WO2018113053A1 - 一种具有类金刚石阵列的结构件及其制备方法 - Google Patents

一种具有类金刚石阵列的结构件及其制备方法 Download PDF

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WO2018113053A1
WO2018113053A1 PCT/CN2017/070889 CN2017070889W WO2018113053A1 WO 2018113053 A1 WO2018113053 A1 WO 2018113053A1 CN 2017070889 W CN2017070889 W CN 2017070889W WO 2018113053 A1 WO2018113053 A1 WO 2018113053A1
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diamond
substrate
array
coating
nanoneedle
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French (fr)
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唐永炳
杨扬
秦盼盼
张文军
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
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    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • 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
    • C23C16/44—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 method of coating
    • C23C16/50—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 method of coating using electric discharges
    • C23C16/513—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 method of coating using electric discharges using plasma jets
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not

Definitions

  • the invention relates to the field of superhydrophobic materials, in particular to a structural member having a diamond-like array and a preparation method thereof.
  • Biomaterials particularly biomaterials used in medical implants (such as auto-implantable cardiac defibrillators, urinary catheters, etc.) and surgical instruments, must meet the various requirements for clinical use due to direct contact with human tissue. In addition to the good physical, chemical and mechanical properties of general materials, it must also be antibacterial to protect against bacterial colonization, which can lead to the formation of biofilms and bacteria on the surface of the equipment.
  • Biofilm is a colony aggregate formed by microbial cells that accumulate on the surface of the medium by the extracellular polymer secreted by the microorganisms in response to changes in the external environment. The formation of biofilms increases the drug resistance of bacteria and improves the difficulty of clinical treatment. Therefore, it is generally required to surface-modify medical metal and ceramic materials to provide antibacterial properties.
  • Diamond-like carbon (DLC) is an amorphous carbon material with sp 2 and sp 3 bonding characteristics. It has high hardness, low friction, high thermal conductivity, high light transmission, strong chemical inertness and good Excellent properties such as biocompatibility, DLC film has broad application prospects in optical windows, tools, molds and other parts, biomedical devices and other fields. DLC coating as a surface modification layer of medical implant materials, its main advantages are: the mechanical strength of 1DLC coating and the adaptability of the implant material not only ensure the firm bonding of the coating and medical implant materials.
  • the high-density DLC coating has excellent wear and corrosion resistance, which not only improves the corrosion resistance of the implant material under the bio-mechanical interaction environment, but also effectively It shields the diffusion of metal ions into surrounding tissues and blood, thereby inhibiting the damage of harmful metal ions into biological tissues and preventing the toxic reaction caused by biological tissues, prolonging the service life of medical materials; 3 low toxicity and high chemical stability
  • the DLC coating can adapt to the implant environment due to its adjustable surface interface properties, reducing the body's rejection of medical implant materials and improving its compatibility with biological tissues.
  • the first aspect of the present invention provides a structural member having a diamond-like array by depositing a diamond-like coating on a substrate and then etching the same to form a needle-like tip structure.
  • Diamond nanoneedle array The structural member with the diamond-like array has good antibacterial properties, and solves the problem of weak or little antibacterial property of the diamond-like coating in the prior art.
  • the present invention provides a structural member having a diamond-like array, comprising a substrate and a diamond-like nanoneedle array having a tip structure disposed on the substrate, the diamond-like nanoneedle array being formed by A type of diamond coating on the substrate is etched.
  • a residual diamond-like coating is further disposed between the substrate and the diamond-like nanoneedle array, and the diamond-like nanoneedle array is formed on the surface of the residual diamond-like coating.
  • the residual diamond-like coating is a complete coating without diamond-like nanoneedles.
  • the residual diamond-like carbon coating has a thickness of 100 nm to 3 ⁇ m. The presence of the residual diamond-like coating is more advantageous for improving the bonding force between the matrix and the diamond-like nanoneedle array.
  • the diamond-like nanoneedle in the diamond nanoneedle array has a tapered structure, and the diamond-like nanoneedle has an aspect ratio of 20 to 80, a tip diameter of 10 to 100 nm, and a bottom diameter of 30 nm to 2 ⁇ m.
  • the needle density is 10 4 to 10 9 ⁇ cm -2 .
  • the aspect ratio refers to a ratio of the height of the nanoneedle to the diameter corresponding to half of the height of the nanoneedle.
  • the bottom diameter should be no smaller than the tip diameter.
  • the height of the diamond-like nanoneedle may be a uniform height, or may be a nanoneedle of different height, and the height thereof varies between 10 nm and 10 ⁇ m.
  • a nanoneedle having a height of 100 nm or less and a nanoneedle having a height of 0.8 to 9 ⁇ m can be simultaneously present.
  • the diamond-like nanoneedle has a height of 400 nm to 10 ⁇ m.
  • the height of the diamond-like nanoneedles is a gradient.
  • the size of the diamond-like nanoneedle is similar to the size of the bacteria, and the long diameter is relatively high.
  • the size of the diamond-like nanoneedles may be the same or may not be exactly the same, and there is a certain level of change.
  • the diamond-like nanoneedle has an aspect ratio of 30 to 60 (preferably 35-55, 40-50); a tip diameter of 10 to 50 nm or 60 to 100 nm; and a bottom diameter of 800 nm to 2 ⁇ m or 200 to 700 nm or 30. ⁇ 200nm.
  • the needle density may be from 10 5 to 10 9 cm 2 , and may be, for example, 10 6 to 10 9 cm 2 and 10 8 cm 2 .
  • the antibacterial properties and mammalian biocellular compatibility of the antibacterial diamond-like array material can be optimized by controlling the size and density of the diamond-like nanoneedle.
  • the substrate is one or more of a metal, a metal alloy, a cemented carbide, a stainless steel, a polymer, a glass, and silicon, but is not limited thereto.
  • commonly used implant materials such as titanium alloy TC4.
  • the metal may be selected from any one of titanium Ti, nickel Ni, molybdenum Mo, niobium Nb, tantalum Ta, niobium Ru, and platinum Pt.
  • the metal alloy may be a titanium-based alloy, a cobalt-based alloy (such as a cobalt-chromium alloy), a Ni-Ti alloy, or a nickel-based alloy;
  • the cemented carbide may be a tungsten carbide-based hard alloy or a titanium carbide-based hard alloy.
  • the antibacterial diamond-like array material further comprises a transition metal layer, the transition metal layer is located The substrate is between the residual diamond-like coating.
  • the transition metal layer has a thickness of 50 to 500 nm.
  • the metal in the transition metal layer is one of transition metal elements such as Cr, Ti, Ni, Zr, W, Mo, Nb, Ta, Ru, Pt.
  • the material of the substrate itself is a transition metal or a metal alloy having a small difference in thermal expansion coefficient (such as titanium Ti, nickel Ni, niobium Nb, tantalum Ta; titanium-based alloy, Ni-Ti alloy, nickel-based alloy),
  • a transition metal layer is first deposited on the substrate, and a diamond-like coating is deposited on the transition metal layer to enhance the strong bonding of the diamond-like coating to the substrate.
  • a structural member having a diamond-like array according to a first aspect of the present invention includes a substrate and a diamond-like nanoneedle array having a tip structure disposed on a surface of the substrate, the diamond-like nanoneedle array passing through a class formed on a surface of the substrate layer
  • the diamond coating is etched.
  • the diamond-like nanoneedle array not only exerts pressure on the cell wall of the bacteria, but also penetrates the cell wall of the bacteria to cause it to stretch and finally dissolve, thereby causing the death of the bacteria, effectively destroying the formation of the biofilm, and imparting significant antibacterial properties to the diamond-like coating.
  • the diamond-like nanoneedle array is almost non-toxic to most cells, especially human cells, and can also support the adhesion of human cells, and can be applied to various medical implants and surgical instruments to prevent Bacterial infection is beneficial to human health.
  • the present invention provides a method of fabricating a structural member having a diamond-like array, comprising the steps of:
  • the diamond-like carbon coating is etched to obtain a diamond-like nanoneedle array having a tip structure.
  • the pretreatment comprises one or more of ultrasonic cleaning, glow cleaning, and ion etching cleaning.
  • the ultrasonic cleaning may be performed first, and then the ultrasonically cleaned substrate is placed in a vacuum chamber of a deposition apparatus, and then glow cleaning is performed first, followed by ion etching cleaning. This will better ensure the cleanliness of the surface of the workpiece to be treated.
  • the ultrasonic cleaning is performed by ultrasonicing in deionized water, acetone and ethanol in sequence for 5-30 min. After ultrasonic cleaning, the substrate needs to be blown dry before other pretreatments are performed.
  • both the glow cleaning and the ion etching cleaning need to be performed under a vacuum of 5.0 ⁇ 10 ⁇ 3 Pa or less.
  • the condition of the glow cleaning is: introducing argon into the vacuum chamber, the flow rate of the argon gas is 300-500 sccm, the working pressure is 1.0-1.7 Pa, and the substrate bias is -500--800 V, and the glow cleaning is performed.
  • the time is 10 to 30 minutes.
  • the ion etching cleaning condition is: turning on the ion source, the ion source voltage is 50-90V; the argon gas flow rate is 70-300sccm, the working gas pressure is 0.5-1.2Pa, and the substrate bias voltage is -100--800V.
  • the ion etching cleaning time is 10 to 30 minutes.
  • the material of the substrate is medical stainless steel, polymer, cobalt-based alloy, cemented carbide, glass and silicon, deposition is also performed after the pretreatment and before depositing the diamond-like coating.
  • a transition metal layer is also performed after the pretreatment and before depositing the diamond-like coating.
  • the step of depositing the transition metal layer comprises: introducing argon into the vacuum chamber, adjusting the pressure of the vacuum chamber to 0.2-1.3 Pa, opening the transition metal arc target, performing arc deposition of the metal transition layer, and controlling the target current. It is 80-200A, the substrate bias is -100 ⁇ -300V, and the deposition time is 2-10min.
  • the transition metal layer has a thickness of 50 to 500 nm.
  • the flow rate of the argon gas is 50 to 400 sccm.
  • the method of depositing the diamond-like carbon coating includes magnetron sputtering, hot wire chemical vapor deposition (HFCVD), plasma enhanced chemical vapor deposition, or other conventional methods for preparing a diamond-like coating.
  • HFCVD hot wire chemical vapor deposition
  • plasma enhanced chemical vapor deposition or other conventional methods for preparing a diamond-like coating.
  • the diamond-like coating is deposited by means of magnetron sputtering, and specifically includes: introducing argon into the vacuum chamber and opening the carbon target for deposition, so that the pressure in the vacuum chamber is 0.5 to 1.0 Pa, the target power of the carbon target is 1 to 5 kW, the substrate has a negative bias of -50 to -200 V, and the deposition time is 30 to 600 min.
  • the plasma-enhanced chemical vapor deposition method is used to deposit the diamond-like carbon coating, specifically, comprising: introducing a gaseous carbon source into the vacuum chamber for deposition, so that the pressure in the vacuum chamber is 0.5. ⁇ 1.0Pa, ion source voltage is 50 ⁇ 100V, substrate negative bias is -50 ⁇ -200V, deposition time is 30 ⁇ 600min.
  • the gaseous carbon source may include methane, acetylene, acetone, and the like.
  • the diamond-like carbon coating has a thickness of 500 nm to 10 ⁇ m.
  • the diamond-like coating is etched by inductively coupled plasma (ICP) etching or electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MWPCVD) etching.
  • ICP inductively coupled plasma
  • ECR-MWPCVD electron cyclotron resonance microwave plasma chemical vapor deposition
  • the diamond-like carbon coating has a thickness of 500 nm to 10 ⁇ m.
  • the ICP etching condition is: placing a matrix deposited with a diamond-like coating in an inductively coupled plasma etching (ICP) cavity, using hydrogen, argon, oxygen, helium, nitrogen, and gaseous states.
  • ICP inductively coupled plasma etching
  • One or more of the carbon source, CF 4 , C 4 F 8 and SF 6 are reaction gases, the flow rate of the reaction gas is 5 to 200 sccm, the reaction gas pressure is 0.1 to 10 Pa, and the power supply power of the ICP is 500 to 3000 W.
  • the RF power P rf on the substrate stage is 50-300 W, and the etching time is 10-600 min. At this time, the thickness of the diamond-like coating to be etched is 400 nm to 10 ⁇ m.
  • the power supply power P ICP of the ICP plays a key role in the ionization rate of the gas;
  • the radio frequency power P rf refers to the bias power loaded on the substrate stage (base), and P rf determines the etching process.
  • the proportion of physical bombardment plays a key role in etch orientation selectivity and rate.
  • the control of the morphology of the resulting structure can be achieved mainly by controlling P ICP and P rf .
  • the step of etching the ECR-MWPCVD comprises: placing a matrix deposited with a diamond-like coating in an electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MWPCVD) apparatus, introducing hydrogen gas, a gaseous carbon source, and One or more kinds of argon gas are used as the reaction gas, the gas pressure is 5-8 mTorr, the DC negative bias voltage is 75-230 V, the bias current is 40-120 mA, and the etching time is 30 minutes to 6 hours.
  • the gaseous carbon source may be a gaseous carbon source such as methane, acetylene or acetone, preferably methane.
  • the thickness of the diamond-like coating to be etched is 400 nm to 10 ⁇ m.
  • the gas that is introduced is a single hydrogen gas, or a mixed gas of hydrogen and a gaseous carbon source, or a mixed gas of hydrogen and argon, or hydrogen, a gaseous carbon source, and hydrogen.
  • a mixture of gases is a single hydrogen gas, or a mixed gas of hydrogen and a gaseous carbon source, or a mixed gas of hydrogen and argon, or hydrogen, a gaseous carbon source, and hydrogen.
  • a diamond-like nanoneedle array can be formed by etching a diamond-like coating by a double bias assisted HFCVD etching method.
  • a method for preparing a structural member having a diamond-like array according to a second aspect of the present invention comprises: depositing a diamond-like coating on a substrate and then etching the same to form a tip having a needle tip
  • the structure of the diamond-like nanoneedle array has the functions of resisting bacterial adhesion and killing bacteria.
  • the preparation method is simple and easy to operate, and can form a large-area diamond-like nanoneedle array having a sharp tip, which is convenient for commercial applications.
  • FIG. 1 is a schematic structural view of a structural member having a diamond-like array prepared according to Embodiments 1 and 2 of the present invention
  • FIG. 2 is a schematic structural view of a structural member having a diamond-like array prepared according to Embodiment 3-5 of the present invention
  • a method for preparing a structural member having a diamond-like array comprising:
  • Cobalt-chromium alloy was provided as the substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen and placed in a blast dry. Drying in a dry box at 100 ° C;
  • the above substrate is placed in a vacuum chamber of a multifunctional ion plating apparatus (V-Tech MF610/610), and the vacuum chamber is first evacuated to a background vacuum of 5.0 ⁇ 10 -3 Pa to open the main valve of the argon cylinder.
  • the pressure reducing valve, the ion source valve, the arc valve and the target valve, and the mass flow meter pass argon gas into the vacuum chamber to perform glow cleaning on the substrate, wherein the conditions of the glow cleaning are: an argon gas flow rate of 300 sccm, and a working pressure of 1.0.
  • the substrate bias is -800V
  • the substrate is cleaned by glow cleaning, the cleaning time is 10min
  • the ion source is turned on to ion bombard the sample, and the ion etching cleaning condition is: the ion source voltage is 90V,
  • the flow rate of argon gas is 300sccm
  • the working pressure of argon gas is 1.2Pa
  • the substrate bias voltage is -800V
  • the cleaning time is 10min;
  • Transition metal layer deposition After the above ion etching cleaning, argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is adjusted to make the pressure of the vacuum chamber 1.3 Pa, the transition metal arc target is turned on, and the target current is 100 A, the substrate is The bias voltage was -300 V, and the metal transition layer was deposited by arc ion plating. The deposition time was 3 min. In this example, pure Ti was used as the arc target, and the thickness of the Ti layer was 80 nm.
  • DLC deposition is carried out by magnetron sputtering on the transition metal layer obtained in the previous step, and argon gas is introduced into the vacuum chamber to open the carbon target (specifically, pure graphite target). Adjusting the argon flow rate so that the pressure in the vacuum chamber is 0.6 Pa, the carbon target power is 5 kW, the substrate negative bias is -30 V, and the deposition time is 1.5 h; wherein the thickness of the DLC layer is 2.5 ⁇ m;
  • Reactive ion etching hydrogen and methane are introduced, methane/hydrogen volume ratio: 3%/97%, total gas flow rate: 20 sccm, gas pressure is 6.6 mTorr, and DC negative bias voltage applied to the substrate is -220 V, bias current 80mA, etching time is 2 hours, after the etching is completed, the bias voltage, microwave power, electromagnetic coil power supply is turned off, and the gas is turned off to obtain a diamond-like nanoneedle array; wherein the thickness of the etched DLC layer (ie, diamond-like diamond) nanoneedle height) was 2 m, the remaining thickness of the DLC layer is 500 nm; aspect ratio of the nano-diamond needle 50, the tip having a diameter of 50 nm, a base diameter of 200 nm, the needle density of ⁇ 10 8 cm -2 .
  • a method for preparing a structural member having a diamond-like array comprising:
  • a polyetheretherketone (PEEK) substrate was provided as a substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen and placed in a blast drying. Drying at 80 ° C in the box;
  • the mass flow meter sends argon gas into the vacuum chamber to clean the substrate, wherein the condition of the glow cleaning is to introduce argon into the vacuum chamber, the flow rate of the argon gas is 400 sccm, the working pressure is 1.4 Pa, and the substrate bias voltage is -500 V.
  • the cleaning time is 30 min; after the glow cleaning is finished, the ion source is turned on to perform ion bombardment cleaning on the sample, and the ion etching cleaning conditions are: ion source voltage is 50V, argon gas flow rate is 70 sccm, argon gas Working pressure is 0.5Pa, substrate bias is -100V; cleaning time is 30min;
  • Transition metal layer deposition After the above ion etching cleaning, argon gas is introduced into the vacuum chamber, and the argon gas flow rate (flow rate is 50-400 sccm) is adjusted to make the pressure of the vacuum chamber 1.0 Pa, and the transition is started.
  • the metal arc target has a target current of 150 A and a substrate bias of -200 V.
  • the deposition of the metal transition layer is performed by arc ion plating for a deposition time of 10 min.
  • the thickness of the Ti layer is obtained by using pure Ti as an arc target. It is 500 nm.
  • DLC deposition was carried out by plasma enhanced chemical vapor deposition (PECVD) on the transition metal layer obtained in the previous step, and acetylene and argon were introduced into the vacuum chamber to adjust the vacuum.
  • PECVD plasma enhanced chemical vapor deposition
  • the pressure in the chamber is 1.0 Pa
  • the ion source voltage is 100 V
  • the substrate negative bias is -50 V
  • the deposition time is 10 h
  • the thickness of the DLC layer is 10 ⁇ m
  • Etching of DLC After the deposition of the above DLC layer is finished, the multifunctional ion plating apparatus (V-Tech MF610/610) is turned off, and the substrate is placed in an inductively coupled plasma etching after the substrate temperature is lowered to room temperature ( In the cavity of the ICP device, the substrate is plasma etched, and the conditions of ICP etching are as follows: oxygen is used as the reaction gas, the flow rate of the reaction gas is 20 sccm, the working pressure is 10 Pa, and the frequency of the ICP is 13.56 MHz. The power supply P ICP of the ICP is 1000W, the RF power P rf on the substrate stage is 200W, and the etching time is 90min.
  • the ICP source is turned off, the gas is turned off, and a diamond-like nanoneedle array is obtained; wherein, the etching is performed.
  • the thickness of the DLC layer ie, the height of the diamond-like nanoneedle
  • the thickness of the residual DLC layer is 1 ⁇ m
  • the diamond-like nanoneedle has an aspect ratio of ⁇ 20, and the tip diameter is 60 to 100 nm, and the bottom portion The diameter is 800 nm to 1 ⁇ m, and the needle density is ⁇ 10 4 cm -2 .
  • Figure 1 is a schematic view showing the structure of an antibacterial diamond-like array material obtained in Examples 1 and 2.
  • 101 is a substrate
  • 102 is a transition metal layer
  • 1031 is a residual diamond-like layer
  • 1031 is a diamond-like nanoneedle array
  • the sum of the thicknesses of 1031 and 1032 is the thickness of the initially deposited DLC layer.
  • a method for preparing a structural member having a diamond-like array comprising:
  • Ni-Ti alloy was provided as the substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen and placed in a blast oven at 120 °C. drying;
  • the above substrate was placed in a multi-functional ion plating apparatus (V-Tech MF610/610), and the main valve of the argon gas cylinder, the pressure reducing valve and the ion source valve were opened under the condition of a background vacuum of 5.0 ⁇ 10 -3 Pa.
  • the arc valve and the target valve and the mass flow meter pass argon gas into the vacuum chamber to perform glow cleaning on the substrate.
  • the conditions of the glow cleaning are: introducing argon into the vacuum chamber, the flow rate of the argon gas is 500 sccm, and the working pressure is 1.5. Pa, substrate bias -600V, the substrate is cleaned by glow cleaning for 20min; after the glow cleaning is finished, the ion source is turned on to ion bombard the sample.
  • the ion etching cleaning conditions are: ion source voltage is 70V, argon gas flow is 150sccm, The working pressure of argon is 0.9Pa, the substrate bias is -550V, and the cleaning time is 20min
  • Transition metal deposition After the above ion etching cleaning is completed, argon gas is introduced into the vacuum chamber, the argon gas flow rate (50-400 sccm) is adjusted to make the pressure of the vacuum chamber 1.0 Pa, and the transition metal arc target is turned on, and the target current is turned on.
  • the substrate bias is -300V
  • the metal transition layer is deposited by arc ion plating for a deposition time of 4 min.
  • pure Ti is used as an arc target, and the thickness of the Ti layer is 100 nm.
  • Diamond-like layer (DLC) deposition After the above ion etching cleaning, the substrate is placed in a multi-functional ion plating apparatus (V-Tech MF610/610) using plasma enhanced chemical vapor deposition (PECVD). The method is to deposit DLC on the surface of the substrate, and introduce acetylene and argon into the vacuum chamber, adjust the pressure in the vacuum chamber to 0.9 Pa, the ion source voltage to be 80 V, the substrate negative bias voltage to be -100 V, and the deposition time to 60 min; The thickness of the DLC layer is 0.5 ⁇ m;
  • the conditions of ICP etching are as follows: CF 4 or SF 6 is used as the reaction gas, the flow rate of the reaction gas is 40 sccm, the working pressure is 10 Pa, and the frequency of ICP is 13.56MHz, the ICP source power of 2000W for the ICP P, the substrate stage P rf RF power is 150W, etching time was 50min, after etching is completed ICP source turned off, closing the gas, to obtain a diamond-like nano-needle array; wherein The thickness of the etched DLC layer (ie, the height of the diamond-like nanoneedle) is 450 nm, and the thickness of the residual DLC layer is 50 nm; the diamond-like nanoneedle has an aspect ratio of ⁇ 10 and a tip diameter of 20 nm. The bottom has a diameter of 100 nm and a needle density of ⁇ 10 9 cm -2 .
  • a method for preparing a structural member having a diamond-like array comprising:
  • Titanium alloy TC4 was provided as the substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen, and placed in a blast drying oven at 150 ° C for drying. ;
  • the above substrate was placed in a multi-functional ion plating apparatus (V-Tech MF610/610), and the main valve of the argon gas cylinder, the pressure reducing valve and the ion source valve were opened under the condition of a background vacuum of 5.0 ⁇ 10 -3 Pa.
  • the arc valve and the target valve and the mass flow meter pass argon gas into the vacuum chamber to perform glow cleaning on the substrate.
  • the conditions of the glow cleaning are: argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is 450 sccm, and the working pressure is 1.7.
  • the ion etching cleaning condition is: ion source voltage is 80V, argon gas The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V, and the cleaning time is 20min;
  • Diamond-like layer (DLC) deposition after the above ion etching cleaning, the use of magnetic control Sputtering method is to deposit DLC on the surface of the substrate, argon gas is introduced into the vacuum chamber and the carbon target (specifically graphite target) is turned on, and the flow rate of the argon gas is adjusted so that the pressure in the vacuum chamber is 0.8 Pa, and the carbon target power is 1 kW.
  • the negative bias is -100V, and the deposition time is 5 hours; wherein the thickness of the DLC layer is 5 ⁇ m;
  • ECR-MWPCVD system vapor deposition
  • ECR-MWPCVD ECR microwave plasma open mode
  • magnetic field intensity of the electromagnetic coil provided in the ECR zone is 875 gauss
  • a diamond-like nanoneedle array is obtained; wherein the thickness of the etched DLC layer (ie, the height of the tapered diamond-like nanoneedle) is 800 nm to 2.5 ⁇ m. The thickness of the residual DLC layer was 2.5 ⁇ m.
  • the diamond-like nanoneedle obtained in the present embodiment has a tip diameter of 10 to 40 nm, a bottom diameter of 350 to 750 ⁇ m, and a needle density of ⁇ 4 ⁇ 10 8 cm -2 .
  • a method for preparing a structural member having a diamond-like array comprising:
  • Titanium alloy TC4 was provided as the substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen, and placed in a blast drying oven at 150 ° C for drying. ;
  • the above substrate was placed in a multi-functional ion plating apparatus (V-Tech MF610/610), and the main valve of the argon gas cylinder, the pressure reducing valve and the ion source valve were opened under the condition of a background vacuum of 5.0 ⁇ 10 -3 Pa.
  • the arc valve and the target valve and the mass flow meter pass argon gas into the vacuum chamber to perform glow cleaning on the substrate.
  • the conditions of the glow cleaning are: argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is 450 sccm, and the working pressure is 1.7.
  • the ion etching cleaning condition is: ion source voltage is 80V, argon gas The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V, and the cleaning time is 20min;
  • DLC deposition After the above-mentioned ion etching cleaning, DLC deposition is performed on the surface of the substrate by magnetron sputtering, argon gas is introduced into the vacuum chamber, and the carbon target (specifically graphite) is turned on. Target), adjusting the flow rate of argon gas to make the pressure in the vacuum chamber is 0.8 Pa, the carbon target power is 1 kW, the substrate negative bias voltage is -100 V, and the deposition time is 5 hours; wherein, the thickness of the DLC layer is 5 ⁇ m;
  • the obtained diamond-like nanoneedle has a needle density of about 1.7 ⁇ 10 8 cm -2 and is divided into two parts, wherein a small part of the diamond-like nano-cone is very small, the height is less than 100 nm, and the tip diameter is 10 to 40 nm. straight The diameter is less than 100 nm; most of the nano-cones have a height of 3 to 4.5 ⁇ m, a bottom diameter of 100 nm to 2 ⁇ m, and a tip diameter of 10 to 40 nm.
  • FIG. 2 is a schematic structural view of an antibacterial diamond-like array material prepared in Example 3-5 of the present invention.
  • 201 is a matrix
  • 2021 is a residual diamond-like layer
  • 2022 is a diamond-like nanoneedle array
  • no transition metal layer is disposed between the residual diamond-like layer and the substrate.
  • Titanium alloy TC4 was provided as the substrate.
  • the substrate was first ultrasonically cleaned with distilled water for 10 min, then ultrasonically washed with acetone and absolute ethanol for 20 min, then the substrate was blown dry with nitrogen, and placed in a blast drying oven at 150 ° C for drying. ;
  • the above substrate was placed in a multi-functional ion plating apparatus (V-Tech MF610/610), and the main valve of the argon gas cylinder, the pressure reducing valve and the ion source valve were opened under the condition of a background vacuum of 5.0 ⁇ 10 -3 Pa.
  • the arc valve and the target valve and the mass flow meter pass argon gas into the vacuum chamber to perform glow cleaning on the substrate.
  • the conditions of the glow cleaning are: argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is 450 sccm, and the working pressure is 1.7.
  • the ion etching cleaning condition is: ion source voltage is 80V, argon gas The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V, and the cleaning time is 20min;
  • DLC deposition After the above-mentioned ion etching cleaning, DLC deposition is performed on the surface of the substrate by magnetron sputtering, argon gas is introduced into the vacuum chamber, and the carbon target (specifically graphite) is turned on. Target), adjusting the flow rate of argon gas to make the pressure in the vacuum chamber is 0.8 Pa, the carbon target power is 1 kW, the substrate negative bias voltage is -100 V, and the deposition time is 5 hours; wherein, the thickness of the DLC layer is 5 ⁇ m;
  • the present invention also provides an effect embodiment.
  • the antibacterial diamond-like array materials prepared in Examples 4 and 5 of the present invention were respectively tested for antibacterial properties, and a 5 ⁇ m thick intact DLC layer was deposited on the titanium alloy TC4 as Comparative Example 1, and the results are shown in FIG.
  • Pseudomonas aeruginosa was respectively applied to Comparative Example 1 (titanium alloy TC4 + intact DLC layer), and the diamond-like nanoarrays obtained in Examples 4 and 5, (a) Pseudomonas aeruginosa bacteria attached to different substrates with different surface topography Total; (b) Percentage of Pseudomonas aeruginosa that died after 1 h.

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Abstract

一种具有类金刚石阵列的结构件，包括基体(101，201)和设置在基体(101，201)上的具有尖端结构的类金刚石纳米针阵列(1032，2022)，类金刚石纳米针阵列(1032，2022)通过对形成在基体(101，201)上的一类金刚石涂层进行刻蚀得到。还包括一种具有类金刚石阵列的结构件的制备方法。

Description

一种具有类金刚石阵列的结构件及其制备方法
本申请要求于2016年12月20日提交中国专利局、申请号为201611185457.X、发明名称为“一种具有类金刚石阵列的结构件及其制备方法”的中国专利申请的优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明涉及超疏水材料领域，具体涉及一种具有类金刚石阵列的结构件及其制备方法。
背景技术
生物材料，特别是用于医用植入体(如自动植入式心脏除颤器，尿导管等)和手术器具上的生物材料，由于直接与人体组织接触，需满足临床使用的各种要求。除具备一般材料的良好物理、化学和力学性能外，还必须具有抗菌性，以免受细菌定植，进而导致在设备表面形成生物膜及感染细菌。生物膜是微生物为应对外界环境变化而自身分泌的胞外聚合物聚集于介质表面所形成的菌落聚集体，生物膜的形成会增加细菌的耐药性，提高临床医疗的难度。因此，一般需要对医用金属、陶瓷材料进行表面改性，以提供其抗菌性。
类金刚石(diamond-like carbon，DLC)是一种含有sp2和sp3键合特征的非晶碳材料，具有高硬度、低摩擦、高热导率、高透光性、化学惰性强及良好的生物相容性等优异性能，DLC膜在光学窗口、刀具、模具等零部件、生物医疗器件等领域都具有广阔的应用前景。DLC涂层作为医学植入体材料表面改性层，其主要优越性表现在：①DLC涂层机械强度与植入体材料的可适配 性不仅保证了涂层与医用植入体材料的牢固结合，而且增强了植入体负载部位的支撑强度；②高致密度DLC涂层其优异的耐磨耐蚀性能不仅提高了生物-力学交互环境下植入体材料的耐腐蚀磨损能力，同时可有效屏蔽金属离子向周围组织和血液的扩散，进而抑制有害金属离子溶入生物组织并阻止其对生物组织产生的毒性反应而引起的组织损伤，延长医用材料服役寿命；③低毒性和高化学稳定性的DLC涂层因其具有可调控表面界面性能而能够适应植入体服役环境，降低人体对医用植入材料的排异性并提高其与生物组织的相容性。但目前还未见单独的DLC涂层就能具有抗菌性的报道。
发明内容
有鉴于此，本发明第一方面提供了一种具有类金刚石阵列的结构件，其通过在基体上先沉积一层类金刚石涂层，然后对其进行刻蚀，形成具有针尖状尖端结构的类金刚石纳米针阵列。该具有类金刚石阵列的结构件具有良好的抗菌性能，用以解决现有技术中类金刚石涂层备杀菌性弱或几乎没有抗菌性能的问题。
第一方面，本发明提供了一种具有类金刚石阵列的结构件，包括基体和设置在所述基体上的具有尖端结构的类金刚石纳米针阵列，所述类金刚石纳米针阵列通过对形成在所述基体上的一类金刚石涂层进行刻蚀得到。
优选地，所述基体和类金刚石纳米针阵列之间还设置有残余类金刚石涂层，所述类金刚石纳米针阵列形成在所述残余类金刚石涂层表面。所述残余类金刚石涂层为一完整的涂层，不具有类金刚石纳米针。进一步地，所述残余类金刚石涂层的厚度为100nm～3μm。所述残余类金刚石涂层的存在，更有利于提高基体和类金刚石纳米针阵列的结合力。
优选地，所述金刚石纳米针阵列中的类金刚石纳米针为锥状结构，所述类金刚石纳米针的长径比为20～80，尖部直径为10～100nm，底部直径为30nm～2μm，针密度为104～109个·cm-2。
其中，所述长径比是指纳米针的高度与所述纳米针高度的一半所对应的直径的比值。显然地，所述底部直径应不小于所述尖部直径。
本申请中，所述金刚石纳米针阵列中，类金刚石纳米针的高度可以为均一的高度，也可以是高度不一的纳米针，其高度在10nm～10μm之间变化。例如可以同时存在高度在100nm以下的纳米针和高度为0.8-9μm的纳米针。
进一步地，所述类金刚石纳米针的高度为400nm～10μm。类金刚石纳米针的高度呈梯度分布。
本申请中，所述类金刚石纳米针的尺寸与细菌尺寸相近，长径比较高。所述类金刚石纳米针的尺寸可以完全一样，也可以不完全一致，有一定的高低变化。所述类金刚石纳米针的长径比为30～60(优选为35-55、40-50)；尖部直径为10～50nm或60～100nm；底部直径为800nm～2μm或者200～700nm或者30～200nm。所述针密度可以为105～109个·cm-2，例如可以是106～×109个·cm-2，108个·cm-2。可以通过对类金刚石纳米针尺寸和密度的调控，来优化所述抗菌类金刚石阵列材料的抗菌性能和哺乳类生物细胞相容性。
优选地，所述基体为金属、金属合金、硬质合金、不锈钢、聚合物、玻璃和硅的一种或多种，但不限于此。特别是常用的植入材料，如钛合金TC4等。
其中，所述金属可以选自钛Ti、镍Ni、钼Mo、铌Nb、钽Ta、钌Ru、铂Pt中的任一种。所述金属合金可以是钛基合金、钴基合金(如钴铬合金)、Ni-Ti合金、镍基合金；所述硬质合金可以是碳化钨基硬质合金、碳化钛基硬 质合金、碳氮化钛基硬质合金、碳化铬基硬质合金中的一种。
优选地，当所述基体的材质为医用不锈钢、聚合物、钴基金属合金、硬质合金、玻璃和硅时，所述抗菌类金刚石阵列材料还包括一过渡金属层，所述过渡金属层位于所述基体与所述残余类金刚石涂层之间。
进一步地，所述过渡金属层的厚度为50～500nm。所述过渡金属层中的金属为Cr、Ti、Ni、Zr、W、Mo、Nb、Ta、Ru、Pt等过渡金属元素中的一种。
本申请中，如果基体的材质本身就是过渡金属或热膨胀系数差异较小的金属合金(如钛Ti、镍Ni、铌Nb、钽Ta；钛基合金、Ni-Ti合金、镍基合金时)，直接在基体表面沉积类金刚石涂层，就可使其牢固结合在基体表面，然后再刻蚀得到阵列。如果基体不为过渡金属，则需要在基底上先沉积一层过渡金属层，再在该过渡金属层的基础上沉积类金刚石涂层，以提高类金刚石涂层牢固结合在基体上。
本发明第一方面提供的具有类金刚石阵列的结构件包括基体和设置在所述基体表面的具有尖端结构的类金刚石纳米针阵列，所述类金刚石纳米针阵列通过对形成在衬底层表面的类金刚石涂层进行刻蚀得到。所述类金刚石纳米针阵列不仅可以对细菌的细胞壁产生压力，穿刺细菌的细胞壁使其伸展并最终溶解，导致细菌死亡，有效破坏生物膜的形成，赋予类金刚石涂层显著的抗菌性能。此外，所述类金刚石纳米针阵列对于大多数细胞，特别是人体细胞而言，几乎不具有毒性，还可支持人体细胞的粘附，可以应用于各种医用植入体以及手术器具上，防止细菌感染，有利于人体健康。
第二方面，本发明提供了一种具有类金刚石阵列的结构件的制备方法，包括以下步骤：
提供基体，对所述基体进行预处理；
将所述预处理后的基体置于镀膜设备的真空室内，在所述预处理后的基体上沉积类金刚石涂层；
对所述类金刚石涂层进行刻蚀，得到具有尖端结构的类金刚石纳米针阵列。
优选地，所述预处理包括超声清洗、辉光清洗和离子刻蚀清洗中的一种或多种。
在本发明一实施方式中，可以先进行超声清洗，之后将超声清洗后的基底置于一沉积设备的真空室内，先进行辉光清洗，再进行离子刻蚀清洗。这样可以更好地保证待处理工件表面的清洁度。
其中，所述超声清洗是依次在去离子水、丙酮、乙醇中进行超声5-30min。在超声清洗后，需要将基底吹干，再进行其他预处理。
其中，所述辉光清洗和所述离子刻蚀清洗均需要在真空度为5.0×10-3Pa以下进行。
具体地，所述辉光清洗的条件为:向真空室内通入氩气，氩气流量300～500sccm，工作气压为1.0～1.7Pa，基底偏压-500～-800V，所述辉光清洗的时间为10～30min。
具体地，所述离子刻蚀清洗的条件为：开启离子源，离子源电压为50～90V；氩气流量为70～300sccm，工作气压为0.5～1.2Pa，基底偏压为-100～-800V；所述离子刻蚀清洗的时间为10～30min。
优选地，当所述基体的材质为医用不锈钢、聚合物、钴基合金、硬质合金、玻璃和硅时，在所述预处理之后以及沉积所述类金刚石涂层之前，还包括沉积 一过渡金属层。
进一步地，所述沉积过渡金属层的步骤包括：向真空室内通入氩气，调节所述真空室的压强为0.2～1.3Pa，开启过渡金属电弧靶，进行电弧沉积金属过渡层，控制靶电流为80～200A，基底偏压为-100～-300V，沉积时间为2～10min。
进一步地，所述过渡金属层的厚度为50～500nm。
优选地，所述氩气的流量为50～400sccm。
其中，沉积所述类金刚石涂层的方法包括磁控溅射、热丝化学气相沉积(HFCVD)、等离子体增强化学气相沉积，或其他常规的制备类金刚石涂层的方法。
在本发明一实施方式中，采用磁控溅射的方式来沉积类金刚石涂层，具体地，包括：向真空室中通入氩气并开启碳靶进行沉积，使所述真空室内的压强为0.5～1.0Pa，所述碳靶的靶功率为1～5kW，基底负偏压为-50～-200V，沉积时间为30～600min。
在本发明一实施方式中，采用等离子体增强化学气相沉积的方式来沉积类金刚石涂层，具体地，包括：向真空室中通入气态碳源进行沉积，使所述真空室内的压强为0.5～1.0Pa，离子源电压为50～100V，基底负偏压为-50～-200V，沉积时间为30～600min。气态碳源包括可以为甲烷、乙炔、丙酮等。此时，所述类金刚石涂层的厚度为500nm-10μm。
其中，所述类金刚石涂层的刻蚀是采用感应耦合等离子体(ICP)刻蚀或者电子回旋共振微波等离子体化学气相沉积(ECR-MWPCVD)刻蚀。此时，所述类金刚石涂层的厚度为500nm-10μm。
进一步地，所述ICP刻蚀的条件为：将沉积有类金刚石涂层的基体置于电 感耦合等离子体刻蚀(ICP)腔体中，利用氢气、氩气、氧气、氦气、氮气、气态碳源、CF4、C4F8和SF6中的一种或多种为反应气体，反应气体的流量为5～200sccm，反应气压为0.1～10Pa，ICP的电源功率PICP为500～3000W，基片台上射频功率Prf为50～300W，刻蚀时间为10～600min。此时，被刻蚀掉的类金刚石涂层的厚度为400nm～10μm。
本申请中，所述ICP的电源功率PICP对于气体的离化率起到关键作用；射射频功率Prf是指加载在基片台上(基体)的偏压功率，Prf决定刻蚀过程中物理轰击所占的比重，对于刻蚀取向选择性和速率起到关键作用。主要通过控制PICP和Prf可以实现对最终刻蚀所得结构的形貌的控制。
进一步地，所述ECR-MWPCVD刻蚀的步骤包括：将沉积有类金刚石涂层的基体置于电子回旋共振微波等离子体化学气相沉积(ECR-MWPCVD)设备中，通入氢气，气态碳源和氩气中的一种或多种作为反应气体，气体压力为5～8mTorr，直流负偏压为75～230V，偏流为40～120mA，刻蚀时间为30分钟～6小时。其中，所述气态碳源可以为甲烷、乙炔、丙酮等气态的碳源，优选为甲烷。此时，此时，被刻蚀掉的类金刚石涂层的厚度为400nm～10μm。
优选地，所述ECR-MWPCVD刻蚀时，通入的气体为单独的氢气，或者是氢气和气态碳源的混合气体，或者氢气和氩气的混合气体，或者是氢气、气态碳源和氢气构成的混合气体。
此外，还可通过双偏压辅助HFCVD刻蚀方法进行刻蚀类金刚石涂层，形成的类金刚石纳米针阵列。
本发明第二方面提供的一种具有类金刚石阵列的结构件的制备方法，通过在基体上先沉积一层类金刚石涂层，然后对其进行刻蚀，形成具有针尖状尖端 结构的类金刚石纳米针阵列，所述类金刚石纳米针阵列具有较好的抗细菌黏附、杀灭细菌的功能。所述制备方法简单易操作，可以形成具有尖锐尖端的大面积类金刚石纳米针阵列，便于商业化的应用。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例1、2制得的具有类金刚石阵列的结构件的结构示意图；
图2为本发明实施例3-5制得的具有类金刚石阵列的结构件的结构示意图；
图3为本发明实施例4、5制得的具有类金刚石阵列的结构件与对比实施例1的抗菌性能测试结果。
具体实施方式
以下所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
实施例1：
一种具有类金刚石阵列的结构件的制备方法，包括：
(1)基体预处理：
提供钴铬合金作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干 燥箱中100℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)的真空腔体中，先将真空腔体抽真空至本底真空度为5.0×10-3Pa，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计向真空室内通入氩气对基体进行辉光清洗，其中，辉光清洗的条件为:氩气流量300sccm，工作压强为1.0Pa，基底偏压为-800V，对基底进行辉光清洗，清洗时间为10min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子刻蚀清洗条件为：离子源电压为90V，氩气流量300sccm，氩气的工作气压为1.2Pa，基底偏压为-800V；清洗时间为10min；
(2)过渡金属层沉积：在上述离子刻蚀清洗结束后，向真空室内通入氩气，调节氩气流量使真空室的压强为1.3Pa，开启过渡金属电弧靶，靶电流为100A，基底偏压为-300V，以电弧离子镀方式进行金属过渡层的沉积，沉积时间为3min；其中，本实施例中以纯Ti作电弧靶，所得Ti层的厚度为80nm。
(3)类金刚石层(DLC)沉积：在上一步得到的过渡金属层上采用磁控溅射的方式进行DLC的沉积，向真空室内通入氩气并开启碳靶(具体为纯石墨靶)，调节氩气流量使真空室内的压强为0.6Pa，碳靶功率为5kW，基底负偏压为-30V，沉积时间为1.5h；其中，DLC层的厚度为2.5μm；
(4)DLC的刻蚀：上述DLC层的沉积结束后，关闭多功能离子镀膜设备(V-Tech MF610/610)，待基体温度降至室温，将基体置于电子回旋共振微波等离子体化学气相沉积系统(ECR-MWPCVD)中，抽真空至10-5Pa，然后重新充氢气至7mTorr，开启ECR微波等离子体模式，外加电磁线圈提供的磁场在ECR区的强度为875高斯，采用如下条件进行反应离子刻蚀：通入氢气和甲烷， 甲烷/氢气体积比：3％/97％，总气体流量：20sccm，使气体压力为6.6mTorr，基体台上加载的直流负偏压为-220V，偏流为80mA，刻蚀时间为2小时，刻蚀完毕后关掉偏压、微波电源、电磁线圈电源，关闭气体，得到类金刚石纳米针阵列；其中，刻蚀掉的DLC层的厚度(即类金刚石纳米针的高度)为2μm，残余的DLC层的厚度为500nm；所述类金刚石纳米针的长径比为50，尖部直径为50nm，底部直径为200nm，针密度为～108cm-2。
实施例2：
一种具有类金刚石阵列的结构件的制备方法，包括：
(1)基体预处理：
提供聚醚醚酮(PEEK)基片作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干燥箱中80℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)中，抽真空至5.0×10-3Pa，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计向真空室内通入氩气对基体进行辉光清洗,其中，辉光清洗的条件为向真空室内通入氩气，氩气流量400sccm，工作压强为1.4Pa,基底偏压-500V，对基底进行辉光清洗，清洗时间为30min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子刻蚀清洗条件为：离子源电压为50V，氩气流量70sccm，氩气的工作气压为0.5Pa，基底偏压为-100V；清洗时间为30min；
(2)过渡金属层沉积：在上述离子刻蚀清洗结束后，向真空室内通入氩气，调节氩气流量(流量为50～400sccm)使真空室的压强为1.0Pa，开启过渡 金属电弧靶，靶电流为150A，基底偏压为-200V，以电弧离子镀方式进行金属过渡层的沉积，沉积时间为10min；其中，本实施例中以纯Ti作电弧靶，所得Ti层的厚度为500nm。
(3)类金刚石层(DLC)沉积：在上一步得到的过渡金属层上采用等离子体增强化学气相沉积(PECVD)的方式进行DLC的沉积，向真空室中通入乙炔和氩气，调节真空室内的压强为1.0Pa，离子源电压为100V，基底负偏压为-50V，沉积时间为10h；其中，DLC层的厚度为10μm；
(4)DLC的刻蚀：待上述DLC层的沉积结束后，关闭多功能离子镀膜设备(V-Tech MF610/610)，待基体温度降至室温，将基体置于电感耦合等离子体刻蚀(ICP)设备的腔体中，对基体进行等离子体刻蚀，采用ICP刻蚀的条件为：通入氧气作为反应气体，反应气体的流量为20sccm，工作压强为10Pa，ICP的频率为13.56MHz，ICP的电源功率PICP为1000W，基片台上射频功率Prf为200W，刻蚀时间为90min，刻蚀完毕后关掉ICP源，关闭气体，得到类金刚石纳米针阵列；其中，刻蚀掉的DLC层的厚度(即类金刚石纳米针的高度)为～9μm，残余的DLC层的厚度为1μm；所述类金刚石纳米针的长径比为～20，尖部直径为60～100nm，底部直径为800nm～1μm，针密度为～104cm-2。
图1为本发明实施例1、2制得的抗菌类金刚石阵列材料的结构示意图。图1中101为基体，102为过渡金属层，1031为残余的类金刚石层，1031为类金刚石纳米针阵列，1031和1032的厚度总和为初始沉积的DLC层的厚度。
实施例3：
一种具有类金刚石阵列的结构件的制备方法，包括：
(1)基体预处理：
提供Ni-Ti合金作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干燥箱中于120℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)中，在本底真空度为5.0×10-3Pa的条件下，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计向真空室内通入氩气对基体进行辉光清洗，其中，辉光清洗的条件为:向真空室内通入氩气，氩气流量500sccm，工作压强为1.5Pa，基底偏压-600V，对基底进行辉光清洗20min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗,离子刻蚀清洗条件为：离子源电压为70V，氩气流量150sccm，氩气的工作气压为0.9Pa，基底偏压为-550V；清洗时间20min；
(2)过渡金属沉积：在上述离子刻蚀清洗结束后，向真空室内通入氩气，调节氩气流量(50～400sccm)使真空室的压强为1.0Pa，开启过渡金属电弧靶，靶电流为100A，基底偏压为-300V，以电弧离子镀方式进行金属过渡层的沉积，沉积时间为4min；其中，本实施例中以纯Ti作电弧靶，所得Ti层的厚度为100nm。
(3)类金刚石层(DLC)沉积：在上述离子刻蚀清洗结束后，将基体置于多功能离子镀膜设备(V-Tech MF610/610)中，采用等离子体增强化学气相沉积(PECVD)的方式在基体表面进行DLC的沉积，向真空室中通入乙炔和氩气，调节真空室内的压强为0.9Pa，离子源电压为80V，基底负偏压为-100V，沉积时间为60min；其中，DLC层的厚度为0.5μm；
(4)DLC的刻蚀：待上述DLC层的沉积结束后，关闭多功能离子镀膜设备(V-Tech MF610/610)，待基体温度降至室温，将基体置于电感耦合等离子体 刻蚀(ICP)设备的腔体中，对基体进行等离子体刻蚀，采用ICP刻蚀的条件为：通入CF4或SF6作为反应气体，反应气体的流量为40sccm，工作压强为10Pa，ICP的频率为13.56MHz，ICP的电源功率PICP为2000W，基片台上射频功率Prf为150W，刻蚀时间为50min，刻蚀完毕后关掉ICP源，关闭气体，得到类金刚石纳米针阵列；其中，刻蚀掉的DLC层的厚度(即类金刚石纳米针的高度)为450nm，残余的DLC层的厚度为50nm；所述类金刚石纳米针的长径比为～10，尖部直径为20nm，底部直径为100nm，针密度为～109cm-2。
实施例4：
一种具有类金刚石阵列的结构件的制备方法，包括：
(1)基体预处理：
提供钛合金TC4作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干燥箱中150℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)中，在本底真空度为5.0×10-3Pa的条件下，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计向真空室内通入氩气对基体进行辉光清洗，其中，辉光清洗的条件为:向真空室内通入氩气，氩气流量450sccm，工作压强为1.7Pa，基底偏压-800V，对基底进行辉光清洗，清洗时间10min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子刻蚀清洗条件为：离子源电压为80V，氩气流量200sccm，氩气的工作气压为1.0Pa，基底偏压为-450V；清洗时间为20min；
(2)类金刚石层(DLC)沉积：在上述离子刻蚀清洗结束后，采用磁控 溅射的方式在基体表面进行DLC的沉积，向真空室内通入氩气并开启碳靶(具体为石墨靶)，调节氩气流量使真空室内的压强为0.8Pa，碳靶功率为1kW，基底负偏压为-100V，沉积时间为5小时；其中，DLC层的厚度为5μm；
(3)DLC的刻蚀：待上述DLC层的沉积结束后，关闭多功能离子镀膜设备(V-Tech MF610/610)，待基体温度降至室温，将基体置于电子回旋共振微波等离子体化学气相沉积系统(ECR-MWPCVD)中，抽真空至10-5Pa，然后重新充氢气至7mTorr，开启ECR微波等离子体模式，外加电磁线圈提供的磁场在ECR区的强度为875高斯，采用如下条件进行反应离子刻蚀：通入氢气，气体流量为：20sccm，使气体压力为8mTorr，基体台上加载的直流负偏压为-150V，偏流为40-60mA，刻蚀时间为120min，刻蚀完毕后关掉偏压、微波电源、电磁线圈电源，关闭气体，得到类金刚石纳米针阵列；其中，刻蚀掉的DLC层的厚度(即锥状类金刚石纳米针的高度)为800nm～2.5μm，残余的DLC层的厚度为2.5μm。本实施例中所得类金刚石纳米针的尖部直径为10～40nm，底部直径为350～750μm，针密度为～4×108cm-2。
实施例5：
一种具有类金刚石阵列的结构件的制备方法，包括：
(1)基体预处理：
提供钛合金TC4作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干燥箱中150℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)中，在本底真空度为5.0×10-3Pa的条件下，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀 以及质量流量计向真空室内通入氩气对基体进行辉光清洗，其中，辉光清洗的条件为:向真空室内通入氩气，氩气流量450sccm，工作压强为1.7Pa，基底偏压-800V，对基底进行辉光清洗，清洗时间10min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子刻蚀清洗条件为：离子源电压为80V，氩气流量200sccm，氩气的工作气压为1.0Pa，基底偏压为-450V；清洗时间为20min；
(2)类金刚石层(DLC)沉积：在上述离子刻蚀清洗结束后，采用磁控溅射的方式在基体表面进行DLC的沉积，向真空室内通入氩气并开启碳靶(具体为石墨靶)，调节氩气流量使真空室内的压强为0.8Pa，碳靶功率为1kW，基底负偏压为-100V，沉积时间为5小时；其中，DLC层的厚度为5μm；
(3)DLC的刻蚀：待上述DLC层的沉积结束后，关闭多功能离子镀膜设备(V-Tech MF610/610)，待基体温度降至室温，将基体置于电子回旋共振微波等离子体化学气相沉积系统(ECR-MWPCVD)中，抽真空至10-5Pa，然后重新充氢气至7mTorr，开启ECR微波等离子体模式，外加电磁线圈提供的磁场在ECR区的强度为875高斯，采用如下条件进行反应离子刻蚀：通入氢气和氩气，氩气/氢气体积比：45％/55％，总气体流量：20sccm，使气体压力为5mTorr，基体台上加载的直流负偏压为-200V，偏流为40-60mA，刻蚀时间为240min，刻蚀完毕后关掉偏压、微波电源、电磁线圈电源，关闭气体，得到类金刚石纳米针阵列；其中，残余的DLC层的厚度为500nm，所得到的类金刚石纳米针的针密度约为1.7×108cm-2，其分为两个部分，其中小部分类金刚石纳米锥非常小，高度小于100nm，尖部直径为10～40nm，底部直径小于100nm；而大多数纳米锥的高度为3～4.5μm，底部直径为100nm～2μm，尖部直径为10～40nm。
图2为本发明实施例3-5制得的抗菌类金刚石阵列材料的结构示意图。图1中201为基体，2021为残余的类金刚石层，2022为类金刚石纳米针阵列，在所述残余类金刚石层与基体之间没有设置过渡金属层。
对比实施例1
(1)基体预处理：
提供钛合金TC4作为基体，首先用蒸馏水将将该基体超声清洗10min，再依次用丙酮和无水乙醇超声清洗20min，然后用氮气将基体吹干，并放入鼓风干燥箱中150℃烘干；
将上述基体置于多功能离子镀膜设备(V-Tech MF610/610)中，在本底真空度为5.0×10-3Pa的条件下，打开氩气瓶主阀，减压阀、离子源阀、弧阀和靶阀以及质量流量计向真空室内通入氩气对基体进行辉光清洗，其中，辉光清洗的条件为:向真空室内通入氩气，氩气流量450sccm，工作压强为1.7Pa，基底偏压-800V，对基底进行辉光清洗，清洗时间10min；辉光清洗结束后，开启离子源对样品进行离子轰击清洗，离子刻蚀清洗条件为：离子源电压为80V，氩气流量200sccm，氩气的工作气压为1.0Pa，基底偏压为-450V；清洗时间为20min；
(2)类金刚石层(DLC)沉积：在上述离子刻蚀清洗结束后，采用磁控溅射的方式在基体表面进行DLC的沉积，向真空室内通入氩气并开启碳靶(具体为石墨靶)，调节氩气流量使真空室内的压强为0.8Pa，碳靶功率为1kW，基底负偏压为-100V，沉积时间为5小时；其中，DLC层的厚度为5μm；
为验证本发明制得的材料具有抗菌性能，本发明还提供了效果实施例。 将本发明实施例4、5制得的抗菌类金刚石阵列材料分别进行抗菌性能测试，并在钛合金TC4上沉积5μm厚的完整DLC层作为对比实施例1，其结果如图3所示，将绿脓杆菌分别作用在对比实施例1(钛合金TC4+完整DLC层)，以及实施例4和实施例5所得类金刚石纳米阵列上，(a)为表面形貌不同的基底附着的绿脓杆菌细菌总数；(b)为1h后死亡的绿脓杆菌所占的百分比。从图(b)中可以看出完整的类金刚石涂层(对比例1)以及实施例4和5所得类金刚石纳米针列都具有一定的抗菌效果，但实施例4和5所得类金刚石纳米针列的杀菌效果明显比普通没有刻蚀的完整类金刚石涂层的杀菌效果好得多。而对比不同条件下刻蚀的纳米针列，可以看出实施例5所制得的类金刚石纳米针列(高度不一的纳米针)的杀菌效果更好一些。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (16)

  1. 一种具有类金刚石阵列的结构件，其特征在于，包括基体和设置在所述基体上的具有尖端结构的类金刚石纳米针阵列，所述类金刚石纳米针阵列通过对形成在所述基体上的一类金刚石涂层进行刻蚀得到。
  2. 如权利要求1所述的具有类金刚石阵列的结构件，其特征在于，所述基体和类金刚石纳米针阵列之间还设置有残余类金刚石涂层，所述类金刚石纳米针阵列形成在所述残余类金刚石涂层表面；所述残余类金刚石涂层的厚度为100nm～3μm。
  3. 如权利要求1所述的具有类金刚石阵列的结构件，其特征在于，所述金刚石纳米针阵列中的类金刚石纳米针为锥状结构，所述类金刚石纳米针的长径比为20～80，尖部直径为10～100nm，底部直径为30nm～2μm，针密度为104～109.个·cm-2。
  4. 如权利要求3所述的具有类金刚石阵列的结构件，其特征在于，所述类金刚石纳米针的高度在10nm～10μm之间。
  5. 如权利要求4所述的具有类金刚石阵列的结构件，其特征在于，所述金刚石纳米针阵列中，类金刚石纳米针的高度不一。
  6. 如权利要求1所述的具有类金刚石阵列的结构件，其特征在于，所述基 体为金属、金属合金、硬质合金、不锈钢、聚合物、玻璃和硅的一种或多种。
  7. 如权利要求6所述的具有类金刚石阵列的结构件，其特征在于，当所述基体的材质为不锈钢、聚合物、钴基金属合金、硬质合金、玻璃和硅时，所述抗菌类金刚石阵列材料还包括一过渡金属层，所述过渡金属层位于所述基体与所述残余类金刚石涂层之间；所述过渡金属层的厚度为50～500nm。
  8. 一种具有类金刚石阵列的结构件的制备方法，其特征在于，包括以下步骤：
    提供结构件基体，对所述基体进行预处理；
    将所述预处理后的基体置于镀膜设备的真空室内，在所述预处理后的基体上沉积类金刚石涂层；
    对所述类金刚石涂层进行刻蚀，得到具有尖端结构的类金刚石纳米针阵列。
  9. 如权利要求8所述的制备方法，其特征在于，所述沉积所述类金刚石涂层的方式为磁控溅射；其中，所述磁控溅射的步骤包括：
    向真空室中通入氩气并开启碳靶进行沉积，使所述真空室内的压强为0.5～1.0Pa，所述碳靶的靶功率为1～5kW，基底负偏压为-50～-200V，沉积时间为30～600min。
  10. 如权利要求8所述的制备方法，其特征在于，所述沉积所述类金刚石 涂层的方式为等离子体增强化学气相沉积；其中，所述等离子体增强化学气相沉积的步骤包括：
    向真空室中通入气态碳源进行沉积，使所述真空室内的压强为0.5～1.0Pa，离子源电压为50～100V，基底负偏压为-50～-200V，沉积时间为30～600min。
  11. 如权利要求8所述的制备方法，其特征在于，所述类金刚石涂层的刻蚀是采用感应耦合等离子体刻蚀；包括以下步骤：
    将沉积有类金刚石涂层的基体置于电感耦合等离子体刻蚀的腔体中，利用氢气、氩气、氧气、氦气、氮气、气态碳源、CF4、C4F8和SF6中的一种或多种为反应气体，反应气体的流量为5～200sccm，反应气压为0.1～10Pa，等离子体的电源功率为500～3000W，基片台上的射频功率为50～300W，刻蚀时间为10～600min。
  12. 如权利要求8所述的制备方法，其特征在于，所述类金刚石涂层的刻蚀是采用电子回旋共振微波等离子体化学气相沉积刻蚀，包括以下步骤：
    将沉积有类金刚石涂层的基体置于电子回旋共振微波等离子体化学气相沉积设备中，通入氢气或者通入混合的氢气、气态碳源和氩气，气体压力为5～8mTorr，直流负偏压为75～230V，偏流为40～120mA，刻蚀时间为30分钟～6小时。
  13. 如权利要求8所述的制备方法，其特征在于，所述预处理依次包括溶剂超声清洗、辉光清洗和离子刻蚀清洗。
  14. 如权利要求13所述的制备方法，其特征在于，所述溶剂超声清洗是依次在去离子水、丙酮、乙醇中进行超声5-30min；
    所述辉光清洗的条件为:将溶剂超声清洗后的基底置于一沉积设备的真空室内，向真空室内通入氩气，氩气流量300～500sccm，工作气压为1.0～1.7Pa，基底偏压-500～-800V，所述辉光清洗的时间为10～30min；
    所述离子刻蚀清洗的条件为：开启离子源，离子源电压为50～90V；氩气流量为70～300sccm，工作气压为0.5～1.2Pa，基底偏压为-100～-800V；所述离子刻蚀清洗的时间为10～30min。
  15. 如权利要求8-14任一项所述的制备方法，其特征在于，在所述预处理之后以及沉积所述类金刚石涂层之前，还包括沉积一过渡金属层；
    其中，所述沉积过渡金属层的步骤包括：向真空室内通入氩气，调节所述真空室的压强为0.2～1.3Pa，开启过渡金属电弧靶，进行电弧沉积金属过渡层，控制靶电流为80～200A，基底偏压为-100～-300V，沉积时间为2～10min。
  16. 如权利要求15所述的制备方法，其特征在于，所述过渡金属层中的过渡金属为Cr、Ti、Ni、Zr、W、Mo、Nb、Ta、Ru和Pt中的一种。
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