Composite film, optical member and method for manufacturing the same, electronic device

Abstract

The application relates to the field of wear-resistant materials, and discloses a composite film, an optical element and a preparation method thereof, and an electronic device. The composite film comprises a plurality of laminated composite layers, and each composite layer comprises a deposition layer and a Si3N4 layer on the deposition layer. The composition of the deposition layer comprises a crystal phase and a strengthening phase. The crystal phase is AN, and A is selected from one or more of Ti, Cr, W, V and Zr. The strengthening phase is X, and X is selected from Cu and / or Ag. In the composite film obtained by the application, Cu or Ag which is completely insoluble in AN is added into the AN coating. The addition of Cu or Ag not only greatly reduces the internal stress of the coating, improves the hardness and fracture toughness of the coating, but also greatly improves the wear resistance, toughness and hardness due to the solid solution strengthening and fine-grain strengthening of Cu or Ag atoms. In addition, the low activity of Si3N4 is adsorbed on the surface of the growing AN particles, thereby hindering the grain growth, and the hardness of the film layer is further strengthened.

Description

Technical Field

[0001] This invention relates to the field of wear-resistant materials, specifically to a composite film, an optical component and its preparation method, and an electronic device. Background Technology

[0002] Currently, coating processes are often used in smart terminals, especially mobile phones, tablets, laptops, projectors, instrument protective windows, and special lenses, to improve product properties and achieve special optical functions and decorative effects.

[0003] Existing composite coating technologies, when used in non-metallic cover plates, have certain limitations in application, and single CrSiCN structural layers exhibit low wear resistance, hardness, and corrosion resistance. Some nanocomposite coatings are quite thick, resulting in poor toughness and increasing the film's brittle fracture tendency. Some carbon-doped TiAlN nanolayered hard thin film coatings contain an underlayer, transition layer, functional layer, and coating layer, resulting in complex structures, cumbersome preparation processes, and difficulty in accurately obtaining optimized modulation cycles and modulation ratios. While some coatings possess high wear resistance and toughness, they do not exhibit the hardness characteristic of nanocrystalline-amorphous multiphase composite coatings.

[0004] Currently, the coatings disclosed in existing technologies are not hard enough and have poor wear resistance. Therefore, there is an urgent need to study coatings or composite film materials with higher performance. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor coating hardness and wear resistance in the prior art, and to provide a composite film, optical components and their preparation methods, and electronic devices.

[0006] To achieve the above objectives, a first aspect of the present invention provides a composite film, wherein the composite film comprises multiple stacked composite layers, the composite layer comprising: a deposition layer and a Si3N4 layer on the deposition layer, wherein the composition of the deposition layer includes a crystalline phase and a reinforcing phase, the crystalline phase being AN, where A is selected from one or more of Ti, Cr, W, V and Zr; the reinforcing phase being X, where X is selected from Cu and / or Ag.

[0007] A second aspect of the present invention provides an optical component, wherein the optical component includes a substrate and a composite film disposed on the surface of the substrate, wherein the substrate includes one or more of metal, glass, ceramic, and sapphire.

[0008] A third aspect of the present invention provides a method for manufacturing an optical component, comprising:

[0009] A substrate is provided, and at least one composite layer is deposited on the surface of the substrate. The composite layer includes a deposited layer and a Si3N4 layer stacked sequentially. The deposited layer comprises a crystalline phase and a reinforcing phase. The crystalline phase is AN, where A is selected from one or more of Ti, Cr, W, V and Zr. The reinforcing phase is X, where X is selected from Cu and / or Ag.

[0010] A fourth aspect of the present invention provides an electronic device, wherein the electronic device comprises the composite film, the optical element, or the optical element obtained by the preparation method described above.

[0011] Through the above technical solution, the composite film obtained in this application selects Cu or Ag, which are completely insoluble in AN, to be added to the AN coating. The addition of Cu or Ag not only greatly reduces the internal stress of the coating and improves the coating hardness and fracture toughness, but also the solid solution strengthening and grain refinement of Cu or Ag atoms bring about a significant improvement in wear resistance, toughness and hardness. At the same time, Si3N4, due to its low activity, is adsorbed on the surface of the grown AN particles, hindering grain growth, and the film layer is further strengthened. Attached Figure Description

[0012] Figure 1 This is a schematic diagram of a composite film with an Al alloy substrate.

[0013] Figure 2 This is a schematic diagram of a composite film with a substrate that is not an Al alloy. Detailed Implementation

[0014] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0015] The first aspect of the present invention provides a composite film, wherein the composite film comprises multiple stacked composite layers, the composite layer comprising: a deposition layer and a Si3N4 layer on the deposition layer, wherein the deposition layer comprises a crystalline phase and a reinforcing phase, the crystalline phase being AN, where A is selected from one or more of Ti, Cr, W, V and Zr; the reinforcing phase being X, where X is selected from Cu and / or Ag.

[0016] In this invention, the composite film obtained in this application comprises a deposition layer composed of a crystalline phase and a reinforcing phase, wherein the Cu or Ag of the reinforcing phase is completely insoluble with the AN of the crystalline phase. The addition of Cu or Ag to the AN coating not only greatly reduces the internal stress of the coating, but also improves the hardness and fracture toughness of the coating. The solid solution strengthening of Cu or Ag atoms and the fine grain strengthening significantly improve the wear resistance, toughness and hardness of the composite film. At the same time, due to the low activity of Si3N4, it is adsorbed on the surface of the grown AN particles, hindering grain growth, and the film layer is further strengthened. The deposition layer and the Si3N4 layer on the deposition layer significantly improve the wear resistance, toughness and hardness of the composite film.

[0017] In this invention, the composite film may include multiple composite layers, with the deposited layer and Si3N4 layer alternately forming a multilayer composite layer stacked structure. By stacking single layers, a composite film structure with a desensitizing layer can be formed, which greatly improves wear resistance, toughness and hardness, and further strengthens the film layer.

[0018] In some specific embodiments of the present invention, in the composite film, the thickness ratio of the deposited layer to the Si3N4 layer is 1:(1-3), preferably 1:2. Within this thickness ratio range, a higher Si3N4 content in the composite film reduces the material's sensitivity to wear, but too much will reduce the reinforcing effect of the deposited layer. Therefore, when the thickness ratio of the deposited layer to the Si3N4 layer is 1:(1-3), the composite film has high hardness and good wear resistance.

[0019] In some specific embodiments of the present invention, the total thickness of the composite film is 600-3000 nm, preferably 800-2000 nm; wherein, the thickness of each layer of the composite film may be the same or different. Within the above thickness range, the composite film has high strength and high wear resistance.

[0020] In some specific embodiments of the present invention, in the composite layer, the thickness of the Si3N4 layer is 20-500 nm, preferably 20-250 nm; the thickness of the deposited layer is 20-600 nm, preferably 50-300 nm. When the thicknesses of the Si3N4 layer and the deposited layer are within the above-mentioned thickness ranges, the composite stack exhibits high strength and high wear resistance.

[0021] In some specific embodiments of the present invention, the composite membrane comprises 6-30 composite layers, preferably 6-18. When the number of multiple layers is in the range of 6-30, preferably 6-18, the internal stress caused by too many layers can be reduced, thus reducing the wear resistance.

[0022] In some specific embodiments of the present invention, preferably, A is Ti, the crystal phase is TiN, and the strengthening phase is Cu.

[0023] In some specific embodiments of the present invention, the composite film has a nanohardness of 17-23 GPa and a pencil hardness of 7-9H. By selecting Cu or Ag, which are completely insoluble with AN, and adding them to the AN coating, the addition of Cu or Ag not only greatly reduces the internal stress of the coating and improves the coating hardness and fracture toughness, but also significantly improves wear resistance, toughness, and hardness due to the solid solution strengthening and grain refinement of Cu or Ag atoms. At the same time, Si3N4, due to its low mobility, adsorbs on the surface of the grown AN particles, hindering grain growth, and the film layer is further strengthened, thereby increasing the nanohardness of the composite film, and the pencil hardness can reach 9H.

[0024] A second aspect of the present invention provides an optical component, wherein the optical component includes a substrate and a composite film disposed on the surface of the substrate, wherein the substrate includes one or more of metal, glass, ceramic, and sapphire.

[0025] In some specific embodiments of the present invention, the lowest deposited layer of the composite film is located on the surface of the substrate. For example... Figure 1 As shown, a deposition layer and a Si3N4 layer are sequentially deposited on the surface of the substrate, and multiple layers are stacked alternately.

[0026] In some specific embodiments of the present invention, such as Figure 2 As shown, when the substrate is an aluminum alloy, the optical component may further include an Al coating. The Al coating is located between the substrate and the lowest deposition layer of the composite film. The thickness of the Al coating is 50-200 nm, preferably 50-100 nm. In this invention, when the electronic device is an aluminum alloy product, it is necessary to deposit an Al underlayer on the substrate surface to improve the adhesion between the coating and the substrate. This ensures a strong bond between the coating and the substrate. Furthermore, pure Al has good plasticity and, as an underlayer and distributed in fine particles within the reinforcing coating, can reduce the internal stress and coefficient of friction of the coating, while simultaneously giving the coating high hardness.

[0027] A third aspect of the present invention provides a method for manufacturing an optical component, comprising:

[0028] A substrate is provided, and at least one composite layer is deposited on the surface of the substrate. The composite layer includes a deposited layer and a Si3N4 layer stacked sequentially. The deposited layer comprises a crystalline phase and a reinforcing phase. The crystalline phase is AN, where A is selected from one or more of Ti, Cr, W, V and Zr. The reinforcing phase is X, where X is selected from Cu and / or Ag.

[0029] In some specific embodiments of the present invention, the surface of the substrate further has an Al coating obtained by deposition.

[0030] In some specific embodiments of the present invention, the substrate includes one or more of metal, glass, ceramic, and sapphire.

[0031] In some specific embodiments of the present invention, the deposition may be performed by sputtering in an atmosphere of N2 and Ar2, wherein the sputtering process is performed in an atmosphere of N2 300 sccm and Ar2 200 sccm.

[0032] In some specific embodiments of the present invention, the sputtering temperature is 25-60°C.

[0033] In some specific embodiments of the present invention, the sputtering is performed using an AX alloy target.

[0034] In some specific embodiments of the present invention, the AX alloy target material is selected from A 90 X 10 Target material or A 80 X 20 The target material is preferably selected from Ti. 90 Cu 10 Target material or Ti 80 Cu 20 Target material. Selecting this ratio of target material allows the reinforcing phase to strengthen the crystalline phase. However, excessive crystalline phase content will inhibit crystalline phase growth, leading to a decrease in the strength and wear resistance of the composite film.

[0035] In some specific embodiments of the present invention, the method for preparing the optical component specifically includes:

[0036] (1) The substrate is sputtered using an AX alloy target to obtain a deposited layer;

[0037] (2) The deposited layer was sputtered using a Si target to obtain a Si3N4 layer;

[0038] (3) Repeat steps (1) and (2) several times to form a multilayer composite layer to obtain the optical component;

[0039] In some specific embodiments of the present invention, when the substrate is an aluminum alloy, the method for preparing the optical component specifically includes:

[0040] (1) An aluminum alloy substrate is sputtered using an Al target to obtain a deposited Al coating;

[0041] (2) The deposited Al coating was sputtered using an AX alloy target to obtain the deposited layer;

[0042] (3) The deposited layer was sputtered using a Si target to obtain a Si3N4 layer;

[0043] (4) Repeat steps (2) and (3) several times to form a multilayer composite layer and obtain the optical component.

[0044] A fourth aspect of the present invention provides an electronic device, wherein the electronic device comprises the composite film, the optical element, or the optical element obtained by the preparation method described above.

[0045] The present invention will be described in detail below through embodiments.

[0046] Unless otherwise specified in the following examples and comparative examples, all conditions were performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available products.

[0047] Example 1

[0048] (1) Polishing and cleaning of substrate surface

[0049] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0050] (2) Depositing Al coating

[0051] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0052] (3) Sedimentary layer

[0053] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0054] (4) Si3N4 layer

[0055] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0056] (5) Repeat steps (3) and (4) 7 times to form a multilayer stack to obtain the composite film;

[0057] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0058] Example 2

[0059] (1) Polishing and cleaning of substrate surface

[0060] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0061] (2) Depositing Al coating

[0062] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0063] (3) Sedimentary layer

[0064] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 flow rate 300 sccm, N2 flow rate 200 sccm, turn on the alloy target power supply, and deposit a TiN-Cu film with a thickness of 20 nm. Then turn off the alloy target power supply.

[0065] (4) Si3N4 layer

[0066] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposit thickness at 40nm.

[0067] (5) Repeat steps (3) and (4) 8 times to form a multilayer stack to obtain the composite film;

[0068] The total thickness of the composite film is 540 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0069] Example 3

[0070] (1) Polishing and cleaning of substrate surface

[0071] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0072] (2) Depositing Al coating

[0073] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0074] (3) Sedimentary layer

[0075] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0076] (4) Si3N4 layer

[0077] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 150nm.

[0078] (5) Repeat steps (3) and (4) 5 times to form a multilayer stack to obtain the composite film;

[0079] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:3.

[0080] Example 4

[0081] (1) Polishing and cleaning of substrate surface

[0082] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0083] (2) Depositing Al coating

[0084] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0085] (3) Sedimentary layer

[0086] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0087] (4) Si3N4 layer

[0088] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0089] (5) Repeat steps (3) and (4) twice to form a multilayer stack to obtain the composite film;

[0090] The total thickness of the composite film is 450 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0091] Example 5

[0092] (1) Polishing and cleaning of substrate surface

[0093] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0094] (2) Depositing Al coating

[0095] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0096] (3) Sedimentary layer

[0097] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 80 Cu 20Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0098] (4) Si3N4 layer

[0099] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0100] (5) Repeat steps (3) and (4) 7 times to form a multilayer stack to obtain the composite film;

[0101] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0102] Example 6

[0103] (1) Polishing and cleaning of substrate surface

[0104] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0105] (2) Depositing Al coating

[0106] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0107] (3) Sedimentary layer

[0108] Sputtering was performed on ZrCu alloy targets with different composition ratios. Zr was used. 80 Cu 20 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a ZrN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0109] (4) Si3N4 layer

[0110] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0111] (5) Repeat steps (3) and (4) 7 times to form a multilayer stack to obtain the composite film;

[0112] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0113] Example 7

[0114] (1) Polishing and cleaning of substrate surface

[0115] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0116] (2) Depositing Al coating

[0117] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0118] (3) Sedimentary layer

[0119] Sputtering was performed on TiAg alloy targets with different composition ratios. Ti was used. 80 Ag 20 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Ag film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0120] (4) Si3N4 layer

[0121] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0122] (5) Repeat steps (3) and (4) 7 times to form a multilayer stack to obtain the composite film;

[0123] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0124] Example 8

[0125] (1) Polishing and cleaning of substrate surface

[0126] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0127] (2) Depositing Al coating

[0128] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0129] (3) Sedimentary layer

[0130] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 150 nm was deposited. The power supply to the alloy target was then turned off.

[0131] (4) Si3N4 layer

[0132] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposit thickness at 50nm.

[0133] (5) Repeat steps (3) and (4) 7 times to form a multilayer stack to obtain the composite film;

[0134] The total thickness of the composite film is 1600 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 3:1.

[0135] Example 9

[0136] (1) Polishing and cleaning of substrate surface

[0137] The glass substrate is cleaned with an oil remover in an ultrasonic container, rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the vacuum sputtering machine fixture.

[0138] (2) Sedimentary layer

[0139] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10Alloy target. Ar2 was introduced at a flow rate of 300 sccm, and N2 at a flow rate of 200 sccm. The power supply to the alloy target was turned on, and a TiN-Cu film with a thickness of 50 nm was deposited. The power supply to the alloy target was then turned off.

[0140] (3) Si3N4 layer

[0141] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0142] (4) Repeat steps (2) and (3) 7 times to form a multilayer stack to obtain the composite film;

[0143] The total thickness of the composite film is 1200 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0144] Comparative Example 1

[0145] (1) Polishing and cleaning of substrate surface

[0146] The Al alloy substrate was polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it was cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate was placed on the fixture of a vacuum sputtering machine.

[0147] (2) Depositing Al coating

[0148] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0149] (3) Sedimentary layer

[0150] Sputtering was performed using a pure Ti target. Ar was introduced. 2 With a flow rate of 300 sccm and an N2 flow rate of 200 sccm, the alloy target power supply was turned on to deposit a TiN film with a thickness of 50 nm. The alloy target power supply was then turned off.

[0151] (4) Si3N4 layer

[0152] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0153] (5) Repeat steps (3) and (4) 7 times. The total thickness of the composite film is 1200 nm. The thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0154] Comparative Example 2

[0155] (1) Polishing and cleaning of substrate surface

[0156] The Al alloy substrate was polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it was cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate was placed on the fixture of a vacuum sputtering machine.

[0157] (2) Depositing Al coating

[0158] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0159] (3) Sedimentary layer

[0160] Using Ti 90 Cu 10 The alloy target is sputtered. Ar is introduced. 2 With a flow rate of 300 sccm and an N2 flow rate of 200 sccm, the alloy target power supply was turned on to deposit a TiN film with a thickness of 20 nm. The alloy target power supply was then turned off.

[0161] (4) Si3N4 layer

[0162] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposit thickness at 40nm.

[0163] (5) Repeat steps (3) and (4) twice. The total thickness of the composite film is 300 nm.

[0164] The total thickness of the composite film is 360 nm; the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0165] Comparative Example 3

[0166] (1) Polishing and cleaning of substrate surface

[0167] The aluminum alloy substrate is polished by grinding and polishing its surface with sandpaper of different roughness in turn; then it is cleaned with degreasing agent in an ultrasonic container, pickled and rinsed with deionized water, and dried with N2 gas; finally, the dried substrate is placed on the fixture of a vacuum sputtering machine.

[0168] (2) Depositing Al coating

[0169] The aluminum alloy substrate is placed on the fixture of the sputtering machine, and a vacuum is drawn; the vacuum level in the coating chamber is increased to 3×10⁻⁶. -3 At Pa, Ar2 is introduced. After the gas stabilizes, the ion source is turned on to perform ion cleaning on the substrate surface for 2-5 minutes. The ion source continues to work, and the sputtering power supply of the Al target is turned on at a power of 5kW and a thickness of 50nm to complete the first layer of the undercoat.

[0170] (3) Sedimentary layer

[0171] Sputtering was performed on TiCu alloy targets with different composition ratios. Ti... 90 Cu 10 Alloy target. Ar2 flow rate 300 sccm, N2 flow rate 200 sccm, turn on the alloy target power supply, and deposit a TiN-Cu film with a thickness of 50 nm. Then turn off the alloy target power supply.

[0172] (4) Si3N4 layer

[0173] Turn on the Si target power supply at 10kW, N2 flow rate at 300sccm, Ar2 flow rate at 300sccm, and deposition thickness at 100nm.

[0174] The total thickness of the composite film is 150 nm, and the thickness ratio of the deposited layer to the Si3N4 layer is 1:2.

[0175] Test example:

[0176] The composite membranes of Examples 1-9 and Comparative Examples 1-3 were subjected to the above performance tests. The test results of Examples 1-9 were good, while the composite membranes of the comparative examples had poor vibration wear resistance.

[0177] 1. Neutral salt spray test: NaCl%: 5% (pH 6.5-7.2), test environment 35℃.

[0178] 2. Acidic sweat test: A sweat formula consisting of 2.5g NaCl + 2.19g NH4Cl + 0.63g urea + 1.88g lactic acid + 0.32g acetic acid + 125mL purified water, adjusted to a pH of 4.7 with sodium hydroxide, is considered acidic sweat.

[0179] 3. Vibration and wear resistance: R180 / 530TE30 (Equipment frequency: 50±0.5Hz, amplitude 1.65±0.1mm).

[0180] 4. Boiling test: temperature 100℃, time 0.5h, 1h, 2h respectively.

[0181] The performance of the composite membranes obtained in Examples 1-9 and Comparative Examples 1-3 was tested, and the results are shown in Table 1.

[0182] Table 1

[0183]

[0184]

[0185] As can be seen from the results in Table 1, the composite laminates prepared in Examples 1-9 of the present invention have significantly better wear resistance and higher hardness, and are not affected by the substrate.

[0186] In the embodiments, the ratio of crystalline phase to reinforcing phase in the deposited layer is crucial for improving the strength and wear resistance of the laminate. Meanwhile, the thickness and number of layers in the composite structure also significantly affect the strength and wear resistance of the composite film. A single-layer structure and a thin film layer cannot reduce internal stress in the coating, strengthen grains, or improve the overall strength of the composite film.

[0187] The composite film comprises a deposition layer consisting of a crystalline phase and a reinforcing phase. Cu or Ag in this layer is completely insoluble with AN. The addition of Cu or Ag to the AN coating not only significantly reduces the internal stress of the coating but also improves its hardness and fracture toughness. The solid solution strengthening and grain refinement of Cu or Ag atoms greatly enhance the wear resistance, toughness, and hardness of the composite film. Meanwhile, due to the low mobility of Si3N4, it adsorbs onto the surface of the growing AN particles, hindering grain growth and further strengthening the film layer. The deposition layer and the Si3N4 layer on the deposition layer greatly enhance the wear resistance, toughness, and hardness of the composite film.

[0188] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composite membrane, characterized in that, The composite film comprises multiple stacked composite layers, each comprising a deposition layer and a Si3N4 layer on the deposition layer. The deposition layer comprises a crystalline phase and a reinforcing phase. The crystalline phase is AN, where A is selected from one or more of Ti, Cr, W, V, and Zr. The reinforcing phase is X, where X is selected from Cu and / or Ag. The total thickness of the composite film is 600-3000 nm. The thickness ratio of the deposition layer to the Si3N4 layer in the composite film is 1:(1-3).

2. The composite membrane according to claim 1, characterized in that, The total thickness of the composite film is 800-2000 nm.

3. The composite membrane according to claim 1 or 2, characterized in that, In the composite layer, the thickness of the Si3N4 layer is 20-500 nm; the thickness of the deposited layer is 20-600 nm.

4. The composite membrane according to claim 3, characterized in that, In the composite layer, the thickness of the Si3N4 layer is 20-250 nm; the thickness of the deposited layer is 50-300 nm.

5. The composite membrane according to claim 1 or 2, characterized in that, The composite membrane comprises 5-30 composite layers.

6. The composite membrane according to claim 5, characterized in that, The composite membrane comprises 6-18 composite layers.

7. The composite membrane according to claim 1 or 2, characterized in that, A is Ti, and the strengthening phase is Cu.

8. The composite membrane according to claim 1 or 2, characterized in that, The composite film has a nanohardness of 17-23 GPa and a pencil hardness of 7-9 H.

9. An optical component, characterized in that, The optical component includes a substrate and a composite film as described in any one of claims 1-8 disposed on the surface of the substrate, wherein the substrate includes one or more of metal, glass, ceramic, and sapphire.

10. The optical component according to claim 9, characterized in that, The lowest deposited layer of the composite film is located on the surface of the substrate.

11. The optical component according to claim 9 or 10, characterized in that, When the substrate is an aluminum alloy, the optical component may further include an Al coating, which is located between the substrate and the lowest deposition layer of the composite film, wherein the thickness of the Al coating is 50-200 nm.

12. The optical component according to claim 11, characterized in that, The thickness of the Al coating is 50-100 nm.

13. A method for manufacturing an optical component, characterized in that, include: A substrate is provided, and at least one composite layer is deposited on the surface of the substrate. The composite layer comprises a deposited layer and a Si3N4 layer stacked sequentially. The deposited layer comprises a crystalline phase and a reinforcing phase. The crystalline phase is AN, where A is selected from one or more of Ti, Cr, W, V, and Zr. The reinforcing phase is X, where X is selected from Cu and / or Ag. The total thickness of the composite film is 600-3000 nm. The thickness ratio of the deposited layer to the Si3N4 layer in the composite film is 1:(1-3).

14. The preparation method according to claim 13, characterized in that, The surface of the substrate also has an Al coating obtained by deposition.

15. The preparation method according to claim 13 or 14, characterized in that, The substrate includes one or more of metal, glass, ceramic, and sapphire.

16. An electronic device, characterized in that, The electronic device includes a composite film as described in any one of claims 1-8, an optical component as described in any one of claims 9-12, or an optical component prepared by the method described in any one of claims 13-15.

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