阅读说明：本技术 一种纳米Ag-Zn双层点阵涂层的制备方法 (Preparation method of nano Ag-Zn double-layer lattice coating ) 是由 唐正强 赵一舟 土旗 刘凡 林诗翔 于 2020-07-16 设计创作，主要内容包括：本发明公开了一种纳米Ag-Zn双层点阵涂层的制备方法,该方法包括步骤为：单晶硅基底经过表面处理；将AAO膜转移到基底贴合形成目标基底；将目标基底安装于仪器托盘底部,调整工作台使目标基底与溅射锌靶材中轴线重合且保持平行；溅射锌点阵和溅射银点阵；撕去AAO膜。本发明制备的涂层在抑制大肠杆菌和金黄色葡萄球菌等菌体的生长繁殖,同时对于受损细胞的分裂增值有促进作用,有益于伤口中细胞组织的愈合,制备完成的涂层呈圆球状单位元的Ag-Zn混合点阵；其表面规整光滑且高度有序；且Ag离子与Zn离子分布均匀；涂层为疏水结构,其带有自清洁功能不易于细菌的粘附滋生。(The invention discloses a preparation method of a nano Ag-Zn double-layer lattice coating, which comprises the following steps: carrying out surface treatment on a monocrystalline silicon substrate; transferring the AAO film to a substrate to form a target substrate; mounting a target substrate at the bottom of an instrument tray, and adjusting a workbench to enable the target substrate to be overlapped with and parallel to the central axis of the sputtering zinc target material; sputtering zinc dot matrix and sputtering silver dot matrix; the AAO film was torn off. The coating prepared by the invention can inhibit the growth and reproduction of thalli such as escherichia coli, staphylococcus aureus and the like, has a promoting effect on the division and proliferation of damaged cells, is beneficial to the healing of cell tissues in wounds, and is in a spherical unit Ag-Zn mixed lattice; the surface is regular, smooth and highly ordered; the Ag ions and the Zn ions are uniformly distributed; the coating is of a hydrophobic structure and has a self-cleaning function, so that bacteria are not easy to adhere and breed.)

1. A preparation method of a nano Ag-Zn double-layer lattice coating is characterized by comprising the following steps: the method comprises the following steps:

(1) carrying out surface treatment on a monocrystalline silicon substrate;

(2) transferring the porous anodic aluminum oxide film to the substrate after surface treatment is finished, and enabling the porous anodic aluminum oxide film to be completely attached to the substrate in a hydrophilic mode to form a new substrate, namely a target substrate;

(3) mounting a target substrate at the bottom of a tray of the multifunctional magnetron sputtering tester, and adjusting a workbench to enable the target substrate to be overlapped with and parallel to a central axis of a sputtered zinc target material;

(4) turning on the multifunctional magnetron sputtering tester, turning on a direct current target power supply of the zinc target material, and starting sputtering the zinc dot matrix;

(5) after zinc dot matrix sputtering is finished, rotating the tray rotating belt to enable the central axis of the sputtered silver target material to be coincident with the substrate and keep parallel, starting an alternating current target power supply of the silver target material, and starting sputtering the silver dot matrix;

(6) and taking out the deposited substrate, tearing off the porous anodic aluminum oxide film attached to the surface of the lattice coating, and finally obtaining the prepared nano Ag-Zn double-layer lattice coating.

2. The method for preparing a nano Ag-Zn double-layer lattice coating according to claim 1, wherein the method comprises the following steps: the method for treating the surface of the monocrystalline silicon substrate in the step (1) comprises the following steps: and (3) placing the substrate in a concentrated sulfuric acid solution, cleaning for 10min by using an ultrasonic cleaning instrument, taking out the substrate, washing with deionized water, placing the substrate in deionized water, performing ultrasonic cleaning for 10min, taking out the substrate again, and placing the substrate in a nitrogen drying oven for baking until the substrate is dried.

3. The method for preparing a nano Ag-Zn double-layer lattice coating according to claim 1, wherein the method comprises the following steps: the porous anodic aluminum oxide film transfer treatment method in the step (2) comprises the following steps: after the monocrystalline silicon substrate is cleaned, preparing a porous anodic alumina film, paving a polymethacrylate supporting layer auxiliary bearing plate of the porous anodic alumina film on the substrate, dripping a few drops of deionized water into one end of a PMMA supporting layer by using a dropper to enable the polymethacrylate supporting layer to be completely attached to the substrate, dripping an acetone solution into the other end of the PMMA supporting layer to enable the acetone solution to pass through the polymethacrylate supporting layer, washing by using the acetone solution repeatedly until the polymethacrylate supporting layer is completely dissolved and is completely treated, and finally obtaining the porous anodic alumina film substrate which is completely attached to the substrate, namely the target substrate.

4. The method for preparing a nano Ag-Zn double-layer lattice coating according to claim 1, wherein the method comprises the following steps: when the nano zinc dot matrix coating is sputtered in the step (4), a zinc target material is arranged at an ion beam target position of a direct current power supply, a backing valve and a molecular pump of the multifunctional magnetron sputtering tester are opened, after the molecular pump reaches 30000r/min, a main valve, a flow limiting valve and a stop valve of the multifunctional magnetron sputtering tester are sequentially opened, the power is adjusted to be 120W, the air pressure is set to be 0.5Pa, the temperature of a cavity is set to be 25 ℃, argon is filled into the working gas, the flow is set to be 30sccm, the direct current target power supply is opened, and the sputtering time is set to be 60 s.

5. The method for preparing a nano Ag-Zn double-layer lattice coating according to claim 4, wherein the method comprises the following steps: and (5) during sputtering of the nano silver dot matrix coating, not opening the box for ventilation after the finished zinc dot matrix sputtering, continuously operating a molecular pump and a main valve of the multifunctional magnetron sputtering tester, continuously depositing the silver dot matrix, rotating a tray rotating belt at the upper end of the substrate, rotating the substrate to a silver target position, aligning the silver target material with the target substrate, arranging the silver target device at an ion beam target position of an alternating current power supply, adjusting the power to 200W, setting the air pressure to be 0.5Pa, setting the cavity temperature to be 25 ℃ at normal temperature, filling working gas to be argon, setting the flow to be 30sccm, opening the alternating current target power supply, and sputtering for 120 s.

6. The method for preparing a nano Ag-Zn double-layer lattice coating according to claim 1, wherein the method comprises the following steps: and (6) tearing off the porous anodic aluminum oxide film (AAO) attached to the surface of the dot matrix coating by using a polyimide high-temperature cleaning adhesive tape.

Technical Field

The invention belongs to the technical field of coating preparation, and relates to a preparation method of a nano Ag-Zn double-layer lattice coating.

Background

Since ancient times, the human society has recognized the antibacterial properties of silver materials and has begun to use silver materials for food toxicity testing or food storage. Researches show that the sterilization efficiency of silver is related to the surface area of the silver, and the release amount of silver ions can be increased by increasing the surface area, so that the sterilization capability is greatly improved. Nowadays, nano-silver materials are used as bacteriostatic materials with smaller particle size and higher purity than elemental silver, have the advantages of stronger antibacterial ability, high temperature resistance, safety and the like in antibacterial property than elemental silver, and have higher economic value. Meanwhile, the nano zinc has the same inactivation effect on a plurality of bacterial mycoprotein. However, the prior art documents do not describe a coating material for the recovery of damaged tissue cells.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: provides a preparation method of a nano Ag-Zn double-layer lattice coating, which aims to solve the problems in the prior art.

The technical scheme adopted by the invention is as follows: a preparation method of a nano Ag-Zn double-layer lattice coating comprises the following steps:

(1) removing surface impurities and static electricity of the monocrystalline silicon substrate through surface treatment;

(2) transferring the porous anodic aluminum oxide film (AAO) to the substrate after the surface treatment is finished, and enabling the porous anodic aluminum oxide film and the substrate to be completely attached in a hydrophilic mode to form a new substrate, namely a target substrate;

(3) mounting a target substrate at the bottom of a tray of the multifunctional magnetron sputtering tester, and adjusting a workbench to enable the target substrate to be overlapped with and parallel to a central axis of a sputtered zinc target material;

(4) turning on the multifunctional magnetron sputtering tester, turning on a direct current target power supply of the zinc target material, and starting sputtering the zinc dot matrix;

(5) after zinc dot matrix sputtering is finished, rotating the tray rotating belt to enable the central axis of the sputtered silver target material to be coincident with the substrate and keep parallel, starting an alternating current target power supply of the silver target material, and starting sputtering the silver dot matrix;

(6) and taking out the deposited substrate, tearing off the porous anodic aluminum oxide film (AAO) attached to the surface of the lattice coating, and finally obtaining the prepared nano Ag-Zn double-layer lattice coating.

The method for treating the surface of the monocrystalline silicon substrate in the step (1) comprises the following steps: and (3) placing the substrate in a concentrated sulfuric acid solution, cleaning for 10min by using an ultrasonic cleaning instrument, taking out the substrate, washing with deionized water, placing the substrate in deionized water, performing ultrasonic cleaning for 10min, taking out the substrate again, and placing the substrate in a nitrogen drying oven for baking until the substrate is dried.

The porous anodic aluminum oxide film (AAO) transfer treatment method in the step (2) comprises the following steps: after the monocrystalline silicon substrate is cleaned, preparing a porous anodic aluminum oxide film (AAO), slowly paving a polymethyl methacrylate (PMMA) supporting layer for supporting an AAO template (the porous anodic aluminum oxide film) on the substrate, dripping a few drops of deionized water into one end of the PMMA supporting layer by using a dropper to completely attach the PMMA supporting layer (the PMMA supporting layer) on the substrate, dripping an acetone solution into the other end of the PMMA supporting layer to enable the acetone solution to pass through the PMMA layer (the polymethyl methacrylate supporting layer), washing by using the repeated acetone solution until the PMMA supporting layer (the polymethyl methacrylate supporting layer) is completely dissolved and completely treated, and finally obtaining the AAO template (the porous anodic aluminum oxide film) substrate completely attached to the substrate, namely the target substrate.

When the nano zinc dot matrix coating is sputtered in the step (4), a zinc target material is arranged at an ion beam target position of a direct current power supply, a backing valve and a molecular pump of the multifunctional magnetron sputtering tester are opened, after the molecular pump reaches 30000r/min, a main valve, a flow limiting valve and a stop valve of the multifunctional magnetron sputtering tester are sequentially opened, the power is adjusted to be 120W, the air pressure is set to be 0.5Pa, the temperature of a cavity is set to be 25 ℃, argon is filled into the working gas, the flow is set to be 30sccm, the direct current target power supply is opened, and the sputtering time is set to be 60 s.

And (5) during sputtering of the nano silver dot matrix coating, not opening the box for ventilation after the finished zinc dot matrix sputtering, continuously operating a molecular pump and a main valve of the multifunctional magnetron sputtering tester, continuously depositing the silver dot matrix, rotating a tray rotating belt at the upper end of the substrate, rotating the substrate to a silver target position, aligning the silver target material with the target substrate, arranging the silver target device at an ion beam target position of an alternating current power supply, adjusting the power to 200W, setting the air pressure to be 0.5Pa, setting the cavity temperature to be 25 ℃ at normal temperature, filling working gas to be argon, setting the flow to be 30sccm, opening the alternating current target power supply, and sputtering for 120 s.

And (6) tearing off the porous anodic aluminum oxide film (AAO) attached to the surface of the dot matrix coating by using a polyimide high-temperature cleaning adhesive tape.

The invention utilizes a physical vapor deposition method and uses a multifunctional magnetron sputtering tester (model: TGP-500) to sputter a silver target material and a zinc target material on a target monocrystalline silicon substrate.

The nano Ag-Zn double-layer lattice coating is formed by taking a porous anodic aluminum oxide film (AAO) as an auxiliary substrate and a monocrystalline silicon substrate and a double-layer lattice layer deposited above the monocrystalline silicon substrate

The invention has the beneficial effects that: compared with the prior art, the invention has the following effects:

(1) the nano Ag-Zn coating prepared by the invention has obvious antibacterial performance on gram-negative bacteria (escherichia coli) and gram-positive bacteria (staphylococcus aureus). The reason for this is that the silver ions and zinc ions having positive charges are generated when the silver nanoparticles and zinc nanoparticles have large specific surface areas and react with water. When the adsorption acts on the microorganism, the respiratory enzyme of the microorganism can be destroyed, and the respiratory action of the bacteria is inhibited. The Ag-Zn nano lattice (as shown in figure 1) arranged regularly can not only inhibit the growth of bacteria, but also promote the tissue proliferation and the wound healing. The Ag-Zn particles arranged at intervals in a high order can generate an exogenous electromagnetic field, can guide the migration of cells, and can reduce the trans-epithelial potential of a wound position, so that an endogenous electric field is enhanced, the generation of Adenosine Triphosphate (ATP) and deoxyribonucleic acid (DNA) is promoted, the blood flow and capillary density are increased, and the healing of the wound is promoted. The electromagnetic field generated by the two can be combined with low-level hydrogen peroxide acting on the dressing to catalyze the decomposition of the hydrogen peroxide to generate hydroxide ions, so that the effects of inhibiting bacteria and promoting wound healing are achieved, and high toxicity caused by excessive hydrogen peroxide during wound disinfection can be avoided; secondly, due to the microscopic physical structure of the nano Ag-Zn lattice, the contact angle of the surface is larger than 90 degrees when no chemical hydrophobic property modification is carried out, the accumulation caused by the seepage of tissue fluid inside the skin or the invasion of external moisture can be prevented, and the adhesion and the breeding of bacteria are not easy to happen.

(2) When the coating is deposited, the nano zinc is deposited as a lower layer, the nano silver is deposited as an upper layer, and the independent silver dot matrix unit not only can interact with the zinc dot matrix unit below to generate an electromagnetic field, but also can interact with eight zinc dot matrices below the periphery in an intersecting manner to generate an electromagnetic field, so that a multi-intersection effect can be generated to the maximum extent;

(3) the nano Ag-Zn double-layer lattice coating has a contact angle of 103.6 degrees and is a hydrophobic material. The surface of the coating after the nano-lattice sputtering can improve the hydrophobicity, can avoid the residue of water and the breeding of bacteria, and has a certain self-cleaning function in practical clinical use;

(4) the surface treatment of the monocrystalline silicon substrate is to remove stains, dust residues and static electricity on the surface of the substrate, so that the substrate is kept dry and smooth before use and is favorable for the attachment of an auxiliary substrate;

(5) the reason for using a PMMA support layer as the transition layer substrate is: the thickness of the porous anodic aluminum oxide film adopted by the invention is 200nm, and the film is extremely thin and is extremely easy to break. The membrane is broken in the operation process by adopting a normal transfer method, so that a PMMA support layer is adopted as transition, and the porous anodic aluminum oxide membrane is completely attached to the surface of the substrate after being dissolved by acetone;

(6) by adopting the power and time control of the invention, the porous anodic aluminum oxide film can be prevented from being broken down and the zinc coating deposited on the substrate has better bonding force, because the porous anodic aluminum oxide film is broken down when zinc ions are sputtered due to overhigh power or time, and the zinc coating deposited on the substrate is peeled off due to insufficient bonding force when the power or time is overlow;

(7) when the power or time is too high, the porous anodic aluminum oxide film can be broken down when silver ions are sputtered, and when the power or time is too low, the silver coating deposited on the substrate can be peeled off due to insufficient bonding force; the silver-zinc dot matrix coated by magnetron sputtering has the advantages that: various materials can be prepared, such as nanostructures of semiconductors, conducting polymers, oxides, carbon, alloys, metals and other materials; the method can prepare the one-dimensional nano material such as the nano tube or the nano fiber with extremely small diameter which is difficult to obtain by other means, and can easily and accurately adjust the relevant parameters of the one-dimensional nano material to be prepared by adjusting the diameter parameters of the holes of the template; because ions are sputtered during starting, the silver target and the zinc target can be better sputtered to the substrate in the form of ions to generate an electric field; the sputtering speed and thickness can be controlled, and the thickness of the coated film is controlled by controlling the sputtering power and the air flow; the sputtering compactness is strong, compared with other deposition technologies, the magnetron sputtering coating has good binding force, and can not fall off due to friction when acting on skin on the surface of the substrate; the lower end of the magnetron sputtering is provided with three ion sources, the sputtering angle can be controlled, and bidirectional sputtering can be carried out at different angles to obtain a silver-zinc mixed dot matrix.

(8) The substrate obtained by tearing off the polyimide high-temperature cleaning adhesive tape is brighter and more complete, because the polyimide high-temperature cleaning adhesive tape serving as a static-free material can not be adhered with dust, can be completely attached to the AAO film when the AAO film is torn off, and simultaneously has extremely strong adhesion, the AAO film can be completely removed, so that a nano Ag-Zn double-layer lattice coating sample is obtained.

Therefore, the Ag-Zn material is prepared into the nano lattice coating, and the nano lattice coating is applied to medical equipment such as dressing band-aids, bile ducts, drainage tubes and the like, can obviously improve the medical performance of nano material engineering and medical instrument coatings, and has important theoretical significance and application value.

Drawings

FIG. 1 is a schematic view of a nano Ag-Zn lattice coating;

FIG. 2 shows the design, application and electric field generation principle of a nano Ag-Zn double-layer lattice coating;

FIG. 3 is a scanning electron microscope dot-matrix diagram of different deposition shapes obtained at different deposition times;

FIG. 4 is a curve of AFM three-dimensional morphology and probe scanning cross section of a nano Ag-Zn double-layer lattice coating;

FIG. 5 is an EDS analysis chart of the coating surface;

FIG. 6 is a comparison graph of the state of water drops on the surface of the matrix material and the nano Ag-Zn double-layer lattice coating;

FIG. 7 is a schematic diagram of the AAO template transfer principle;

FIG. 8 is a schematic view of magnetron sputtering substrate mounting.

Detailed Description

The invention is further described below with reference to specific examples.