WO2020124382A1 - 具有多级次微纳结构的金刚石薄膜及其制备方法和应用 - Google Patents

具有多级次微纳结构的金刚石薄膜及其制备方法和应用 Download PDF

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WO2020124382A1
WO2020124382A1 PCT/CN2018/121832 CN2018121832W WO2020124382A1 WO 2020124382 A1 WO2020124382 A1 WO 2020124382A1 CN 2018121832 W CN2018121832 W CN 2018121832W WO 2020124382 A1 WO2020124382 A1 WO 2020124382A1
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diamond
density
thin film
seeding
nano
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PCT/CN2018/121832
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English (en)
French (fr)
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唐永炳
王陶
李星星
黄磊
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深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only

Definitions

  • the present application relates to the technical field of diamond thin films, in particular, to a diamond thin film with a multi-level sub-nano structure, and a preparation method and application thereof.
  • the wettability of the diamond film surface has attracted much attention, because the wettability directly affects its applications in the fields of chemistry, biology, and medicine, especially in the use of macro or micro devices, and the need for hydrophilic or super hydrophobic Diamond film.
  • some biosensors require a hydrophilic surface to promote the adsorption of cells on the probe; on the contrary, the surface of the device working in harsh environments such as seawater, blood or mechanical impact wear needs to be protected, and the super-hydrophobic surface is used to prevent chemical corrosion, Prevent biological fouling and mechanical wear, such as anti-thrombosis artificial stents, artificial joints, deep-sea precision detection devices and microfluidic devices, etc.
  • diamond Compared with other polymers, metals and ceramic materials, diamond has the highest hardness, the best abrasion resistance, the highest thermal conductivity, has a strong chemical inertness, stable chemical properties and biocompatibility. It is an ideal hydrophilic/ Super hydrophobic material. Therefore, how to effectively control the hydrophilic/superhydrophobic properties of diamond has become an urgent problem to be solved.
  • One of the purposes of the present application is to provide a diamond film with a multi-level sub-nano structure of lotus-like papillary bodies to achieve a super-hydrophobic effect.
  • the second objective of the present application is to provide a method for preparing the above diamond thin film, which is obtained by successively using low-density and high-density seeding using chemical vapor deposition technology, and has strong applicability, easy preparation, low cost, simple operation and stable process , Suitable for industrial production.
  • the third object of the present application is to provide an application of the diamond thin film prepared by the above diamond thin film or the preparation method of the diamond thin film in chemical corrosion resistance, self-cleaning, mechanical wear resistance or oil-water separation.
  • a diamond thin film in a first aspect, includes a discontinuous micron-sized diamond island formed outwardly from a surface of a substrate, and a nanodiamond film layer composed of continuous nano-sized diamond grains, formed to have Multi-level sub-nano structure of lotus-like papillae.
  • the size of the micron-sized diamond island is 1-10 ⁇ m, preferably 2-7 ⁇ m;
  • the thickness of the nano-diamond film layer is 10-800 nm, preferably 20-200 nm.
  • the substrate includes one of silicon, copper alloy, stainless steel, glass or ceramic.
  • a method for preparing a diamond thin film including the following steps:
  • low-density seeding is carried out on the pretreated substrate, and diamond is grown once by chemical vapor deposition;
  • the pretreatment includes cleaning, corrosion treatment or sandblasting, and re-cleaning.
  • the seed density of the low-density seed crystal is 10 4 -10 8 pieces/cm 2 , preferably (2-3) ⁇ 10 6 pieces/cm 2 ; and/or, high
  • the density of the density seed crystal is 10 9 -10 12 pieces/cm 2 , (1-7) ⁇ 10 11 pieces/cm 2 .
  • the low-density seed crystal adjusts the zeta potential of the diamond seed crystal solution to make the nano-diamond and the substrate surface electrically the same;
  • the seeding solution used for low-density seeding includes nano-diamond powder, anionic surfactant and water.
  • the mass of the nano-diamond powder accounts for 0.005-0.5% of the mass of the seeding solution, and the concentration of the anionic surfactant in the seeding solution 10 -6 -10 -3 mol/L, the pH of the plant crystal solution is 2-8; preferably the anionic surfactant is oxalic acid or citric acid;
  • the high-density seed crystal adjusts the zeta potential of the diamond seed crystal solution to make the nano-diamond and the substrate surface electrically opposite;
  • the planting solution used for high-density planting includes nano-diamond powder, cationic surfactant and water, the mass of the nano-diamond powder accounts for 0.005-0.5% of the mass of the planting solution, and the concentration of the cationic surfactant in the planting solution 10 -6 -10 -3 mol/L, the pH of the seed crystal solution is 5.5-6; preferably the cationic surfactant is lysine or methacryloyloxyethyltrimethylammonium chloride;
  • the low-density seeding and the high-density seeding are independently seeded by placing the substrate in the seeding solution and sonicating for 20 to 60 minutes, and then taking out and drying.
  • the preferred drying method is to blow dry with nitrogen.
  • the process parameters of one-step diamond growth by hot-wire chemical vapor deposition method include: using hydrogen, methane and optional inert gas as the reaction gas, and the total flow rate of the reaction gas is 500-850 sccm, Among them, the flow rate of methane gas accounts for 1-5% of the total flow rate, the flow rate of hydrogen and optional inert gas accounts for 95-99% of the total flow rate, the deposition pressure is 1500-6000Pa, the filament temperature is 1800-2800°C, and the wire sample distance is 7 -15mm, deposition time is 1-1.5h.
  • the process parameters of secondary diamond growth by hot wire chemical vapor deposition method include: using hydrogen, methane and inert gas as the reaction gas, and the total flow rate of the reaction gas is 500-850 sccm, of which methane
  • the gas flow rate is 1-5% of the total flow rate
  • the hydrogen flow rate is 25-45% of the total flow rate
  • the inert gas flow rate is 50-70% of the total flow rate
  • the deposition pressure is 1500-6000Pa
  • the filament temperature is 1800-2800°C
  • the filament The sample distance is 20-25mm and the deposition time is 20-30min.
  • the method for preparing the diamond thin film further includes fluorinating the surface of the diamond thin film to obtain a fluorinated diamond thin film.
  • This application designed a lotus leaf bionic multi-level sub-nano composite diamond film material, that is, a diamond film with micron and nano grain composites, the micro-nano composite structure has a morphology similar to the surface morphology of the lotus leaf , There are one micron-sized protrusions (diamond islands), the surface of the protrusions is nano-grain, to achieve super-hydrophobic effect, can achieve self-cleaning and oil-water separation and other functions, and the chemical stability of diamond, anti-wear impact resistance and resistance Strong corrosion and long life.
  • the preparation method of the diamond film of the present application uses chemical vapor deposition technology to prepare a diamond surface with a micro-nano structure similar to a lotus leaf on the omentum, which is easy to obtain, firstly through low-density seeding and deposition, and then through high-density seeding And deposition.
  • This method has strong applicability.
  • the water contact angle of 80°-170° can be effectively controlled by adjusting the density of micrometer particles, and the wettability of the surface can be effectively controlled; it is suitable for lotus-like micro-nano structure diamonds on any flat or mesh substrate
  • the method has simple preparation process and stable process, is suitable for industrial production, and can deposit micro-nano structure diamond with good binding force.
  • Figure 1 is a schematic diagram of the structure of the diamond film of this application.
  • Example 2 is a microscopic morphology diagram of the surface and cross section of the diamond thin film obtained in Example 1 of the present application, where the left side is the surface microtopography and the right side is the cross section microtopography;
  • Example 3 is a microscopic morphology diagram of the surface and cross section of the diamond thin film obtained in Example 2 of the present application, in which the microscopic morphology of the surface is on the left, and the microscopic morphology of the cross section is on the right;
  • Example 4 is a schematic diagram of the water contact angle of the diamond film obtained in Example 1 of the present application and the diamond film obtained in Example 7, wherein the left side is a schematic diagram of the water contact angle of the diamond film obtained in Example 1, and the right side is obtained in Example 7 Schematic diagram of diamond film water contact angle.
  • Icon 100-substrate; 200-diamond film; 210-mastoid; 211-diamond island; 212-nanodiamond film.
  • a diamond thin film comprising discontinuous micron-sized diamond islands formed sequentially from the surface of a substrate, and a nanodiamond film layer composed of continuous nano-sized diamond grains to form Multi-level sub-nano structure with lotus-like papillary bodies.
  • the substrate may be a planar substrate or a mesh substrate.
  • a typical but non-limiting example of the planar substrate is silicon, copper alloy, stainless steel, glass or ceramic;
  • a typical but non-limiting example of the mesh substrate is a metal mesh or fabric mesh , Preferably metal mesh; metal mesh includes but is not limited to copper mesh, titanium mesh or stainless steel mesh.
  • the substrate 100 of the present application has a diamond film 200 with a multi-level sub-nano structure of lotus-like papillary bodies 210.
  • the diamond film 200 includes non-continuous micron-sized diamond islands formed sequentially from the surface of the substrate 100. 211, and a nano-diamond film layer 212 composed of continuous nano-sized diamond grains.
  • a diamond island is a single micron diamond particle, or an aggregate formed by multiple nanodiamond particles.
  • Micro-nano structure refers to a micro-feature morphology of a solid surface, which needs to be observed under an electron microscope.
  • the multi-scale (multi-level, hierarchical) structure composed of micro-scale surface fluctuations superimposed on nano-scale fluctuations is a This kind of layered structure, that is, an island-like structure with a size in the order of micrometers is the first level, and the continuous nano-sized grains on each island are the second level.
  • the micro-nano structure of lotus-like papillary body refers to the micro-feature morphology of the surface of the diamond film of this application is similar to the micro-feature morphology of the surface of the lotus leaf, and has a micro-papilla structure rough surface similar to that of lotus leaf.
  • the size of the micron-sized diamond island is 1-10 ⁇ m, preferably 2-7 ⁇ m, such as 2 ⁇ m, 5 ⁇ m or 7 ⁇ m.
  • the thickness of the nano-diamond film layer is 10-800 nm, preferably 20-200 nm, such as 50 nm, 100 nm or 200 nm.
  • the diamond film of this application has a bionic lotus-like multi-level sub-nano structure.
  • the surface morphology of the diamond film is similar to the surface morphology of the lotus leaf.
  • the film has super-hydrophobic properties, stable diamond chemistry, strong resistance to abrasion, strong corrosion resistance and long life.
  • a method for preparing a diamond thin film including the following steps:
  • low-density seeding is carried out on the pre-treated substrate, and the diamond is grown once by chemical vapor deposition; then high-density seeding is carried out on the diamond film grown once, and the diamond is grown again by chemical vapor deposition. A diamond film is obtained.
  • Chemical vapor deposition methods include but are not limited to hot wire or microwave plasma enhanced chemical vapor deposition methods, preferably hot wire chemical vapor deposition methods.
  • Chemical vapor deposition diamond growth requires implantation of diamond seed crystals, and then epitaxial growth at the implanted seed point, using the selective adsorption of diamond seed crystals on the substrate to build a micro-nano structure with super-hydrophobicity.
  • a diamond surface similar to a lotus leaf micro-nano structure is prepared by two implants and two depositions on the omentum, that is, one implantation-one hot filament deposition-second implantation-second hot filament deposition, once The implant is a low-density implant, and the secondary implant is a high-density implant.
  • the height here is a relative concept.
  • Low-density seed crystal refers to the monodisperse state of diamond seed crystals on the substrate, so that a dense cauliflower-shaped diamond island is formed on the substrate after one-time deposition.
  • the seed density of the low-density seed crystal is 10 4 -10 8 pieces/cm 2 , preferably (2-3) ⁇ 10 6 pieces/cm 2 .
  • High-density seed crystal refers to the continuous arrangement of diamond seeds on the substrate, so as to form a continuous diamond film after secondary deposition.
  • the high-density seed crystal has a seed crystal density of 10 9 -10 12 pieces/cm 2 , preferably (1-7) ⁇ 10 11 pieces/cm 2 .
  • the pretreatment includes cleaning, corrosion treatment or sandblasting, and re-cleaning.
  • the cleaning and the re-cleaning independently include ultrasonic cleaning with water 2-3 times, 5-10min each time, and ultrasonic cleaning with alcohol 1-2 times, 5-10min each time;
  • the corrosion treatment includes ultrasonic cleaning in an alkali solution and/or acid solution for 1-2 min; preferably the alkali solution is 0.5-1 mol/L NaOH or KOH solution; preferably the acid solution is 1-4 mol/L HCl, H 2 SO 4 or HNO 3 solution.
  • Corrosion treatment or sand blasting on the substrate increases the surface roughness on one hand and increases the adsorption density of the diamond particles.
  • the electrical properties of the surface of the substrate are the same as that of the nano-diamonds used for seeding through pretreatment.
  • Low-density seeding can be achieved by adjusting the zeta potential of the diamond seeding solution so that the electrical properties of the nanodiamond and the substrate are the same.
  • the seeding solution used for low-density seeding includes nano-diamond powder, anionic surfactant and water.
  • the mass of the nano-diamond powder accounts for 0.005-0.5% of the mass of the seeding solution, for example, 0.005%, 0.006%, 0.007%, 0.008%, 0.009% or 0.01%
  • the concentration of the anionic surfactant in the seeding solution is 10 -6 -10 -3 mol/L, for example 10 -6 mol/L, 10 -5 mol/L, 10 -4 mol/L or 10 -3 mol/L
  • the pH of the seeding solution is 2-8, such as pH2, pH3, pH4, pH5, pH6, pH7 or pH8; preferably the anionic surfactant is oxalic acid or citric acid. Seed the monodisperse seed crystals on the substrate by selecting a suitable seeding solution.
  • High-density seeding can be achieved by adjusting the zeta potential of the diamond seeding solution to make the electrical conductivity of the nanodiamond and the substrate surface opposite.
  • the high-density seeding solution includes nanodiamond powder, cationic surfactant and water.
  • the mass of the nanodiamond powder accounts for 0.005-0.5% of the mass of the seeding solution, for example, 0.005%, 0.006%, 0.007%, 0.008%, 0.009% or 0.01%
  • the concentration of the cationic surfactant in the seeding solution is 10 -6 -10 -3 mol/L, for example 10 -6 mol/L, 10 -5 mol/L, 10 -4 mol/L or 10 -3 mol/L
  • the pH of the seeding solution is 5.5-6; preferably the cationic surfactant is lysine or methacryloyloxyethyltrimethylammonium chloride.
  • the low-density and high-density implants are independently implanted by placing the substrate in the implant solution for 20-60 minutes and then taken out and dried.
  • the preferred drying method is nitrogen drying.
  • Ultrasonic seeding method has low cost and simple operation, which is suitable for industrial production.
  • hot wire/microwave chemical vapor deposition is used for two-step deposition, that is, firstly, it is preferred to adjust the nano-diamond size and zeta potential of the diamond planting solution to make the nano-diamond and the substrate surface electrically consistent, and the diamond adsorbed on the substrate
  • the seed crystal density is low (10 4 -10 8 cm -2 )
  • the first layer of discontinuous diamond islands size 1-10 ⁇ m) is deposited; then the first layer is re-sonicated with ultra-dispersed nano diamond solution.
  • the water contact angle of 80°-170° can be effectively controlled by adjusting the density of the micron particles, and the wetting performance can be controlled.
  • the diamond thin film with multi-level micro-nano composite is prepared by changing the properties of the diamond seeding solution.
  • the superhydrophobic diamond film is obtained only by changing the seeding solution. The process is extremely simple and low in cost. It is suitable for large-scale industrial production and can deposit micro-nano composite diamond with good binding force on a three-dimensional or two-dimensional substrate.
  • the chemical vapor deposition method is hot filament chemical vapor deposition.
  • the process parameters of hot filament chemical vapor deposition for one-time diamond growth include: using hydrogen, methane, and optional inert gas as reaction gases.
  • the non-limiting inert gas is argon
  • the total flow of the reaction gas is 500-850 sccm, such as 500 sccm, 600 sccm, 700 sccm, 800 sccm, or 850 sccm, wherein the methane gas flow accounts for 1-5% of the total flow, such as 1%, 2%, 3%, 4% or 5%
  • the flow rate of hydrogen and optional inert gas accounts for 95-99% of the total flow rate
  • the deposition pressure is 1500-6000Pa, such as 1500Pa, 1600Pa, 1700Pa, 1800Pa, 1900Pa, 2000Pa, 3000Pa, 4000Pa, 5000Pa or 6000Pa
  • filament temperature is 1800-2800 °C, such
  • a low-density monodisperse seed crystal seed crystal is deposited with good quality and not dense cauliflower-shaped diamond islands.
  • the chemical vapor deposition method is a hot wire chemical vapor deposition method.
  • the process parameters of the hot wire chemical vapor deposition method for secondary diamond growth include: using hydrogen, methane, and an inert gas as reaction gases, and the total flow rate of the reaction gases 500-850sccm, such as 500sccm, 600sccm, 700sccm, 800sccm or 850sccm, where methane gas flow accounts for 1-5% of the total flow, such as 1%, 2%, 3%, 4% or 5%, and hydrogen flow accounts for the total flow 25-45%, such as 25%, 28%, 30%, 35%, 40% or 45%, the flow of inert gas accounts for 50-70% of the total flow, such as 50%, 55%, 60%, 65% or 70%, the deposition pressure is 1500-6000Pa, such as 1500Pa, 1600Pa, 1700Pa, 1800Pa, 1900Pa, 2000Pa, 3000Pa, 4000Pa, 5000Pa or
  • ultra-thin diamond films of good quality are grown on high-density continuous seed crystal seeds, and finally a lotus leaf-like bionic micro-nano structure with papillae is formed.
  • the method of preparing the diamond film further includes fluorinating the surface of the diamond film to obtain a fluorinated diamond film.
  • Surface fluorination treatment includes but is not limited to chemical wet method or plasma fluorination treatment.
  • the deposited sample surface can further increase its water contact angle.
  • a typical diamond film preparation method includes the following steps:
  • the substrate after the second seeding is placed in a hot gas chemical vapor deposition or microwave plasma enhanced chemical vapor deposition equipment to grow an ultra-thin diamond film using an ultra-low temperature process.
  • step (a) and step (c) the substrate is cleaned by deionized water ultrasonic cleaning twice, 5 minutes each time, and finally ultrasonic cleaning with alcohol for 5 minutes;
  • the corrosion treatment in step (b) is ultrasonic cleaning in alkali or acid solution for 1 minute;
  • the planting solution is a detonation nanodiamond suspension
  • the composition is a diamond powder mass fraction of 0.5%-0.005%
  • the concentration of oxalic acid or citric acid is 10 -6 M-10 -3 M
  • the solvent is deionized water.
  • the pH is 2-8.
  • the method of seeding is to put the sample into the seeding solution and sonicate for 30 minutes, take it out, and blow dry with nitrogen;
  • the component of the planting solution in step (f) is diamond powder mass fraction 0.5%-0.005%, lysine or methacryloyloxyethyl trimethylammonium chloride, the concentration is 10 -6 M-10 -3 M, The solvent is deionized water and the pH is 6.
  • an application of the diamond thin film prepared by the diamond thin film or the diamond thin film preparation method to chemical corrosion resistance, self-cleaning, mechanical wear resistance or oil-water separation.
  • the diamond thin film of the present application has high hydrophobicity and strong corrosion resistance, it can be used in chemical corrosion resistance, self-cleaning, mechanical wear resistance or oil-water separation, and has broad application prospects.
  • a method for preparing diamond thin film includes the following steps:
  • the base silicon after low-density seeding is put into the hot-wire chemical vapor deposition equipment to perform diamond growth once.
  • the process parameters include: using hydrogen and methane as reaction gases, and controlling the flow rates of hydrogen and methane to 800 sccm and 32 sccm, respectively.
  • the deposition pressure is 2000Pa
  • the filament temperature is 2600°C
  • the filament sample distance is 7mm
  • the deposition time is 1 hour;
  • step (6) Carry out high-density seeding, put the base silicon obtained in step (5) into a high-density seeding solution and sonicate for 30 minutes, take it out, and blow dry with nitrogen; high-density seeding solution lysine is added as a surfactant In the diamond suspension, the concentration of lysine is 10 -5 mol/l, pH 4, and the concentration of diamond powder is 0.005wt%;
  • the high-density implanted base silicon is placed in the hot wire chemical vapor deposition equipment for secondary diamond growth.
  • the process parameters include: using hydrogen, methane and argon as reaction gases to control the hydrogen, methane and argon gas.
  • the flow rates were 200 sccm, 18 sccm and 282 sccm respectively, the deposition pressure was 1500 Pa, the filament temperature was 2000° C., the filament sample distance was 20 mm, and the deposition time was 30 min to obtain diamond thin film substrate silicon.
  • FIG. 2 is a microscopic morphology diagram of the surface and cross section of the diamond film obtained in Example 1.
  • FIG. 1 is a microscopic morphology diagram of the surface and cross section of the diamond film obtained in Example 1.
  • a method for preparing diamond thin film includes the following steps:
  • the substrate after low-density seeding is put into the hot-wire chemical vapor deposition equipment for diamond growth.
  • the process parameters include: using hydrogen and methane as reaction gases, and controlling the flow rates of hydrogen and methane to 800sccm and 16sccm, respectively.
  • the air pressure is 2000Pa
  • the filament temperature is 2600°C
  • the filament sample distance is 7mm
  • the deposition time is 1 hour;
  • step (6) Carry out high-density seeding, put the copper alloy substrate obtained in step (5) into the high-density seeding solution for 20 minutes, take it out, and blow dry with nitrogen; high-density seeding solution glutamic acid as the surfactant Add to the diamond suspension, the concentration of glutamic acid is 7 ⁇ 10 -5 mol/l, pH 4, the concentration of diamond powder is 0.05wt%;
  • the copper alloy substrate after high-density seeding is placed in the hot wire chemical vapor deposition equipment for secondary diamond growth.
  • the process parameters include: using hydrogen and methane as reaction gases, and controlling the flow rates of hydrogen and methane and argon respectively. 800sccm and 32sccm, the deposition pressure is 2000Pa, the filament temperature is 2200°C, the filament sample distance is 7mm, and the deposition time is 30min.
  • the diamond thin film copper alloy substrate is obtained.
  • FIG. 3 is a microscopic morphology diagram of the surface and cross section of the diamond film obtained in Example 2.
  • FIG. 3 is a microscopic morphology diagram of the surface and cross section of the diamond film obtained in Example 2.
  • a method for preparing diamond thin film includes the following steps:
  • the substrate after low-density seeding is placed in the hot-wire chemical vapor deposition equipment for one-time diamond growth.
  • the process parameters include: using hydrogen and methane as reaction gases, and controlling the flow rates of hydrogen and methane to 800 sccm and 32 sccm, respectively.
  • the air pressure is 2000Pa
  • the filament temperature is 2500°C
  • the filament sample distance is 10mm
  • the deposition time is 1.5 hours;
  • step (5) Carry out high-density seeding, put the glass substrate obtained in step (5) into the high-density seeding solution and sonicate for 20 minutes, take it out, and blow dry with nitrogen; high-density seeding solution methacryloyloxyethyl trioxide Methyl ammonium chloride is added as a surfactant to the diamond suspension.
  • concentration of methacryloyloxyethyl trimethyl ammonium chloride is 10 -4 mol/l, pH 7, and the concentration of diamond powder is 0.5wt% ;
  • the glass substrate after high-density seeding is placed in the hot wire chemical vapor deposition equipment for secondary diamond growth.
  • the process parameters include: using hydrogen, methane and argon as reaction gases to control the hydrogen, methane and argon gas.
  • the flow rates were 200 sccm, 18 sccm and 282 sccm respectively, the deposition pressure was 1500 Pa, the filament temperature was 6000 W, the filament sample distance was 25 mm, and the deposition time was 30 min to obtain a diamond thin film glass substrate.
  • a method for preparing diamond thin film includes the following steps:
  • the process parameters are: the flow rate of hydrogen and tetramethylsilyl methane are 800sccm and 80sccm, the deposition pressure is 2000Pa, and the filament temperature is 2000°C ;
  • the sample is subjected to low-density seeding treatment of nano-diamonds.
  • the low-density seeding solution is a detonation nano-diamond suspension.
  • Oxalic acid is added to the diamond suspension as a surfactant.
  • the concentration of oxalic acid is 7 ⁇ 10 -5 mol /l, pH 8, the concentration of diamond powder is 0.005wt%.
  • the seeding method is to put the sample into the seeding solution and sonicate for 30 minutes, take it out, and blow dry with nitrogen;
  • the process parameters are as follows: take hydrogen, argon and methane as reaction gases, and control the flow rates of hydrogen, argon and methane to be 200 sccm, 282 sccm and 18sccm, deposition pressure is 2000Pa, filament temperature is 2500°C, filament sample distance is 15mm, deposition time is 0.5 hours;
  • methacryloyloxyethyltrimethylammonium chloride is added as a surfactant to the diamond suspension, methacryloyloxyethyltrichloride
  • concentration of methyl ammonium chloride is 5 ⁇ 10 -6 mol/l, pH 4, and the concentration of diamond powder is 0.005wt%;
  • the high-density implanted stainless steel substrate is placed in the hot wire chemical vapor deposition equipment for secondary diamond growth.
  • the process parameters include: using hydrogen, methane and argon as reaction gases to control the hydrogen, methane and argon gas.
  • the flow rates were 200sccm, 18sccm and 282sccm respectively, the deposition pressure was 1500Pa, the filament temperature was 2200°C, the wire sample distance was 20mm, and the deposition time was 30min.
  • a diamond film stainless steel substrate was obtained.
  • a method for preparing diamond thin film includes the following steps:
  • the substrate after low-density seeding is placed in hot-wire chemical vapor deposition equipment for diamond growth once.
  • the process parameters include: using hydrogen and methane as reaction gases, and controlling the flow rates of hydrogen and methane to 800 sccm and 32 sccm, respectively.
  • the air pressure is 2000Pa
  • the filament temperature is 2600°C
  • the filament sample distance is 7mm
  • the deposition time is 1.5 hours;
  • the quartz glass substrate after high-density seeding is placed in the hot wire chemical vapor deposition equipment for secondary diamond growth.
  • the process parameters include: using hydrogen, methane and argon as reaction gases to control hydrogen, methane and argon
  • the flow rates are 200sccm, 18sccm and 282sccm respectively, the deposition pressure is 1500Pa, the filament temperature is 6000W, the wire sample distance is 20mm, and the deposition time is 20min.
  • the diamond thin film quartz glass substrate is obtained.
  • Example 6 silicon nitride ceramic substrate
  • a method for preparing diamond thin film includes the following steps:
  • Nano-diamond seeding treatment is carried out on the sample.
  • the seeding solution is a detonation nano-diamond suspension.
  • Oxalic acid is added as a surfactant to the diamond suspension.
  • the concentration of oxalic acid is 10 -7 mol/l, pH 7.
  • the concentration of diamond powder is 0.005wt%.
  • the seeding method is to put the sample into the seeding solution and sonicate for 30 minutes, take it out, and blow dry with nitrogen;
  • micro-nano composite diamond film is prepared after the substrate is implanted, and the metal mesh prepared above is placed in the hot wire chemical vapor deposition equipment.
  • the process parameters are as follows: hydrogen and methane are used as reaction gases to control hydrogen and The flow directions of methane are 800sccm and 16sccm respectively, the deposition pressure is 2000Pa, the filament temperature is 2700°C, the filament sample distance is 7mm, and the deposition time is 1 hour;
  • lysine is added as a surfactant to the diamond suspension, the concentration of lysine is 5 ⁇ 10 -5 mol/l, pH 4, The concentration of diamond powder is 0.005wt%;
  • the process parameters are as follows: take hydrogen, methane, and argon as reaction gases to control hydrogen, The flow rates of methane and argon are 200sccm, 18sccm and 282sccm respectively, the deposition pressure is 1500Pa, the filament temperature is 2200°C, the filament sample distance is 20mm, and the deposition time is 20min to obtain a diamond thin film substrate.
  • the preparation method of the diamond film further includes step (8): chemical wet surface fluorination treatment, that is, first put the sample into H 2 SO 4 +H 2 O 2 (3:1 ) To oxidize the surface, then treat the sample in a hexane solution containing perfluorododecyltrichlorosilane in an atmosphere containing only nitrogen for 2 hours.
  • FIG. 4 The schematic diagram of the water contact angle of the diamond film before and after fluorination is shown in FIG. 4.
  • a diamond film substrate includes a substrate and a diamond film combined with the surface of the substrate.
  • the preparation method of diamond film includes the following steps:
  • Corrosion treatment is performed on the cleaned substrate, first ultrasonic cleaning in alkali solution for 5 minutes, and then in acid solution for 30 seconds.
  • the alkali solution is 1M NaOH, and the acid solution is 4M HCl;
  • step (3) Carry out seeding, put the substrate obtained in step (3) into the seeding solution and sonicate for 30 minutes, take it out, and blow dry with nitrogen; the seeding solution methacryloyloxyethyltrimethylammonium chloride is used as the surface
  • the active agent is added to the diamond suspension, the concentration of methacryloyloxyethyltrimethylammonium chloride is 10 -4 mol/l, pH 7, and the concentration of diamond powder is 0.5wt%;
  • the substrate after implantation is placed in hot wire chemical vapor deposition equipment to grow diamond.
  • the process parameters include: use hydrogen, methane, and argon as reaction gases, and control the flow rates of hydrogen, methane, and argon to 200 sccm, respectively. , 18sccm and 282sccm, deposition pressure 1500Pa, filament temperature 6000W, filament sample distance 20mm, deposition time 30min, to obtain a diamond film substrate.
  • Comparative Example 1 A continuous diamond film was grown by hot wire CVD, and the hydrophobic effect of the continuous and flat microstructured diamond film was inferior to the diamond film with bumps on the surface similar to the micro-nano structure on the surface of the lotus leaf.
  • Example 7 further fluorinated the surface of the diamond film on the basis of Example 1 to further improve the hydrophobicity.

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Abstract

一种具有多级次微纳结构的金刚石薄膜（200），包括自基体（100）表面依次向外形成的非连续的微米尺寸金刚石岛（211），以及由连续的纳米尺寸金刚石晶粒构成的纳米金刚石膜层（212），形成具有类荷叶乳突体（210）的多级次微纳结构。还包括一种具有多级次微纳结构的金刚石薄膜（200）的制备方法和应用。

Description

具有多级次微纳结构的金刚石薄膜及其制备方法和应用 技术领域
本申请涉及金刚石薄膜技术领域，具体而言，涉及一种具有多级次微纳结构的金刚石薄膜及其制备方法和应用。
背景技术
近前来，金刚石薄膜表面的润湿性倍受关注，因为润湿性能直接影响其在化学、生物和医药等领域的应用，尤其在宏观或微观器件的使用中，亟需亲水或超疏水的金刚石薄膜。例如，某些生物传感器需要亲水表面来促进细胞在探头上的吸附；相反，在海水、血液或机械冲击磨损等恶劣环境下工作的器件表面需要被保护，用超疏水的表面防化学腐蚀、防生物污损和抗机械磨损，例如抗血栓的人工支架、人工关节、深海精密探测器件和微流体器件等等。与其他高分子、金属和陶瓷材料相比，金刚石的硬度最高、抗磨损性能最佳、热导率最高、具有极强的化学惰性、化学性质稳定和生物相容性，是理想的亲水/超疏水材料。因此，如何有效控制金刚石的亲水/超疏水性能成为亟待解决的问题。
一般来说，改变表面的亲疏水性可通过两种方法，一是对金刚石表面进行化学改性，包括氢化、氧化和氟化处理等，二是通过改变金刚石表面的微米纳米形貌，往往采用等离子体刻蚀金刚石涂层的方法，需要等离子体反应刻蚀(RIE)真空设备以及金做为掩膜，过程复杂，价格昂贵。
现有技术中，论文Langmuir 30(2014)12647.采用等离子体刻蚀法在金刚石表面形成微米/纳米柱阵列的结构，接触角达153°；论文Journal of Materials Chemistry 20(2010)10671，通过离子刻蚀的方法将金刚石涂层刻蚀成表面呈纳米针状阵列，然后进行表面氟化处理，使接触角最高达到160°；论文Applied Surface Science 346(2015)189，采用热处理方法处理自支撑金刚石，得到针状结构，并经过后续氢等离子体处理，得到最高接触角109°；论文Carbon 139(2018)361首先采用光刻和反应离子刻蚀工艺将硅基体刻蚀成支柱状结构，然后沉积致密的纳米金刚石薄膜，然后进行氟等离子体处理，最高接触角达174°。但这些制备超疏水金刚石的技术一般都需要采用反应离子刻蚀设备(RIE)制备针/柱状纳米结构，即先制备出致密的金刚石薄膜，再采用金或其它金属做为掩膜，通入CF 4、O 2或H 2等反应气体，产生等离子体，具有耗时长，工艺复杂，且RIE设备昂贵等缺陷。
因此，所期望的是提供一种超疏水金刚石薄膜及其制备方法，其能够解决上述问题中的至少一个。
有鉴于此，特提出本申请。
发明内容
本申请的目的之一在于提供一种金刚石薄膜，具有类荷叶乳突体的多级次微纳结构，达到超疏水的效果。
本申请的目的之二在于提供一种上述金刚石薄膜的制备方法，采用化学气相沉积技术，依次经过低密度和高密度植晶获得，适用性强，容易制得，成本低，操作简单，工艺稳定，适合工业化生产。
本申请的目的之三在于提供一种上述金刚石薄膜或上述金刚石薄膜的制备方法制备得到的金刚石薄膜在防化学腐蚀、自清洁、抗机械磨损或油水分离中的应用。
为了实现本申请的上述目的，特采用以下技术方案：
第一方面，提供了一种金刚石薄膜，所述金刚石薄膜包括自基体表面依次向外形成的非连续的微米尺寸金刚石岛，以及由连续的纳米尺寸金刚石晶粒构成的纳米金刚石膜层，形成具有类荷叶乳突体的多级次微纳结构。
优选地，在本申请技术方案的基础上，所述微米尺寸金刚石岛的尺寸为1-10μm，优选为2-7μm；
优选地，纳米金刚石膜层的厚度为10-800nm，优选为20-200nm。
优选地，在本申请技术方案的基础上，所述基体包括硅、铜合金、不锈钢、玻璃或陶瓷中的一种。
第二方面，提供了一种金刚石薄膜的制备方法，包括以下步骤：
先在预处理后的基体上进行低密度植晶，并通过化学气相沉积法进行一次生长金刚石；
再在一次生长金刚石薄膜上进行高密度植晶，并通过化学气相沉积法进行二次生长金刚石，得到金刚石薄膜；
优选地，预处理包括清洗、腐蚀处理或喷砂处理、以及再清洗。
优选地，在本申请技术方案的基础上，低密度植晶的植晶密度为10 4-10 8个/cm 2，优选(2-3)×10 6个/cm 2；和/或，高密度植晶的植晶密度为10 9-10 12个/cm 2，(1-7)×10 11个/cm 2。
优选地，在本申请技术方案的基础上，低密度植晶通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相同；
优选地，低密度植晶采用的植晶溶液包括纳米金刚石粉、阴离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，阴离子表面活性剂在植晶溶液中的浓度为10 -6-10 -3mol/L，植晶溶液pH为2-8；优选阴离子表面活性剂为草酸或柠檬酸；
优选地，高密度植晶通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相反；
优选地，高密度植晶采用的植晶溶液包括纳米金刚石粉、阳离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，阳离子表面活性剂在植晶溶液中的浓度为 10 -6-10 -3mol/L，植晶溶液pH为5.5-6；优选阳离子表面活性剂为赖氨酸或甲基丙烯酰氧乙基三甲基氯化铵；
优选地，低密度植晶和高密度植晶的植晶方式均独立地为将基体放入植晶溶液中超声20-60min后取出干燥，优选干燥方式为用氮气吹干。
优选地，在本申请技术方案的基础上，热丝化学气相沉积法进行一次生长金刚石的工艺参数包括：以氢气、甲烷和任选的惰性气体为反应气体，反应气体总流量为500-850sccm，其中甲烷气体流量占总流量的1-5％，氢气和任选的惰性气体流量占总流量的95-99％，沉积压强为1500-6000Pa，灯丝温度为1800-2800℃，丝样距为7-15mm，沉积时间为1-1.5h。
优选地，在本申请技术方案的基础上，热丝化学气相沉积法进行二次生长金刚石的工艺参数包括：以氢气、甲烷和惰性气体为反应气体，反应气体总流量为500-850sccm，其中甲烷气体流量占总流量的1-5％，氢气流量占总流量的25-45％，惰性气体流量占总流量的50-70％，沉积压强为1500-6000Pa，灯丝温度为1800-2800℃，丝样距为20-25mm，沉积时间为20-30min。
优选地，在本申请技术方案的基础上，所述金刚石薄膜的制备方法还包括得到金刚石薄膜后再对其进行表面氟化处理，得到氟化的金刚石薄膜。
第三方面，提供了一种上述金刚石薄膜或上述金刚石薄膜的制备方法制备得到的金刚石薄膜在防化学腐蚀、自清洁、抗机械磨损或油水分离中的应用。
与已有技术相比，本申请具有如下有益效果：
(1)本申请设计了一种荷叶仿生多级次微纳复合金刚石薄膜材料，即具有微米和纳米晶粒复合的金刚石薄膜，该微纳复合结构的形貌类似于荷叶的表面形貌，有一个个微米尺寸凸起(金刚石岛)，凸起表面为纳米晶粒，达到超疏水的效果，可以实现自清洁和油水分离等功能，且金刚石化学性质稳定、抗磨损冲击能力和抗耐腐蚀性强，寿命长。
(2)本申请金刚石薄膜的制备方法采用化学气相沉积技术在网膜上制备出类似荷叶的微纳结构的金刚石表面，容易获得，先经过低密度植晶和沉积，再经过高密度植晶和沉积。此方法适用性强，通过调节微米颗粒的密度可有效控制水接触角80°-170°，表面的润湿性可得到有效控制；适用于任何平面或网状基体上类荷叶微纳结构金刚石涂层的沉积，该方法制备工艺简单，工艺稳定，适合工业化生产，能沉积出结合力良好的微纳结构金刚石。
附图说明
图1为本申请金刚石薄膜的结构示意图；
图2为本申请实施例1得到的金刚石薄膜表面与截面的微观形貌图，其中左侧为表面微观形貌图，右侧为截面微观形貌图；
图3为本申请实施例2得到的金刚石薄膜表面与截面的微观形貌图，其中左侧为表面 微观形貌图，右侧为截面微观形貌图；
图4为本申请实施例1得到的金刚石薄膜与实施例7得到的金刚石薄膜的水接触角示意图，其中左侧为实施例1得到的金刚石薄膜水接触角示意图，右侧为实施例7得到的金刚石薄膜水接触角示意图。
图标：100-基体；200-金刚石薄膜；210-乳突体；211-金刚石岛；212-纳米金刚石膜层。
具体实施方式
下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
根据本申请的第一个方面，提供了一种金刚石薄膜，包括自基体表面依次向外形成的非连续的微米尺寸金刚石岛，以及由连续的纳米尺寸金刚石晶粒构成的纳米金刚石膜层，形成具有类荷叶乳突体的多级次微纳结构。
基体可以为平面基体，也可以为网状基体，平面基体典型但非限制性的例如为硅、铜合金、不锈钢、玻璃或陶瓷；网状基体典型但非限制性的例如为金属网或织物网，优选为金属网；金属网包括但不限于铜网、钛网或不锈钢网等。
如图1所示，本申请基体100上具有类荷叶乳突体210多级次微纳结构的金刚石薄膜200，金刚石薄膜200包括自基体100表面依次向外形成的非连续的微米尺寸金刚石岛211，以及由连续的纳米尺寸金刚石晶粒构成的纳米金刚石膜层212。
金刚石岛是单个微米金刚石颗粒，或，多个纳米金刚石颗粒形成的聚集体。
微纳结构是指固体表面的一种微观特征形貌，需要在电子显微镜下才能观察得到，微米尺度的表面起伏上叠加纳米尺度的起伏所构成的多尺度(多级次，hierarchical)结构是一种分层状结构，即以微米量级尺寸的岛状结构为第一级，在每一个岛上分部连续的纳米尺寸晶粒为第二级。类荷叶乳突体微纳结构指本申请金刚石薄膜表面的微观特征形貌与荷叶表面的微观特征形貌类似，具有与荷叶类似的微纳乳突(papilla)结构粗糙表面。
在一种实施方式中，微米尺寸金刚石岛的尺寸为1-10μm，优选为2-7μm，例如2μm、5μm或7μm。
在一种实施方式中，纳米金刚石膜层的厚度为10-800nm，优选为20-200nm，例如50nm、100nm或200nm。
本申请金刚石薄膜具有仿生类荷叶多级次微纳结构，金刚石薄膜表面形貌类似于荷叶的表面形貌，有一个个乳突体，并且仿似荷叶表面的脂类物质，形成仿生超疏水表面，具有高疏水性和自清洁能力。此外，该薄膜在超疏水特性的同时金刚石化学性质稳定、抗磨 损冲击能力强、抗耐腐蚀性强并且寿命长。
根据本申请的第二个方面，提供了一种金刚石薄膜的制备方法，包括以下步骤：
先在预处理后的基体上进行低密度植晶，并通过化学气相沉积法进行一次生长金刚石；再在一次生长金刚石薄膜上进行高密度植晶，并通过化学气相沉积法进行二次生长金刚石，得到金刚石薄膜。
化学气相沉积法包括但不限于热丝或微波等离子体增强化学气相沉积法，优选热丝化学气相沉积法。
化学气相沉积金刚石生长需要植入金刚石晶种，然后在植入的晶种点进行外延生长，利用金刚石晶种在基体上的选择性吸附，构筑具有超疏水的微纳结构。本申请经过两次植晶和两次沉积在网膜上制备出类似荷叶的微纳结构的金刚石表面，即一次植晶-一次热丝沉积-二次植晶-二次热丝沉积，一次植晶为低密度植晶，二次植晶为高密度植晶，这里的高低是一个相对概念。
低密度植晶是指金刚石晶种在基体上呈单分散状态，从而一次沉积后基体上形成不致密的菜花状金刚石岛。
优选地，低密度植晶的植晶密度为10 4-10 8个/cm 2，优选(2-3)×10 6个/cm 2。
高密度植晶是指金刚石晶种在基体上呈连续排布状态，从而二次沉积后形成连续的金刚石薄膜。
优选地，高密度植晶的植晶密度为10 9-10 12个/cm 2，优选(1-7)×10 11个/cm 2。
在一种实施方式中，预处理包括清洗、腐蚀处理或喷砂处理、以及再清洗。
优选地，清洗和再清洗均独立地包括先用水超声清洗2-3次，每次5-10min，再用酒精超声清洗1-2次，每次5-10min；
优选地，腐蚀处理包括在碱溶液和/或酸溶液中超声清洗1-2min；优选碱溶液为0.5-1mol/L的NaOH或KOH溶液；优选酸溶液为1-4mol/L的HCl、H 2SO 4或HNO 3溶液。
对基体进行腐蚀处理或喷砂处理，一方面增加表面粗糙度，提高金刚石颗粒的吸附密度，另一方面通过预处理使基体表面电性与植晶所用的纳米金刚石电性相同。
低密度植晶可以通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相同来实现。
在一种实施方式中，低密度植晶采用的植晶溶液包括纳米金刚石粉、阴离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，例如0.005％、0.006％、0.007％、0.008％、0.009％或0.01％，阴离子表面活性剂在植晶溶液中的浓度为10 -6-10 -3mol/L，例如10 -6mol/L、10 -5mol/L、10 -4mol/L或10 -3mol/L，植晶溶液pH为2-8，例如pH2、pH3、pH4、pH5、pH6、pH7或pH8；优选阴离子表面活性剂为草酸或柠檬酸。通过选择适宜植晶溶液 在基体上植晶单分散晶种。
高密度植晶可以通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相反来实现。
在一种实施方式中，高密度植晶采用的植晶溶液包括纳米金刚石粉、阳离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，例如0.005％、0.006％、0.007％、0.008％、0.009％或0.01％，阳离子表面活性剂在植晶溶液中的浓度为10 -6-10 -3mol/L，例如10 -6mol/L、10 -5mol/L、10 -4mol/L或10 -3mol/L，植晶溶液pH为5.5-6；优选阳离子表面活性剂为赖氨酸或甲基丙烯酰氧乙基三甲基氯化铵。通过选择适宜植晶溶液继续植晶连续晶种。
在一种实施方式中，低密度植晶和高密度植晶的植晶方式均独立地为将基体放入植晶溶液中超声20-60min后取出干燥，优选干燥方式为用氮气吹干。超声植晶方法成本低，操作简单，适合工业化生产。
本申请采用热丝/微波化学气相沉积法进行两步法沉积，即首先优选通过调控金刚石植晶溶液的纳米金刚石尺寸和zeta电位，使纳米金刚石与基体表面电性一致，吸附在基体上的金刚石晶种密度较低(10 4-10 8cm -2)，沉积第一层不连续的金刚石岛(大小1-10μm)；然后采用超分散的纳米金刚石溶液对上述第一层再超声植晶，优选使纳米金刚石与基体表面电性相反，使吸附在样品表面的金刚石晶种密度较高(>10 8cm -2)，然后在第一层的表面沉积一层超薄纳米金刚石薄膜(厚度<500nm)。通过调节微米颗粒的密度可有效控制水接触角80°-170°，润湿性能可控。
本申请无需RIE刻蚀，在制备金刚石薄膜前，通过改变金刚石植晶溶液性质来制备出具有多级次微纳复合的金刚石薄膜。本申请由于只改变了植晶溶液而得到超疏水金刚石薄膜，工艺极其简单并且成本低，适合大面积工业化生产，能在三维或二维基体上沉积出结合力良好的微纳复合的金刚石。
在一种实施方式中，化学气相沉积法为热丝化学气相沉积法，热丝化学气相沉积法进行一次生长金刚石的工艺参数包括：以氢气、甲烷和任选的惰性气体为反应气体，典型但非限制性的惰性气体为氩气，反应气体总流量为500-850sccm，例如500sccm、600sccm、700sccm、800sccm或850sccm，其中甲烷气体流量占总流量的1-5％，例如1％、2％、3％、4％或5％，氢气和任选的惰性气体流量占总流量的95-99％，沉积压强为1500-6000Pa，例如1500Pa、1600Pa、1700Pa、1800Pa、1900Pa、2000Pa、3000Pa、4000Pa、5000Pa或6000Pa，灯丝温度为1800-2800℃，例如2000℃、2400℃或2600℃，丝样距(上和下热丝的离样距离)为7-15mm，例如7mm、8mm、9mm、10mm、12mm、14mm或15mm，沉积时间为1-1.5h，例如1h、1.2h或1.5h。
通过控制沉积工艺参数，在低密度单分散植晶晶种上沉积出质量好的不致密的菜花状金刚石岛。
在一种实施方式中，化学气相沉积法为热丝化学气相沉积法，热丝化学气相沉积法进行二次生长金刚石的工艺参数包括：以氢气、甲烷和惰性气体为反应气体，反应气体总流量为500-850sccm，例如500sccm、600sccm、700sccm、800sccm或850sccm，其中甲烷气体流量占总流量的1-5％，例如1％、2％、3％、4％或5％，氢气流量占总流量的25-45％，例如25％、28％、30％、35％、40％或45％，惰性气体流量占总流量的50-70％，例如50％、55％、60％、65％或70％，沉积压强为1500-6000Pa，例如1500Pa、1600Pa、1700Pa、1800Pa、1900Pa、2000Pa、3000Pa、4000Pa、5000Pa或6000Pa，灯丝温度为1800-2800℃，例如2000℃、2400℃或2600℃，丝样距(上和下热丝的离样距离)为20-25mm，例如20mm、21mm、22mm、23mm、24mm或25mm，沉积时间为20-30min，例如20min、25min或30min。
通过控制沉积工艺参数，在高密度连续植晶晶种上生长质量好的超薄金刚石薄膜，最终形成具有乳突的类荷叶仿生微纳结构。
在一种实施方式中，金刚石薄膜的制备方法还包括得到金刚石薄膜后再对其进行表面氟化处理，得到氟化的金刚石薄膜。
表面氟化处理包括但不限于化学湿法或等离子体氟化处理。
通过进一步的表面氟化处理处理沉积后的样品表面，能进一步提升其水接触角。
作为一种优选的实施方式，一种典型的金刚石薄膜的制备方法包括以下步骤：
(a)对基体表面进行清洗，保持试样表面清洁干净；
(b)对清洗好的基体进行腐蚀或喷砂处理，使基体表面电性与植晶用纳米金刚石相同；
(c)对基体进行清洗，将残留在基体中的腐蚀溶液清洗干净；
(d)对基体进行金刚石的植晶处理；
(e)将上述基体置入热丝化学气相沉积或微波等离子体增强化学气相沉积设备中沉积不致密的金刚石岛；
(f)将上述沉积完金刚石岛的样品进行二次植晶，使基体表面电性与植晶用纳米金刚石相反；
(g)二次植晶完的基体置入热气化学气相沉积或微波等离子体增强化学气相沉积设备中利用超低温工艺生长超薄金刚石薄膜。
其中：步骤(a)和步骤(c)中对基体清洗为先去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟；
步骤(b)中的腐蚀处理为在碱或酸溶液中超声清洗1分钟；
步骤(d)中植晶溶液为爆轰纳米金刚石悬浮液，成分为金刚石粉质量分数0.5％-0.005％， 草酸或柠檬酸浓度为10 -6M-10 -3M，溶剂为去离子水，pH为2-8。植晶方式为将试样放入植晶溶液中超声30分钟，取出，用氮气吹干；
步骤(f)的植晶溶液成分为金刚石粉质量分数0.5％-0.005％，赖氨酸或甲基丙烯酰氧乙基三甲基氯化铵，浓度为10 -6M-10 -3M，溶剂为去离子水，pH为6。
根据本申请的第三个方面，提供了一种上述金刚石薄膜或上述金刚石薄膜的制备方法制备得到的金刚石薄膜在防化学腐蚀、自清洁、抗机械磨损或油水分离中的应用。
由于本申请的金刚石薄膜具有高疏水性，同时耐腐蚀性强，能够应用在防化学腐蚀、自清洁、抗机械磨损或油水分离中，具有广阔的应用前景。
下面通过具体的实施例和对比例进一步说明本申请，但是，应当理解为，这些实施例仅是用于更详细地说明之用，而不应理解为用于以任何形式限制本申请。本申请涉及的各原料均可通过商购获取。
实施例1 基体硅
一种金刚石薄膜的制备方法，包括以下步骤：
(1)对基体硅表面进行清洗，首先使用去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(2)对清洗好的基体硅进行腐蚀处理，将样品放入10ml 32％H 2O 2+10ml NH 3·H 2O+50ml H 2O溶液中，80摄氏度处理10min；
(3)对基体硅进行再清洗，用去离子水超声3次，每次5分钟，最后用氮气吹干；
(4)对基体硅进行低密度植晶，将基体硅放入低密度植晶溶液中超声30分钟，取出，用氮气吹干；低密度植晶溶液为爆轰纳米金刚石悬浮液，草酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为7×10 -5mol/l，pH 5，金刚石粉的浓度为0.005wt％；
(5)低密度植晶后的基体硅置入热丝化学气相沉积设备中，进行一次生长金刚石，工艺参数包括：以氢气和甲烷为反应气体，控制氢气和甲烷的流量分别为800sccm和32sccm，沉积气压为2000Pa，灯丝温度为2600℃，丝样距为7mm，沉积时间为1小时；
(6)进行高密度植晶，将步骤(5)得到的基体硅放入高密度植晶溶液中超声30分钟，取出，用氮气吹干；高密度植晶溶液赖氨酸作为表面活性剂添加到金刚石悬浮液中，赖氨酸的浓度为10 -5mol/l，pH 4，金刚石粉的浓度为0.005wt％；
(7)高密度植晶后的基体硅置入热丝化学气相沉积设备中，进行二次生长金刚石，工艺参数包括：以氢气、甲烷和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度2000℃，丝样距20mm，沉积时间30min，得到金刚石薄膜基体硅。
图2为实施例1得到的金刚石薄膜表面与截面的微观形貌图。
实施例2 铜合金基体
一种金刚石薄膜的制备方法，包括以下步骤：
(1)对铜合金基体表面进行清洗，首先使用去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(2)对清洗好的铜合金基体进行腐蚀处理，先在碱溶液中超声清洗5分钟，然后在酸溶液中清洗30秒，其中碱溶液为1M的NaOH，酸溶液为4M的HCl；
(3)对铜合金基体进行再清洗，首先使用去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(4)对铜合金基体进行低密度植晶，将铜合金基体放入低密度植晶溶液中超声20分钟，取出，用氮气吹干；低密度植晶溶液为爆轰纳米金刚石悬浮液，柠檬酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为7×10 -5mol/l，pH 6，金刚石粉的浓度为0.05wt％；
(5)低密度植晶后的基体置入热丝化学气相沉积设备中，进行一次生长金刚石，工艺参数包括：以氢气和甲烷为反应气体，控制氢气和甲烷的流量分别为800sccm和16sccm，沉积气压为2000Pa，灯丝温度为2600℃，丝样距为7mm，沉积时间为1小时；
(6)进行高密度植晶，将步骤(5)得到的铜合金基体放入高密度植晶溶液中超声20分钟，取出，用氮气吹干；高密度植晶溶液谷氨酸作为表面活性剂添加到金刚石悬浮液中，谷氨酸的浓度为7×10 -5mol/l，pH 4，金刚石粉的浓度为0.05wt％；
(7)高密度植晶后的铜合金基体置入热丝化学气相沉积设备中，进行二次生长金刚石，工艺参数包括：以氢气和甲烷为反应气体，控制氢气和甲烷氩气的流量分别为800sccm和32sccm，沉积气压2000Pa，灯丝温度2200℃，丝样距7mm，沉积时间30min，得到金刚石薄膜铜合金基体。
图3为实施例2得到的金刚石薄膜表面与截面的微观形貌图。
实施例3 玻璃基体
一种金刚石薄膜的制备方法，包括以下步骤：
(1)对玻璃基体表面进行清洗，首先使用去离子水超声清洗2次，每次10分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(2)对清洗好的玻璃基体进行喷砂处理；
(3)对玻璃基体进行低密度植晶，将玻璃基体放入低密度植晶溶液中超声30分钟，取出，用氮气吹干；低密度植晶溶液为爆轰纳米金刚石悬浮液，草酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为7×10 -4mol/l，pH 3，金刚石粉的浓度为0.5wt％；
(4)低密度植晶后的基体置入热丝化学气相沉积设备中，进行一次生长金刚石，工艺 参数包括：以氢气和甲烷为反应气体，控制氢气和甲烷的流量分别为800sccm和32sccm，沉积气压为2000Pa，灯丝温度2500℃，丝样距为10mm，沉积时间为1.5小时；
(5)进行高密度植晶，将步骤(5)得到的玻璃基体放入高密度植晶溶液中超声20分钟，取出，用氮气吹干；高密度植晶溶液甲基丙烯酰氧乙基三甲基氯化铵作为表面活性剂添加到金刚石悬浮液中，甲基丙烯酰氧乙基三甲基氯化铵的浓度为10 -4mol/l，pH 7，金刚石粉的浓度为0.5wt％；
(6)高密度植晶后的玻璃基体置入热丝化学气相沉积设备中，进行二次生长金刚石，工艺参数包括：以氢气、甲烷和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度6000W，丝样距25mm，沉积时间30min，得到金刚石薄膜玻璃基体。
实施例4 不锈钢基体
一种金刚石薄膜的制备方法，包括以下步骤：
(1)对不锈钢基体表面喷砂，然后用酒精超声清洗15min，用氮气吹干；
(2)将样品置入热丝化学气相沉积设备中，沉积碳化硅中间层，工艺参数为：氢气和四甲基硅烷甲烷的流量分别为800sccm和80sccm，沉积气压为2000Pa，灯丝温度为2000℃；
(3)对样品进行纳米金刚石的低密度植晶处理，低密度植晶溶液为爆轰纳米金刚石悬浮液，草酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为7×10 -5mol/l，pH 8，金刚石粉的浓度为0.005wt％。植晶方式为将试样放入植晶溶液中超声30分钟，取出，用氮气吹干；
(4)将上述制得的不锈钢基体置入热丝化学气相沉积设备中，工艺参数如下：以氢气、氩气和甲烷为反应气体，控制氢气、氩气和甲烷的流量分别为200sccm、282sccm和18sccm，沉积气压为2000Pa，灯丝温度2500℃，丝样距为15mm，沉积时间为0.5小时；
(5)将样品重新置入金刚石悬浮液中进行高密度植晶，甲基丙烯酰氧乙基三甲基氯化铵作为表面活性剂添加到金刚石悬浮液中，甲基丙烯酰氧乙基三甲基氯化铵的浓度为5×10 -6mol/l，pH 4，金刚石粉的浓度为0.005wt％；
(6)高密度植晶后的不锈钢基体置入热丝化学气相沉积设备中，进行二次生长金刚石，工艺参数包括：以氢气、甲烷和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度2200℃，丝样距20mm，沉积时间30min，得到金刚石薄膜不锈钢基体。
实施例5 石英玻璃基体
一种金刚石薄膜的制备方法，包括以下步骤：
(1)用水、酒精和丙酮分别对石英玻璃超声清洗5分钟，用氮气吹干；
(2)对石英玻璃基体进行低密度植晶，将石英玻璃基体放入低密度植晶溶液中超声30分钟，取出，用氮气吹干；低密度植晶溶液为爆轰纳米金刚石悬浮液，草酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为7×10 -5mol/l，pH 3，金刚石粉的浓度为0.005wt％；
(3)低密度植晶后的基体置入热丝化学气相沉积设备中，进行一次生长金刚石，工艺参数包括：以氢气和甲烷为反应气体，控制氢气和甲烷的流量分别为800sccm和32sccm，沉积气压为2000Pa，灯丝温度2600℃，丝样距为7mm，沉积时间为1.5小时；
(4)进行高密度植晶，将步骤(5)得到的石英玻璃基体放入高密度植晶溶液中超声30分钟，取出，用氮气吹干；高密度植晶溶液赖氨酸作为表面活性剂添加到金刚石悬浮液中，赖氨酸的浓度为5×10 -6mol/l，pH 6，金刚石粉的浓度为0.005wt％；
(5)高密度植晶后的石英玻璃基体置入热丝化学气相沉积设备中，进行二次生长金刚石，工艺参数包括：以氢气、甲烷和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度6000W，丝样距20mm，沉积时间20min，得到金刚石薄膜石英玻璃基体。
实施例6 氮化硅陶瓷基体
一种金刚石薄膜的制备方法，包括以下步骤：
(1)对氮化硅陶瓷基体表面进行清洗，首先使用去离子水超声清洗2次每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(2)对样品进行纳米金刚石的植晶处理，植晶溶液为爆轰纳米金刚石悬浮液，草酸作为表面活性剂添加到金刚石悬浮液中，草酸的浓度为10 -7mol/l，pH 7，金刚石粉的浓度为0.005wt％，植晶方式为将试样放入植晶溶液中超声30分钟，取出，用氮气吹干；
(3)将植晶之后的基体进行微纳复合金刚石薄膜的制备，将上述制得的金属网置入热丝化学气相沉积设备中，工艺参数如下：以氢气和甲烷为反应气体，控制氢气和甲烷的流向分别为800sccm和16sccm，沉积气压为2000Pa，灯丝温度2700℃，丝样距为7mm，沉积时间为1小时；
(4)将样品重新置入金刚石悬浮液中进行二次植晶，赖氨酸作为表面活性剂添加到金刚石悬浮液中，赖氨酸的浓度为5×10 -5mol/l，pH 4，金刚石粉的浓度为0.005wt％；
(5)将二次植完晶的金属网置入热丝化学气相沉积设备中，进行二次生长超薄金刚石薄膜，工艺参数如下：以氢气、甲烷、和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度2200℃，丝样距20mm，沉积时间20min，得到金刚石薄膜基体。
实施例7
本实施例与实施例1的区别在于，金刚石薄膜的制备方法还包括步骤(8)：化学湿法 表面氟化处理，即先将样品放入H 2SO 4+H 2O 2(3:1)中氧化表面，再在只含有氮气的气氛里将样品至于含全氟十二烷基三氯硅烷的己烷溶液中处理2h。
氟化处理前后的金刚石薄膜的水接触角示意图如图4所示。
对比例1
一种金刚石薄膜基体，包括基体以及与基体表面结合的金刚石薄膜。
金刚石薄膜的制备方法，包括以下步骤：
(1)对基体表面进行清洗，首先使用去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(2)对清洗好的基体进行腐蚀处理，先在碱溶液中超声清洗5分钟，然后在酸溶液中清洗30秒。其中碱溶液为1M的NaOH，酸溶液为4M的HCl；
(3)对基体进行再清洗，首先使用去离子水超声清洗2次，每次5分钟，最后用酒精超声清洗5分钟，用氮气吹干；
(4)进行植晶，将步骤(3)得到的基体放入植晶溶液中超声30分钟，取出，用氮气吹干；植晶溶液甲基丙烯酰氧乙基三甲基氯化铵作为表面活性剂添加到金刚石悬浮液中，甲基丙烯酰氧乙基三甲基氯化铵的浓度为10 -4mol/l，pH 7，金刚石粉的浓度为0.5wt％；
(5)植晶后的基体置入热丝化学气相沉积设备中，进行生长金刚石，工艺参数包括：以氢气、甲烷、和氩气为反应气体，控制氢气、甲烷和氩气的流量分别为200sccm、18sccm和282sccm，沉积气压1500Pa，灯丝温度6000W，丝样距20mm，沉积时间30min，得到金刚石薄膜基体。
试验例
用接触角测量仪测量实施例和对比例得到的金刚石薄膜基体，测量基体表面对3微升的水的接触角，结果如表1所示。
表1
实施例或对比例 水接触角
实施例1 147°
实施例2 130°
实施例3 145°
实施例4 150°
实施例5 135°
实施例6 120°
实施例7 163°
对比例1 101°
从表1的结果可以看出，本申请方法流程简单，得到的金刚石薄膜具有超疏水特性，同时金刚石化学性质稳定、抗磨损冲击能力强、抗耐腐蚀性强并且寿命长。
对比例1用热丝CVD生长连续地金刚石薄膜，连续且微观结构平整的金刚石薄膜的疏水效果差于表面一颗颗凸起类似荷叶表面微纳结构的金刚石薄膜。
实施例7在实施例1的基础上进一步对金刚石薄膜进行表面氟化处理，疏水性进一步提高。
尽管已用具体实施例来说明和描述了本申请，然而应意识到，在不背离本申请的精神和范围的情况下可作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本申请范围内的所有这些变化和修改。

Claims (10)

  1. 一种金刚石薄膜，其特征在于，所述金刚石薄膜包括自基体表面依次向外形成的非连续的微米尺寸金刚石岛，以及由连续的纳米尺寸金刚石晶粒构成的纳米金刚石膜层，形成具有类荷叶乳突体的多级次微纳结构。
  2. 按照权利要求1所述的金刚石薄膜，其特征在于，所述微米尺寸金刚石岛的尺寸为1-10μm，优选为2-7μm；
    优选地，纳米金刚石膜层的厚度为10-800nm，优选为20-200nm。
  3. 按照权利要求1或2所述的金刚石薄膜，其特征在于，所述基体包括硅、铜合金、不锈钢、玻璃或陶瓷中的一种。
  4. 一种权利要求1-3任一项所述的金刚石薄膜的制备方法，其特征在于，包括以下步骤：
    先在预处理后的基体上进行低密度植晶，并通过化学气相沉积法进行一次生长金刚石；
    再在一次生长金刚石薄膜上进行高密度植晶，并通过化学气相沉积法进行二次生长金刚石，得到金刚石薄膜；
    优选地，预处理包括清洗、腐蚀处理或喷砂处理、以及再清洗。
  5. 按照权利要求4所述的金刚石薄膜的制备方法，其特征在于，低密度植晶的植晶密度为10 4-10 8个/cm 2，优选(2-3)×10 6个/cm 2；和/或，高密度植晶的植晶密度为10 9-10 12个/cm 2，(1-7)×10 11个/cm 2。
  6. 按照权利要求4或5所述的金刚石薄膜的制备方法，其特征在于，低密度植晶通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相同；
    优选地，低密度植晶采用的植晶溶液包括纳米金刚石粉、阴离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，阴离子表面活性剂在植晶溶液中的浓度为10 -6-10 -3mol/L，植晶溶液pH为2-8；优选阴离子表面活性剂为草酸或柠檬酸；
    优选地，高密度植晶通过调控金刚石植晶溶液的zeta电位，使纳米金刚石与基体表面电性相反；
    优选地，高密度植晶采用的植晶溶液包括纳米金刚石粉、阳离子表面活性剂和水，纳米金刚石粉质量占植晶溶液质量的0.005-0.5％，阳离子表面活性剂在植晶溶液中的浓度为10 -6-10 -3mol/L，植晶溶液pH为4-6；优选阳离子表面活性剂为赖氨酸或甲基丙烯酰氧乙基三甲基氯化铵；
    优选地，低密度植晶和高密度植晶的植晶方式均独立地为将基体放入植晶溶液中 超声20-60min后取出干燥，优选干燥方式为用氮气吹干。
  7. 按照权利要求4或5所述的金刚石薄膜的制备方法，其特征在于，热丝化学气相沉积法进行一次生长金刚石的工艺参数包括：以氢气、甲烷和任选的惰性气体为反应气体，反应气体总流量为500-850sccm，其中甲烷气体流量占总流量的1-5％，氢气和任选的惰性气体流量占总流量的95-99％，沉积压强为1500-6000Pa，灯丝温度为1800-2800℃，丝样距为7-15mm，沉积时间为1-1.5h。
  8. 按照权利要求4或5所述的金刚石薄膜的制备方法，其特征在于，热丝化学气相沉积法进行二次生长金刚石的工艺参数包括：以氢气、甲烷和惰性气体为反应气体，反应气体总流量为500-850sccm，其中甲烷气体流量占总流量的1-5％，氢气流量占总流量的25-45％，惰性气体流量占总流量的50-70％，沉积压强为1500-6000Pa，灯丝温度为1800-2800℃，丝样距为20-25mm，沉积时间为20-30min。
  9. 按照权利要求4或5所述的金刚石薄膜的制备方法，其特征在于，所述金刚石薄膜的制备方法还包括得到金刚石薄膜后再对其进行表面氟化处理，得到氟化的金刚石薄膜。
  10. 一种权利要求1-3任一项所述的金刚石薄膜或权利要求4-9任一项所述的金刚石薄膜的制备方法制备得到的金刚石薄膜在防化学腐蚀、自清洁、抗机械磨损或油水分离中的应用。
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