrosion films, etc. As an anti-corrosion film, it can be used for corrosion protection of certain shells, valves and other important components of marine equipment facilities to improve service life.

[0036] (5) The silver nanocrystal film of the present invention can enhance the antibacterial and antioxidant properties of the nanocrystal film. The amorphous / nanocrystal interface is conducive to hindering the penetration of substances and the expansion of micro-defects, further improving the corrosion resistance of the film, reducing the elastic modulus of the film, and improving the brittleness of the amorphous film.

[0037] (6) The thin film of the present invention is prepared by magnetron sputtering technology. The resulting multilayer thin film has uniform composition, dense structure and excellent anti-corrosion performance. The preparation method is low cost, simple process, easy parameter control and suitable for large-scale promotion. Attached Figure Description

[0038] Figure 1 This is a schematic diagram of the structure of a single-cycle zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film in an embodiment of the present invention;

[0039] Figure 2 This is a schematic diagram of the structure of the multi-period zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film in an embodiment of the present invention;

[0040] Figure 3 This is a comparison diagram of the hardness of the thin films in the embodiments and comparative examples of the present invention;

[0041] Figure 4 This is a comparison chart of the Young's modulus of the thin films in the embodiments and comparative examples of the present invention.

[0042] Explanation of markings in the diagram:

[0043] 1—Substrate, 2—Zirconium-titanium-silver amorphous thin film, 3—Silver nanocrystalline thin film. Detailed Implementation

[0044] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0045] Unless otherwise specified, the equipment used in the following embodiments is conventional equipment in the art; unless otherwise specified, the reagents used are commercially available products or prepared by conventional methods in the art. In the following embodiments, unless otherwise described in detail, conventional experimental methods in the art can be used.

[0046] Example 1:

[0047] A zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film, such as Figure 1 and Figure 2 As shown, the substrate 1 includes a zirconium-titanium-silver (Zr-Ti-Ag) amorphous thin film 2 and a silver (Ag) nanocrystalline thin film 3, which are sequentially deposited on the surface of the substrate 1 and have a periodic modulation structure. The thickness of the zirconium-titanium-silver amorphous thin film 2 is 15 nm, the thickness of the silver nanocrystalline thin film 3 is 60 nm, the total thickness of the multilayer film is 75 nm when one cycle is used, and the number of cycles of the multilayer film is 10.

[0048] The above-mentioned method for preparing zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin films involves depositing zirconium-titanium-silver amorphous thin film 2 and silver nanocrystalline thin film 3 on the surface of substrate 1 by DC magnetron sputtering. The specific steps are as follows:

[0049] S1. Target material preparation: Convert the atomic percentage of element content to mass percentage, balance the raw materials, and melt the balanced raw materials into zirconium-titanium alloy targets and pure silver targets. The atomic ratio of zirconium to titanium in the zirconium-titanium alloy target is 80:20, and the purity of zirconium and titanium is 99.9%. The purity of silver in the pure silver target is 99.9%.

[0050] S2. Surface cleaning: The substrate 1 is selected with a size of 10×10mm. 2 The glass slide was used to clean the surface of substrate 1 in sequence with acetone and anhydrous ethanol. After cleaning, it was dried and clamped into the sputtering chamber of the magnetron sputtering equipment.

[0051] S3. Vacuum Pre-Pumping: Roughly evacuate the sputtering chamber to 8 Pa, run the molecular pump, open the solenoid valve, and then evacuate to a high vacuum of 3.5 × 10⁻⁶ Pa. -4 Pa;

[0052] S4. Gas introduction: Introduce argon (Ar) gas at a flow rate of 90 sccm into the sputtering chamber to create an inert environment and maintain a vacuum at 1.0 Pa;

[0053] S5. Glow Glow Cleaning: Turn on the target power and adjust the power of the zirconium-titanium alloy target to 200W and the power of the pure silver target to 25W. Perform glow glow cleaning on the target material for 5 minutes.

[0054] S6. Amorphous thin film preparation: To ensure uniform sputtering, the substrate 1 needs to be turned on and the rotation speed of the substrate 1 needs to be adjusted to 80 r / min. The target baffle is turned on and sputtering is started. The power of the zirconium-titanium alloy target is adjusted to 180 W and the power of the pure silver target is adjusted to 30 W. The zirconium-titanium alloy target and the pure silver target are deposited on the surface of the substrate 1 for 100 min to obtain a 15 nm zirconium-titanium-silver amorphous thin film 2.

[0055] S7. Preparation of nanocrystalline thin film: The power of the pure silver target was adjusted to 30W, and pure silver target was used to deposit on the surface of zirconium-titanium-silver amorphous thin film 2 for 130min to obtain a 60nm silver nanocrystalline thin film 3.

[0056] S8. Multilayer film preparation: The zirconium-titanium-silver amorphous film 2 in step S6 and the silver nanocrystalline film 3 in step S7 are deposited alternately on the surface of the silver nanocrystalline film 3 10 times to obtain a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film.

[0057] Comparative Example 1:

[0058] A zirconium-titanium-silver amorphous thin film and its preparation method are basically the same as those in Example 1, except that the silver nanocrystalline thin film 3 is not deposited in step S7, the time for depositing the zirconium-titanium-silver amorphous thin film 2 in step S6 is changed to 230 min, and a 75 nm zirconium-titanium-silver amorphous thin film 2 is obtained. In step S8, the zirconium-titanium-silver amorphous thin film 2 is deposited 10 times on the surface of the zirconium-titanium-silver amorphous thin film 2 as in step S6.

[0059] Example 2:

[0060] A zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film and its preparation method are basically the same as those in Example 1, except that the deposition time of silver nanocrystalline thin film 3 in step S7 is changed to 140 min to obtain a 70 nm silver nanocrystalline thin film 3, and in step S8, the deposition of zirconium-titanium-silver amorphous thin film 2 in step S6 is repeated 10 times on the surface of zirconium-titanium-silver amorphous thin film 2.

[0061] Comparative Example 2:

[0062] A zirconium-titanium-silver amorphous thin film and its preparation method are basically the same as those in Example 2, except that the silver nanocrystalline thin film 3 is not deposited in step S7, the time for depositing the zirconium-titanium-silver amorphous thin film 2 in step S6 is changed to 240 min, and an 85 nm zirconium-titanium-silver amorphous thin film 2 is obtained. In step S8, the zirconium-titanium-silver amorphous thin film 2 is deposited 10 times on the surface of the zirconium-titanium-silver amorphous thin film 2 as in step S6.

[0063] Example 3:

[0064] A zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film and its preparation method are basically the same as those in Example 1, except that the deposition time of silver nanocrystalline thin film 3 in step S7 is changed to 150 min to obtain an 80 nm silver nanocrystalline thin film 3, and in step S8, the deposition of zirconium-titanium-silver amorphous thin film 2 in step S6 is repeated 10 times on the surface of zirconium-titanium-silver amorphous thin film 2.

[0065] Comparative Example 3:

[0066] A zirconium-titanium-silver amorphous thin film and its preparation method are basically the same as those in Example 2, except that the silver nanocrystalline thin film 3 is not deposited in step S7, the time for depositing the zirconium-titanium-silver amorphous thin film 2 in step S6 is changed to 250 min, and a 95 nm zirconium-titanium-silver amorphous thin film 2 is obtained. In step S8, the zirconium-titanium-silver amorphous thin film 2 is deposited 10 times on the surface of the zirconium-titanium-silver amorphous thin film 2 as in step S6.

[0067] The specific steps for the mechanical property experiments of the above-mentioned thin films are as follows:

[0068] The mechanical properties of the thin films were tested using the continuous stiffness method and the constant force 8 mN nanoindentation method. Each sample was measured 10 times, and the average value was recorded to minimize error. The experimental results of the mechanical properties of each embodiment and comparative example are shown below. Figure 3 and Figure 4 .

[0069] like Figure 3 and Figure 4 As shown, the hardness of the multilayer films in Examples 1 to 3 are 6.1 GPa, 7.4 GPa, and 6.7 GPa, respectively, while the hardness of the amorphous films in Comparative Examples 1 to 3 are 6.3 GPa, 7.6 GPa, and 6.8 GPa, respectively. The difference is between 0.1 and 0.2 GPa. The hardness of the zirconium-titanium-silver amorphous / silver nanocrystalline multilayer films is not significantly different from that of the zirconium-titanium-silver amorphous films. The Young's moduli of the multilayer films in Examples 1 to 3 are 100 GPa, 113 GPa, and 98 GPa, respectively, while the Young's moduli of the amorphous films in Comparative Examples 1 to 3 are 125 GPa, 135 GPa, and 120 GPa, respectively. The Young's moduli of the zirconium-titanium-silver amorphous / silver nanocrystalline multilayer films is significantly lower by 22-25 GPa compared to the zirconium-titanium-silver amorphous films. The lower Young's moduli indicates that the brittleness of the amorphous films has been improved. In summary, the mechanical properties of the zirconium-titanium-silver amorphous / silver nanocrystalline multilayer films prepared by this invention meet the design expectations.

[0070] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film, characterized in that, The multilayer film includes a zirconium-titanium-silver amorphous film (2) and a silver nanocrystalline film (3) with periodic modulation structure, which are sequentially deposited on the surface of a substrate (1). The total thickness of the multilayer film is 70-100 nm when one period is used, and the number of periods of the multilayer film is 5-15. The method includes the following steps: S1. Amorphous thin film preparation: Zirconium-titanium-silver amorphous thin film (2) is deposited on the surface of the substrate (1) using a zirconium-titanium alloy target and a pure silver single target. S2. Preparation of nanocrystalline thin film: Silver nanocrystalline thin film (3) is deposited on the surface of zirconium-titanium-silver amorphous thin film (2) using pure silver elemental target. S3. Multilayer film preparation: The zirconium-titanium-silver amorphous film (2) in step S1 and the silver nanocrystalline film (3) in step S2 are deposited alternately on the surface of the silver nanocrystalline film (3) multiple times to obtain zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film. In step S1, the power of the zirconium-titanium alloy target is 120-200 W, the power of the pure silver target is 25-40 W, and the deposition time is 90-110 min. In step S2, the power of the pure silver target is 25-40 W, and the deposition time is 130-150 min.

2. The method for preparing a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 1, characterized in that, Before step S1, take the following steps: Surface cleaning: Cleaning the surface of the substrate; Vacuum pre-evacuation: The equipment is roughly evacuated to a vacuum, and then a high vacuum is evacuated; Gas introduction: Inert gas is introduced into the equipment to maintain a vacuum; Glow Glow Cleaning: Glow Glow cleaning is performed on zirconium-titanium alloy targets and pure silver targets.

3. The method for preparing a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 2, characterized in that, The rough vacuum level is 5-10 Pa, and the high vacuum level is 1×10 Pa. -4 -1×10 -3 Pa.

4. The method for preparing a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 2, characterized in that, The flow rate of the inert gas is 80-100 sccm, and the vacuum level for maintaining the vacuum is 1-5 Pa.

5. The method for preparing a zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 2, characterized in that, The power of the zirconium-titanium alloy target is 120-200 W, the power of the pure silver target is 25-40 W, and the glow discharge cleaning time is 3-7 min.

6. A zirconium-titanium-silver amorphous / silver nanocrystalline multilayer film prepared by the method as described in claim 1.

7. The zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 6, characterized in that, The thickness of the zirconium-titanium-silver amorphous thin film (2) is 10-20 nm.

8. The zirconium-titanium-silver amorphous / silver nanocrystalline multilayer thin film according to claim 6, characterized in that, The thickness of the silver nanocrystal film (3) is 60-80 nm.

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