CN106835011B - A kind of structural member and preparation method thereof with diamond-like array - Google Patents
A kind of structural member and preparation method thereof with diamond-like array Download PDFInfo
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- CN106835011B CN106835011B CN201611185457.XA CN201611185457A CN106835011B CN 106835011 B CN106835011 B CN 106835011B CN 201611185457 A CN201611185457 A CN 201611185457A CN 106835011 B CN106835011 B CN 106835011B
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- 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
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- 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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- 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
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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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- 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
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- 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
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- 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
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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
- C23C14/22—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
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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
- 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
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- 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
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- 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
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- 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
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Abstract
The present invention provides a kind of structural members with diamond-like array, the diamond-like nano needle arrays with cutting-edge structure including matrix and setting on the matrix, the diamond-like nano needle arrays to the diamond-like coating formed on the matrix by performing etching to obtain.The structural member with diamond-like array can generate pressure to the cell wall of bacterium, and the cell wall for puncturing bacterium stretches it and finally dissolves, and lead to bacterial death, the formation of effective disrupting biofilm assigns the structural member significant anti-microbial property.The present invention also provides the preparation methods of the structural member with diamond-like array.
Description
Technical field
The present invention relates to super hydrophobic material fields, and in particular to a kind of structural member and its preparation with diamond-like array
Method.
Background technique
Biomaterial, especially for medical implant (such as automatic implantable cardiac defibrillator, catheter etc.) and operation
Biomaterial on utensil need to meet the various requirement of clinical use due to directly contacting with tissue.Except having general material
Outside the good physical of material, chemistry and mechanical property, it is necessary to there is antibiotic property, against bacteria planting, and then cause in equipment
Surface forms biomembrane and bacterial infection.Biomembrane is that microorganism is the extracellular polymer for coping with external environment variation and itself secretion
Object is gathered in dielectric surface and is formed by bacterium colony aggregation, and the formation of biomembrane will increase the drug resistance of bacterium, improves clinical doctor
The difficulty for the treatment of.Therefore, it generally requires and medical metal, ceramic material progress surface is modified, to provide its antibiotic property.
Diamond-like (diamond-like carbon, DLC) is that one kind contains sp2And sp3The amorphous carbon materials of keyed feature
Material has high rigidity, low friction, high heat conductance, high light transmittance, chemical inertness strong and the superiority such as good biocompatibility
Can, DLC film all has broad application prospects in fields such as the components such as optical window, cutter, mold, biomedical devices.
DLC coating is shown as Medical implant material surface modifying layer, main advantages: 1. DLC coating mechanical strength and plant
Enter body material can suitability not only ensure that the firm connection of coating Yu medical implant material, but also it is negative to enhance implant
Carry the support strength at position；2. its excellent wear and corrosion behavior of high-compactness DLC coating not only increases biology-mechanics interaction
The anti-corrosion wear ability of implant material under environment, while can effectively shield expansion of the metal ion to surrounding tissue and blood
It dissipates, and then inhibits harmful metal ion to dissolve in biological tissue and prevent group caused by its toxic reaction to biological tissue's generation
Damage is knitted, medical material service life is extended；3. the DLC coating of hypotoxicity and high chemical stability is because it is with controllable surface
Interface performance and can adapt to implant Service Environment, reduce human body to the rejection of medical embedded material and improve itself and biology
The compatibility of tissue.But it yet there are no the report that individual DLC coating can have antibiotic property.
Summary of the invention
In view of this, first aspect present invention provides a kind of structural member with diamond-like array, by base
One layer of diamond-like coating is first deposited on body, then it is performed etching, and forms the diamond-like with tip-like cutting-edge structure
Nano needle arrays.The structural member with diamond-like array has good anti-microbial property, to solve class in the prior art
Diamond coatings are weak or the problem of almost without anti-microbial property for bactericidal properties.
In a first aspect, the present invention provides a kind of structural member with diamond-like array, including matrix and setting are in institute
State the diamond-like nano needle arrays with cutting-edge structure on matrix, the diamond-like nano needle arrays are by being formed in
A diamond-like coating in described matrix performs etching to obtain.
Preferably, remaining diamond-like coating is additionally provided between described matrix and diamond-like nano needle arrays, it is described
Diamond-like nano needle arrays are formed in the remaining diamond-like coating surface.The remnants diamond-like coating is one complete
Coating, do not have diamond-like nanoneedle.Further, the remaining diamond-like coating with a thickness of 100nm~3 μm.
The presence of the remnants diamond-like coating, is more advantageous to the binding force for improving matrix and diamond-like nano needle arrays.
Preferably, the diamond-like nanoneedle in the diamond nano needle array is cone structure, the diamond-like
The draw ratio of nanoneedle is 20~80, and tip diameter is 10~100nm, and base diameter is 30nm~2 μm, pin density 104~
109A cm-2。
Wherein, the draw ratio refers to the ratio of diameter corresponding to the height of nanoneedle and the half of the nanoneedle height
Value.It is apparent that the base diameter should be not less than the tip diameter.
In the application, in the diamond-like nano needle arrays, the height of diamond-like nanoneedle can be uniform height
Degree, is also possible to the different nanoneedle of height, and height changes between 10nm~10 μm.Such as height can be existed simultaneously and existed
The nanoneedle that 100nm nanoneedle below and height are 0.8-9 μm.
Further, the height of the diamond-like nanoneedle is 400nm~10 μm.The height of diamond-like nanoneedle is in
Gradient distribution.
In the application, the size of the diamond-like nanoneedle is close with bacterium-sized, and major diameter is relatively high.The diamond-like
The size of stone nanoneedle can be just the same, can also be not quite identical, there is certain height variation.The diamond-like nanometer
The draw ratio of needle is 30~60 (preferably 35-55,40-50)；Tip diameter is 10~50nm or 60~100nm；Base diameter
For 800nm~2 μm or 200~700nm or 30~200nm.The pin density can be 105~109A cm-2, such as
It can be 106~× 109A cm-2, 108A cm-2.Can by the regulation to diamond-like nanoneedle size and density,
To optimize the anti-microbial property and mammality biological cell compatibility of the antibacterial diamond-like array material.
Preferably, described matrix is one kind of metal, metal alloy, hard alloy, stainless steel, polymer, glass and silicon
Or it is a variety of, but not limited to this.Especially commonly implantation material, such as titanium alloy TC 4.
Wherein, the metal can be selected from any one of titanium Ti, nickel, molybdenum Mo, niobium Nb, tantalum Ta, ruthenium Ru, platinum Pt.Institute
Stating metal alloy can be titanium-base alloy, cobalt-base alloys (such as cochrome), Ni-Ti alloy, nickel-base alloy；The hard alloy
Can be tungsten carbide base carbide alloy, titanium carbide base hard alloy, boride based cemented carbide, in type chromium carbide base hard alloy
One kind.
Preferably, when the material of described matrix is medical stainless steel, polymer, cobalt-based metal alloy, hard alloy, glass
When with silicon, the structural member with diamond-like array further includes a transition metal layer, and the transition metal layer is located at described
Between matrix and the remaining diamond-like coating.
Further, the transition metal layer with a thickness of 50~500nm.Metal in the transition metal layer be Cr,
One of transition metal elements such as Ti, Ni, Zr, W, Mo, Nb, Ta, Ru, Pt.
In the application, if the material of matrix inherently transition metal or the lesser metal alloy of thermal expansion coefficient difference
(such as titanium Ti, nickel, niobium Nb, tantalum Ta；When titanium-base alloy, Ni-Ti alloy, nickel-base alloy), directly eka-gold is deposited in matrix surface
Hard rock coating, so that it may make it be firmly bonded to matrix surface, then etch to obtain array again.If matrix is not transition metal,
Then need first to deposit one layer of transition metal layer, then the depositing diamond-like coating on the basis of transition metal layer in substrate,
It is firmly bonded on matrix with improving diamond-like coating.
The structural member with diamond-like array that first aspect present invention provides includes matrix and is arranged in described matrix
The diamond-like nano needle arrays with cutting-edge structure on surface, the diamond-like nano needle arrays are by being formed in substrate
The diamond-like coating of layer surface performs etching to obtain.The diamond-like nano needle arrays not only can be to the cell wall of bacterium
Pressure is generated, the cell wall for puncturing bacterium stretches it and finally dissolves, and leads to bacterial death, the shape of effective disrupting biofilm
At the significant anti-microbial property of imparting diamond-like coating.In addition, the diamond-like nano needle arrays are for most cells,
Especially for human body cell, hardly there is toxicity, can also support the adherency of human body cell, can be applied to various medical plants
Enter on body and surgical instrument, prevent bacterium infection, is conducive to human health.
Second aspect, the present invention provides a kind of preparation method of structural member with diamond-like array, including it is following
Step:
Matrix is provided, described matrix is pre-processed；
The pretreated matrix is placed in the vacuum chamber of filming equipment, is deposited on the pretreated matrix
Diamond-like coating；
The diamond-like coating is performed etching, the diamond-like nano needle arrays with cutting-edge structure are obtained.
Preferably, the pretreatment includes one of ultrasonic cleaning, aura cleaning and ion etching cleaning or a variety of.
In an embodiment of the present invention, it can be first cleaned by ultrasonic, the substrate after ultrasonic cleaning is placed in one later
In the vacuum chamber of depositing device, aura cleaning is first carried out, then carry out ion etching cleaning.It can better ensure that so to be processed
The cleannes of workpiece surface.
Wherein, the ultrasonic cleaning is that ultrasound 5-30min is successively carried out in deionized water, acetone, ethyl alcohol.Ultrasonic clear
It after washing, needs to dry up substrate, then carries out other pretreatments.
Wherein, the aura cleaning and ion etching cleaning are required in vacuum degree be 5.0 × 10-3Pa or less into
Row.
Specifically, the condition of aura cleaning are as follows: it is passed through argon gas into vacuum chamber, 300~500sccm of argon flow,
Operating air pressure is 1.0~1.7Pa, and the time of substrate bias -500~-800V, the aura cleaning is 10~30min.
Specifically, the condition of the ion etching cleaning are as follows: open ion source, ion source voltage is 50~90V；Argon gas stream
Amount is 70~300sccm, and operating air pressure is 0.5~1.2Pa, and substrate bias is -100~-800V；The ion etching cleaning
Time is 10~30min.
Preferably, when the material of described matrix is medical stainless steel, polymer, cobalt-base alloys, hard alloy, glass and silicon
When, it further include one transition metal layer of deposition after the pretreatment and before the deposition diamond-like coating.
Further, the step of deposition transition metal layer includes: that argon gas is passed through into vacuum chamber, adjusts the vacuum
The pressure of room is 0.2~1.3Pa, opens transition metal electric arc target, carries out arc deposited intermediate metal, and control target current is 80
~200A, substrate bias are -100~-300V, and sedimentation time is 2~10min.
Further, the transition metal layer with a thickness of 50~500nm.
Preferably, the flow of the argon gas is 50~400sccm.
Wherein, the method for depositing the diamond-like coating include magnetron sputtering, hot-wire chemical gas-phase deposition (HFCVD),
Plasma enhanced chemical vapor deposition or other conventional methods for preparing diamond-like coating.
In an embodiment of the present invention, come depositing diamond-like coating by the way of magnetron sputtering, specifically, packet
It includes: being passed through argon gas into vacuum chamber and open carbon target and deposited, make the indoor 0.5~1.0Pa of pressure of the vacuum, it is described
The target power output of carbon target is 1~5kW, and negative substrate bias is -50~-200V, and sedimentation time is 30~600min.
In an embodiment of the present invention, the mode of using plasma enhancing chemical vapor deposition carrys out depositing diamond-like
Coating, specifically, comprising: be passed through gaseous carbon source into vacuum chamber and deposited, make the indoor pressure of the vacuum 0.5~
1.0Pa, ion source voltage are 50~100V, and negative substrate bias is -50~-200V, and sedimentation time is 30~600min.Gaseous carbon
Source is including that can be methane, acetylene, acetone etc..At this point, the diamond-like coating with a thickness of 500nm-10 μm.
Wherein, the etching of the diamond-like coating is returned using inductively coupled plasma (ICP) etching or electronics
Revolve resonant microwave plasma activated chemical vapour deposition (ECR-MWPCVD) etching.At this point, the diamond-like coating with a thickness of
500nm-10μm。
Further, the condition of the ICP etching are as follows: the matrix for being deposited with diamond-like coating is placed in inductive coupling etc.
In plasma etching (ICP) cavity, hydrogen, argon gas, oxygen, helium, nitrogen, gaseous carbon source, CF are utilized4、C4F8And SF6In
One or more is reaction gas, and the flow of reaction gas is 5~200sccm, and reaction pressure is 0.1~10Pa, the power supply of ICP
Power PICPFor 500~3000W, radio-frequency power P on chip benchrfFor 50~300W, etch period is 10~600min.At this point, by
The diamond-like coating etched away with a thickness of 400nm~10 μm.
In the application, the power P of the ICPICPIt plays a key effect for the ionization level of gas；Penetrate radio-frequency power
PrfRefer to the substrate bias power for loading on chip bench (matrix), PrfDetermine specific gravity shared by physical bombardment in etching process, for
Etching orientation selectivity and rate play a key effect.It is main to pass through control PICPAnd PrfIt may be implemented to final etching gained knot
The control of the pattern of structure.
Further, the step of ECR-MWPCVD is etched includes: to be placed in the matrix for being deposited with diamond-like coating
In electron cyclotron resonance microwave plasmas chemical vapor deposition (ECR-MWPCVD) equipment, it is passed through hydrogen, gaseous carbon source and argon
One of gas is a variety of as reaction gas, and gas pressure is 5~8mTorr, and DC negative bias voltage is 75~230V, and bias current is
40~120mA, etch period are 30 minutes~6 hours.Wherein, the gaseous carbon source can be the gaseous states such as methane, acetylene, acetone
Carbon source, preferably methane.At this point, at this point, the diamond-like coating being etched away with a thickness of 400nm~10 μm.
Preferably, when the ECR-MWPCVD is etched, the gas being passed through is individual hydrogen or hydrogen and gaseous carbon
The gaseous mixture that the mixed gas or hydrogen and the mixed gas or hydrogen of argon gas, gaseous carbon source and hydrogen in source are constituted
Body.
In addition, also HFCVD lithographic method can be assisted to perform etching diamond-like coating, the diamond-like of formation by double biass
Stone nano needle arrays.
The preparation method for a kind of structural member with diamond-like array that second aspect of the present invention provides, by matrix
It is upper first to deposit one layer of diamond-like coating, then it is performed etching, being formed, there is the diamond-like of tip-like cutting-edge structure to receive
Rice needle array, the diamond-like nano needle arrays have the function of that preferable antibacterium sticks, kills bacterium.The preparation side
Method is simple to operation, can form the large area eka-diamond nano needle arrays with sharp tip, is convenient for commercialized application.
Advantages of the present invention will be illustrated partially in the following description, and a part is apparent according to specification
, or can implementation through the embodiment of the present invention and know.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the structural member obtained with diamond-like array of the embodiment of the present invention 1,2；
Fig. 2 is the structural schematic diagram of 3-5 of the embodiment of the present invention structural member obtained with diamond-like array；
Fig. 3 is the antibacterial of the structural member and comparative example 1 obtained with diamond-like array of the embodiment of the present invention 4,5
The performance test results.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Embodiment 1:
A kind of preparation method of the structural member with diamond-like array, comprising:
(1) substrate pretreated:
Cochrome is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then successively use acetone
It is cleaned by ultrasonic 20min with dehydrated alcohol, is then dried up matrix with nitrogen, and is put into 100 DEG C of drying in air dry oven；
Above-mentioned matrix is placed in the vacuum cavity of multifunction ion filming equipment (V-Tech MF610/610), it first will be true
It is 5.0 × 10 that cavity body, which is evacuated to background vacuum,-3Pa opens argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target
Valve and mass flowmenter are passed through argon gas into vacuum chamber and carry out aura cleaning to matrix, wherein the condition of aura cleaning are as follows: argon
Throughput 300sccm, operating pressure 1.0Pa, substrate bias are -800V, carry out aura cleaning to substrate, scavenging period is
10min；After aura cleans, opens ion source and icon bombardment cleaning, ion etching cleaning condition are as follows: ion are carried out to sample
Source voltage is 90V, and argon flow 300sccm, the operating air pressure of argon gas is 1.2Pa, and substrate bias is -800V；Scavenging period is
10min；
(2) transition metal layer deposits: after above-mentioned ion etching cleaning, argon gas is passed through into vacuum chamber, adjusts argon
Throughput makes the pressure 1.3Pa of vacuum chamber, opens transition metal electric arc target, target current 100A, and substrate bias is -300V,
The deposition of intermediate metal, sedimentation time 3min are carried out in a manner of arc ion plating；Wherein, electricity is made with pure Ti in the present embodiment
Arc target, Ti layers of gained with a thickness of 80nm.
(3) diamond-like rock layers (DLC) deposit: on transition metal layer obtained in the previous step by the way of magnetron sputtering into
The deposition of row DLC is passed through argon gas into vacuum chamber and opens carbon target (specially pure graphite target), and adjusting argon flow makes vacuum chamber
Interior pressure is 0.6Pa, and carbon target power is 5kW, and negative substrate bias is -30V, sedimentation time 1.5h；Wherein, the thickness of DLC layer
Degree is 2.5 μm；
(4) etching of DLC: after the deposition of above-mentioned DLC layer, multifunction ion filming equipment (V-Tech is closed
MF610/610), it is down to room temperature to substrate temperature, matrix is placed in electron cyclotron resonance microwave plasmas chemical vapor deposition
In system (ECR-MWPCVD), it is evacuated to 10-5Then Pa is flushed with hydrogen gas to 7mTorr again, opens ECR microwave plasma mould
Formula, intensity of the magnetic field that additional electromagnetic coil provides in the area ECR is 875 Gausses, carries out reactive ion etching using following condition:
It is passed through hydrogen and methane, methane/hydrogen volume ratio: 3%/97%, total gas couette: 20sccm makes gas pressure
6.6mTorr, the DC negative bias voltage loaded on substrate of substrate stage are -220V, and bias current 80mA, etch period is 2 hours, and etching finishes
After turn off bias, microwave power supply, electromagnetic coil power supply, close gas, obtain diamond-like nano needle arrays；Wherein, it etches away
DLC layer thickness (i.e. the height of diamond-like nanoneedle) be 2 μm, remaining DLC layer with a thickness of 500nm；The eka-gold
The draw ratio of hard rock nanoneedle is 50, tip diameter 50nm, base diameter 200nm, and pin density is~108cm-2。
Embodiment 2:
A kind of preparation method of the structural member with diamond-like array, comprising:
(1) substrate pretreated:
Polyether-ether-ketone (PEEK) substrate is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then
Successively it is cleaned by ultrasonic 20min with acetone and dehydrated alcohol, is then dried up matrix with nitrogen, and be put into air dry oven 80 DEG C
Drying；
Above-mentioned matrix is placed in multifunction ion filming equipment (V-Tech MF610/610), is evacuated to 5.0 × 10- 3Pa opens argon bottle main valve, and pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter are passed through argon gas into vacuum chamber
Aura cleaning is carried out to matrix, wherein the condition of aura cleaning is that argon gas, argon flow 400sccm, work are passed through into vacuum chamber
Making pressure is 1.4Pa, substrate bias -500V, carries out aura cleaning, scavenging period 30min to substrate；Aura cleaning terminates
Afterwards, it opens ion source and icon bombardment cleaning, ion etching cleaning condition are as follows: ion source voltage 50V, argon gas stream is carried out to sample
70sccm is measured, the operating air pressure of argon gas is 0.5Pa, and substrate bias is -100V；Scavenging period is 30min；
(2) transition metal layer deposits: after above-mentioned ion etching cleaning, argon gas is passed through into vacuum chamber, adjusts argon
The pressure 1.0Pa that throughput (flow is 50~400sccm) makes vacuum chamber, opens transition metal electric arc target, target current is
150A, substrate bias are -200V, and the deposition of intermediate metal, sedimentation time 10min are carried out in a manner of arc ion plating；Its
In, electric arc target is made with pure Ti in the present embodiment, Ti layers of gained with a thickness of 500nm.
(3) diamond-like rock layers (DLC) deposit: the using plasma enhancing chemistry on transition metal layer obtained in the previous step
The mode of vapor deposition (PECVD) carries out the deposition of DLC, and acetylene and argon gas are passed through into vacuum chamber, adjusts the indoor pressure of vacuum
It is by force 1.0Pa, ion source voltage 100V, negative substrate bias is -50V, sedimentation time 10h；Wherein, DLC layer with a thickness of
10μm；
(4) etching of DLC: after the deposition to above-mentioned DLC layer, multifunction ion filming equipment (V-Tech is closed
MF610/610), it is down to room temperature to substrate temperature, matrix is placed in the cavity of inductively coupled plasma etching (ICP) equipment
In, plasma etching is carried out to matrix, the condition etched using ICP are as follows: it is passed through oxygen as reaction gas, reaction gas
Flow is 20sccm, and the frequency of operating pressure 10Pa, ICP are 13.56MHz, the power P of ICPICPFor 1000W, substrate
Radio-frequency power P on platformrfFor 200W, etch period 90min turns off ICP source after etching, closes gas, obtain diamond-like
Stone nano needle arrays；Wherein, the thickness (i.e. the height of diamond-like nanoneedle) of the DLC layer etched away is~9 μm, remaining
DLC layer with a thickness of 1 μm；The draw ratio of the diamond-like nanoneedle is~20, and tip diameter is 60~100nm, and bottom is straight
Diameter is 800nm~1 μm, and pin density is~104cm-2。
Fig. 1 is the structural schematic diagram of antibacterial diamond-like array material made from the embodiment of the present invention 1,2.101 are in Fig. 1
Matrix, 102 be transition metal layer, and 1031 be remaining diamond-like rock layers, and 1031 be diamond-like nano needle arrays, 1031 Hes
1032 thickness summation is the thickness of the DLC layer of embryo deposit.
Embodiment 3:
A kind of preparation method of the structural member with diamond-like array, comprising:
(1) substrate pretreated:
Ni-Ti alloy is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then successively with third
Ketone and dehydrated alcohol are cleaned by ultrasonic 20min, are then dried up matrix with nitrogen, and are put into air dry oven and dry in 120 DEG C；
Above-mentioned matrix is placed in multifunction ion filming equipment (V-Tech MF610/610), is in background vacuum
5.0×10-3Under conditions of Pa, open argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter to
It is passed through argon gas in vacuum chamber, aura cleaning is carried out to matrix, wherein the condition of aura cleaning are as follows: argon gas is passed through into vacuum chamber,
Argon flow 500sccm, operating pressure 1.5Pa, substrate bias -600V carry out aura to substrate and clean 20min；Aura is clear
After washing, opens ion source and icon bombardment cleaning, ion etching cleaning condition are carried out to sample are as follows: ion source voltage 70V,
Argon flow 150sccm, the operating air pressure of argon gas are 0.9Pa, and substrate bias is -550V；Scavenging period 20min；
(2) transition metal deposits: after above-mentioned ion etching cleaning, argon gas is passed through into vacuum chamber, adjusts argon gas
Flow (50~400sccm) makes the pressure 1.0Pa of vacuum chamber, opens transition metal electric arc target, target current 100A, and substrate is inclined
Pressure is -300V, and the deposition of intermediate metal, sedimentation time 4min are carried out in a manner of arc ion plating；Wherein, in the present embodiment
Make electric arc target with pure Ti, Ti layers of gained with a thickness of 100nm.
(3) diamond-like rock layers (DLC) deposit: after above-mentioned ion etching cleaning, matrix being placed in multifunction ion
In filming equipment (V-Tech MF610/610), using plasma enhances the mode of chemical vapor deposition (PECVD) in matrix
Surface carries out the deposition of DLC, and acetylene and argon gas are passed through into vacuum chamber, and the adjusting indoor pressure of vacuum is 0.9Pa, ion source electricity
Pressure is 80V, and negative substrate bias is -100V, sedimentation time 60min；Wherein, DLC layer with a thickness of 0.5 μm；
(4) etching of DLC: after the deposition to above-mentioned DLC layer, multifunction ion filming equipment (V-Tech is closed
MF610/610), it is down to room temperature to substrate temperature, matrix is placed in the cavity of inductively coupled plasma etching (ICP) equipment
In, plasma etching is carried out to matrix, the condition etched using ICP are as follows: be passed through CF4Or SF6As reaction gas, reaction gas
The flow of body is 40sccm, and the frequency of operating pressure 10Pa, ICP are 13.56MHz, the power P of ICPICPFor 2000W,
Radio-frequency power P on chip benchrfFor 150W, etch period 50min turns off ICP source after etching, closes gas, obtain class
Diamond nano needle array；Wherein, the thickness (i.e. the height of diamond-like nanoneedle) of the DLC layer etched away is 450nm, remaining
DLC layer with a thickness of 50nm；The draw ratio of the diamond-like nanoneedle is~10, tip diameter 20nm, base diameter
For 100nm, pin density is~109cm-2。
Embodiment 4:
A kind of preparation method of the structural member with diamond-like array, comprising:
(1) substrate pretreated:
Titanium alloy TC 4 is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then successively with third
Ketone and dehydrated alcohol are cleaned by ultrasonic 20min, are then dried up matrix with nitrogen, and are put into 150 DEG C of drying in air dry oven；
Above-mentioned matrix is placed in multifunction ion filming equipment (V-Tech MF610/610), is in background vacuum
5.0×10-3Under conditions of Pa, open argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter to
It is passed through argon gas in vacuum chamber, aura cleaning is carried out to matrix, wherein the condition of aura cleaning are as follows: argon gas is passed through into vacuum chamber,
Argon flow 450sccm, operating pressure 1.7Pa, substrate bias -800V carry out aura cleaning, scavenging period to substrate
10min；After aura cleans, opens ion source and icon bombardment cleaning, ion etching cleaning condition are as follows: ion are carried out to sample
Source voltage is 80V, and argon flow 200sccm, the operating air pressure of argon gas is 1.0Pa, and substrate bias is -450V；Scavenging period is
20min；
(2) diamond-like rock layers (DLC) deposit: above-mentioned ion etching cleaning after, by the way of magnetron sputtering
Matrix surface carries out the deposition of DLC, and argon gas is passed through into vacuum chamber and is opened carbon target (specially graphite target), adjusts argon flow
Make the indoor pressure 0.8Pa of vacuum, carbon target power is 1kW, and negative substrate bias is -100V, and sedimentation time is 5 hours；Wherein,
DLC layer with a thickness of 5 μm；
(3) etching of DLC: after the deposition to above-mentioned DLC layer, multifunction ion filming equipment (V-Tech is closed
MF610/610), it is down to room temperature to substrate temperature, matrix is placed in electron cyclotron resonance microwave plasmas chemical vapor deposition
In system (ECR-MWPCVD), it is evacuated to 10-5Then Pa is flushed with hydrogen gas to 7mTorr again, opens ECR microwave plasma mould
Formula, intensity of the magnetic field that additional electromagnetic coil provides in the area ECR is 875 Gausses, carries out reactive ion etching using following condition:
It is passed through hydrogen, gas flow are as follows: 20sccm makes gas pressure 8mTorr, and the DC negative bias voltage loaded on substrate of substrate stage is-
150V, bias current 40-60mA, etch period 120min turn off bias, microwave power supply, electromagnetic coil power supply after etching,
Gas is closed, diamond-like nano needle arrays are obtained；Wherein, thickness (the i.e. cone cell diamond-like nanoneedle of the DLC layer etched away
Height) be 800nm~2.5 μm, remaining DLC layer with a thickness of 2.5 μm.Gained diamond-like nanoneedle in the present embodiment
Tip diameter is 10~40nm, and base diameter is 350~750 μm, and pin density is~4 × 108cm-2。
Embodiment 5:
A kind of preparation method of the structural member with diamond-like array, comprising:
(1) substrate pretreated:
Titanium alloy TC 4 is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then successively with third
Ketone and dehydrated alcohol are cleaned by ultrasonic 20min, are then dried up matrix with nitrogen, and are put into 150 DEG C of drying in air dry oven；
Above-mentioned matrix is placed in multifunction ion filming equipment (V-Tech MF610/610), is in background vacuum
5.0×10-3Under conditions of Pa, open argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter to
It is passed through argon gas in vacuum chamber, aura cleaning is carried out to matrix, wherein the condition of aura cleaning are as follows: argon gas is passed through into vacuum chamber,
Argon flow 450sccm, operating pressure 1.7Pa, substrate bias -800V carry out aura cleaning, scavenging period to substrate
10min；After aura cleans, opens ion source and icon bombardment cleaning, ion etching cleaning condition are as follows: ion are carried out to sample
Source voltage is 80V, and argon flow 200sccm, the operating air pressure of argon gas is 1.0Pa, and substrate bias is -450V；Scavenging period is
20min；
(2) diamond-like rock layers (DLC) deposit: above-mentioned ion etching cleaning after, by the way of magnetron sputtering
Matrix surface carries out the deposition of DLC, and argon gas is passed through into vacuum chamber and is opened carbon target (specially graphite target), adjusts argon flow
Make the indoor pressure 0.8Pa of vacuum, carbon target power is 1kW, and negative substrate bias is -100V, and sedimentation time is 5 hours；Wherein,
DLC layer with a thickness of 5 μm；
(3) etching of DLC: after the deposition to above-mentioned DLC layer, multifunction ion filming equipment (V-Tech is closed
MF610/610), it is down to room temperature to substrate temperature, matrix is placed in electron cyclotron resonance microwave plasmas chemical vapor deposition
In system (ECR-MWPCVD), it is evacuated to 10-5Then Pa is flushed with hydrogen gas to 7mTorr again, opens ECR microwave plasma mould
Formula, intensity of the magnetic field that additional electromagnetic coil provides in the area ECR is 875 Gausses, carries out reactive ion etching using following condition:
It is passed through hydrogen and argon gas, argon gas/hydrogen volume ratio: 45%/55%, total gas couette: 20sccm makes gas pressure
5mTorr, the DC negative bias voltage loaded on substrate of substrate stage are -200V, and bias current 40-60mA, etch period 240min have been etched
Turn off bias, microwave power supply, electromagnetic coil power supply after finishing, closes gas, obtain diamond-like nano needle arrays；Wherein, remaining
DLC layer with a thickness of 500nm, the pin density of obtained diamond-like nanoneedle is about 1.7 × 108cm-2, it is divided into two
Part, wherein fraction diamond-like nanocone is very small, is highly less than 100nm, and tip diameter is 10~40nm, base diameter
Less than 100nm；And the height of most of nanocones be 3~4.5 μm, base diameter be 100nm~2 μm, tip diameter be 10~
40nm。
Fig. 2 is the structural schematic diagram of antibacterial diamond-like array material made from 3-5 of the embodiment of the present invention.201 are in Fig. 1
Matrix, 2021 be remaining diamond-like rock layers, and 2022 be diamond-like nano needle arrays, in the remaining diamond-like rock layers and base
Transition metal layer is not provided between body.
Comparative example 1
(1) substrate pretreated:
Titanium alloy TC 4 is provided as matrix, the matrix will be cleaned by ultrasonic 10min with distilled water first, then successively with third
Ketone and dehydrated alcohol are cleaned by ultrasonic 20min, are then dried up matrix with nitrogen, and are put into 150 DEG C of drying in air dry oven；
Above-mentioned matrix is placed in multifunction ion filming equipment (V-Tech MF610/610), is in background vacuum
5.0×10-3Under conditions of Pa, open argon bottle main valve, pressure reducing valve, ion source valve, arc valve and target valve and mass flowmenter to
It is passed through argon gas in vacuum chamber, aura cleaning is carried out to matrix, wherein the condition of aura cleaning are as follows: argon gas is passed through into vacuum chamber,
Argon flow 450sccm, operating pressure 1.7Pa, substrate bias -800V carry out aura cleaning, scavenging period to substrate
10min；After aura cleans, opens ion source and icon bombardment cleaning, ion etching cleaning condition are as follows: ion are carried out to sample
Source voltage is 80V, and argon flow 200sccm, the operating air pressure of argon gas is 1.0Pa, and substrate bias is -450V；Scavenging period is
20min；
(2) diamond-like rock layers (DLC) deposit: above-mentioned ion etching cleaning after, by the way of magnetron sputtering
Matrix surface carries out the deposition of DLC, and argon gas is passed through into vacuum chamber and is opened carbon target (specially graphite target), adjusts argon flow
Make the indoor pressure 0.8Pa of vacuum, carbon target power is 1kW, and negative substrate bias is -100V, and sedimentation time is 5 hours；Wherein,
DLC layer with a thickness of 5 μm；
Effect example
There is anti-microbial property to verify material produced by the present invention, the present invention also provides effect examples.
Antibacterial diamond-like array material made from the embodiment of the present invention 4,5 is subjected to anti-microbial property test respectively, and
The complete DLC layers of 5 μ m-thicks embodiment 1 as a comparison is deposited on titanium alloy TC 4, result is as shown in figure 3, Pseudomonas aeruginosa is distinguished
Act on comparative example 1 (titanium alloy TC 4+complete DLC layer) and embodiment 4 and 5 gained diamond-like nanometer battle array of embodiment
On column, (a) is the P aeruginosa bacteria sum of the different substrate attachment of surface topography；It (b) is Pseudomonas aeruginosa institute dead after 1h
The percentage accounted for.It can be seen that complete diamond-like coating (comparative example 1) and the institute of embodiment 4 and 5 from (b) in Fig. 3
Obtaining diamond-like nanoneedle column all has certain antibacterial effect, but the sterilization of the gained diamond-like nanoneedle of embodiment 4 and 5 column
Bactericidal effect of the effect obviously than the complete diamond-like coating not etched commonly is much better.And it compares and is etched under different condition
Nanoneedle column, it can be seen that the sterilization effect of the column of diamond-like nanoneedle obtained by embodiment 5 (height different nanoneedle)
Fruit is much better.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of structural member with diamond-like array, which is characterized in that including the tool of matrix and setting on the matrix
There are a diamond-like nano needle arrays of cutting-edge structure, the diamond-like nano needle arrays are by forming on the matrix
One diamond-like coating performs etching to obtain；Diamond-like nanoneedle in the diamond-like nano needle arrays is cone cell knot
Structure, the draw ratio of the diamond-like nanoneedle are 20~80, and tip diameter is 10~100nm, and base diameter is the μ of 30nm~2
M, pin density 108~109A cm-2。
2. as described in claim 1 with the structural member of diamond-like array, which is characterized in that described matrix and diamond-like
Remaining diamond-like coating is additionally provided between nano needle arrays, the diamond-like nano needle arrays are formed in the remaining class
Diamond coatings surface；It is described remnants diamond-like coating with a thickness of 100nm~3 μm.
3. as claimed in claim 2 with the structural member of diamond-like array, which is characterized in that the diamond-like nanoneedle
Height between 10nm~10 μm.
4. as claimed in claim 2 with the structural member of diamond-like array, which is characterized in that described matrix is metal, gold
Belong to the one or more of alloy, hard alloy, polymer, glass and silicon.
5. as claimed in claim 4 with the structural member of diamond-like array, which is characterized in that when the material of described matrix is
When stainless steel, polymer, cobalt-based metal alloy, hard alloy, glass and silicon, the structural member with diamond-like array is also
Including a transition metal layer, the transition metal layer is located between described matrix and the remaining diamond-like coating；The mistake
Cross metal layer with a thickness of 50~500nm.
6. a kind of preparation method of the structural member with diamond-like array, which comprises the following steps:
Structural member matrix is provided, described matrix is pre-processed；
The pretreated matrix is placed in the vacuum chamber of filming equipment, deposits eka-gold on the pretreated matrix
Hard rock coating；
The diamond-like coating is performed etching, obtains the diamond-like nano needle arrays with cutting-edge structure, wherein described
Diamond-like nanoneedle in diamond-like nano needle arrays is cone structure, and the draw ratio of the diamond-like nanoneedle is 20
~80, tip diameter is 10~100nm, and base diameter is 30nm~2 μm, pin density 108~109A cm-2。
7. preparation method as claimed in claim 6, which is characterized in that the method for the deposition diamond-like coating includes
Magnetron sputtering or plasma enhanced chemical vapor deposition；
Wherein, the step of magnetron sputtering includes: and is passed through argon gas into vacuum chamber and opens carbon target to be deposited, and makes described true
Empty indoor pressure is 0.5~1.0Pa, and the target power output of the carbon target is 1~5kW, and negative substrate bias is -50~-200V, deposition
Time is 30~600min；
Wherein, the step of plasma enhanced chemical vapor deposition includes: and is passed through gaseous carbon source into vacuum chamber to be sunk
Product, makes the indoor 0.5~1.0Pa of pressure of the vacuum, and ion source voltage is 50~100V, negative substrate bias for -50~-
200V, sedimentation time are 30~600min.
8. preparation method as claimed in claim 6, which is characterized in that the etching of the diamond-like coating is using induction coupling
Close plasma etching or electron cyclotron resonance microwave plasmas chemical vapor deposition etching；
Wherein, the step of sense coupling includes: that the matrix for being deposited with diamond-like coating is placed in electricity
In the cavity for feeling coupled plasma etch, hydrogen, argon gas, oxygen, helium, nitrogen, gaseous carbon source and SF are utilized6One of
Or a variety of is reaction gas, the flow of reaction gas is 5~200sccm, and reaction pressure is 0.1~10Pa, the electricity of plasma
Source power is 500~3000W, and the radio-frequency power on chip bench is 50~300W, and etch period is 10~600min；
Wherein, the step of electron cyclotron resonance microwave plasmas chemical vapor deposition etches includes: that will be deposited with eka-gold
The matrix of hard rock coating is placed in electron cyclotron resonance microwave plasmas chemical vapor depsotition equipment, is passed through hydrogen or is passed through
Mixed hydrogen, gaseous carbon source and argon gas, gas pressure be 5~8mTorr, DC negative bias voltage be 75~230V, bias current be 40~
120mA, etch period are 30 minutes~6 hours.
9. such as the described in any item preparation methods of claim 6-8, which is characterized in that after the pretreatment and deposition institute
It further include one transition metal layer of deposition before stating diamond-like coating；
Wherein, the step of deposition transition metal layer includes: that argon gas is passed through into vacuum chamber, adjusts the pressure of the vacuum chamber
For 0.2~1.3Pa, transition metal electric arc target to be opened, carries out arc deposited intermediate metal, control target current is 80~200A,
Substrate bias is -100~-300V, and sedimentation time is 2~10min.
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| CN104553124A (en) * | 2014-12-02 | 2015-04-29 | 中国科学院深圳先进技术研究院 | Diamond nano needle array composite material and preparation method and application thereof |
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