WO2018113053A1

WO2018113053A1 - Structural member with diamond-like array, and preparation method therefor

Info

Publication number: WO2018113053A1
Application number: PCT/CN2017/070889
Authority: WO
Inventors: 唐永炳; 杨扬; 秦盼盼; 张文军
Original assignee: 深圳先进技术研究院
Priority date: 2016-12-20
Filing date: 2017-01-11
Publication date: 2018-06-28
Also published as: CN106835011B; CN106835011A

Abstract

Disclosed is a structural member with a diamond-like array. The structural member comprises a matrix (101, 201) and a diamond-like nano-needle array (1032, 2022) arranged on the matrix (101, 201) and having a tip structure. The diamond-like nano-needle array (1032, 2022) is obtained by means of etching a diamond-like coating formed on the matrix (101, 201). Further disclosed is a preparation method for the structural member with a diamond-like array.

Description

Structural member with diamond-like array and preparation method thereof

The present application claims priority to Chinese Patent Application No. 201611185457.X filed on Dec. 20, 2016, entitled "A Structural Member Having a Diamond-Like Array and Its Preparation Method", The content of the first application is incorporated herein by reference.

Technical field

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.

Background technique

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. And enhance the support strength of the implant load site; 2 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. However, there have been no reports of antibacterial properties of individual DLC coatings.

Summary of the invention

In view of the above, 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.

In a first aspect, 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.

Preferably, 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. Further, the residual diamond-like carbon coating has a thickness of 100 nm to 3 μm. 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.

Preferably, 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 μm. The needle density is 10 ⁴ to 10 ⁹ · cm ^-2 .

Wherein, 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. Obviously, the bottom diameter should be no smaller than the tip diameter.

In the present application, in the diamond nanoneedle array, 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 μm. For example, a nanoneedle having a height of 100 nm or less and a nanoneedle having a height of 0.8 to 9 μm can be simultaneously present.

Further, the diamond-like nanoneedle has a height of 400 nm to 10 μm. The height of the diamond-like nanoneedles is a gradient.

In the present application, 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 μm 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.

Preferably, 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. In particular, commonly used implant materials, such as titanium alloy TC4.

Wherein, 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. One of a mass alloy, a titanium carbonitride-based cemented carbide, or a chromium carbide-based cemented carbide.

Preferably, when the material of the substrate is medical stainless steel, polymer, cobalt-based metal alloy, cemented carbide, glass and silicon, 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.

Further, 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.

In the present application, if 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), Depositing a diamond-like coating directly on the surface of the substrate allows it to be firmly bonded to the surface of the substrate and then etched to form an array. If the substrate is not a transition metal, 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. In addition, 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.

In a second aspect, the present invention provides a method of fabricating a structural member having a diamond-like array, comprising the steps of:

Providing a substrate for pretreating the substrate;

Depositing the pretreated substrate in a vacuum chamber of a coating apparatus, depositing a diamond-like coating on the pretreated substrate;

The diamond-like carbon coating is etched to obtain a diamond-like nanoneedle array having a tip structure.

Preferably, the pretreatment comprises one or more of ultrasonic cleaning, glow cleaning, and ion etching cleaning.

In an embodiment of the invention, 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.

Wherein, 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.

Wherein, both the glow cleaning and the ion etching cleaning need to be performed under a vacuum of 5.0×10 ⁻³ Pa or less.

Specifically, 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.

Specifically, 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.

Preferably, when 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.

Further, 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.

Further, the transition metal layer has a thickness of 50 to 500 nm.

Preferably, the flow rate of the argon gas is 50 to 400 sccm.

Among them, 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.

In an embodiment of the invention, 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.

In an embodiment of the invention, 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. At this time, the diamond-like carbon coating has a thickness of 500 nm to 10 μm.

Wherein, the diamond-like coating is etched by inductively coupled plasma (ICP) etching or electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MWPCVD) etching. At this time, the diamond-like carbon coating has a thickness of 500 nm to 10 μm.

Further, 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. 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 μm.

In the present application, 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 .

Further, 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. Wherein, the gaseous carbon source may be a gaseous carbon source such as methane, acetylene or acetone, preferably methane. At this time, at this time, the thickness of the diamond-like coating to be etched is 400 nm to 10 μm.

Preferably, in the ECR-MWPCVD etching, 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.

In addition, 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.

The advantages of the invention will be set forth in part in the description which follows.

DRAWINGS

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;

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;

3 is a test result of antibacterial properties of a structural member having a diamond-like array prepared in Examples 4 and 5 of the present invention and Comparative Example 1.

detailed description

The following is a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It is the scope of protection of the present invention.

Example 1:

A method for preparing a structural member having a diamond-like array, comprising:

(1) Matrix pretreatment:

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. Pa, the substrate bias is -800V, the substrate is cleaned by glow cleaning, the cleaning time is 10min; after the glow cleaning is finished, 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, and the cleaning time is 10min;

(2) 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.

(3) Diamond-like layer (DLC) deposition: 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 μm;

(4) Etching of DLC: After the deposition of the above DLC layer is completed, the multi-function ion plating equipment (V-Tech MF610/610) is turned off, and the substrate is placed in an electron cyclotron resonance microwave plasma chemical vapor phase after the substrate temperature is lowered to room temperature. In the deposition system (ECR-MWPCVD), evacuate to 10 ^-5 Pa, then recharge the hydrogen to 7 mTorr, turn on the ECR microwave plasma mode, and the magnetic field provided by the electromagnetic coil is 875 Gauss in the ECR region, using the following conditions. 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 .

Example 2:

(1) Matrix pretreatment:

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;

Place the above substrate in the multi-function ion plating equipment (V-Tech MF610/610), evacuate to 5.0×10 ^-3 Pa, open the main valve of the argon cylinder, pressure reducing valve, ion source valve, arc valve and target valve. And 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. Glow cleaning of the substrate, 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;

(2) 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. In this embodiment, the thickness of the Ti layer is obtained by using pure Ti as an arc target. It is 500 nm.

(3) Diamond-like layer (DLC) deposition: 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. The pressure in the chamber is 1.0 Pa, the ion source voltage is 100 V, the substrate negative bias is -50 V, and the deposition time is 10 h; wherein the thickness of the DLC layer is 10 μm;

(4) 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. After the etching is completed, 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) is ～9 μm, and the thickness of the residual DLC layer is 1 μm; 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 μm, and the needle density is ～10 ⁴ cm ^-2 .

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view showing the structure of an antibacterial diamond-like array material obtained in Examples 1 and 2. In Fig. 1, 101 is a substrate, 102 is a transition metal layer, 1031 is a residual diamond-like layer, and 1031 is a diamond-like nanoneedle array, and the sum of the thicknesses of 1031 and 1032 is the thickness of the initially deposited DLC layer.

Example 3:

(1) Matrix pretreatment:

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;

(2) 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. For 100A, the substrate bias is -300V, and the metal transition layer is deposited by arc ion plating for a deposition time of 4 min. In this embodiment, pure Ti is used as an arc target, and the thickness of the Ti layer is 100 nm.

(3) 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 μm;

(4) 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. 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 .

Example 4:

(1) Matrix pretreatment:

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. Pa, substrate bias -800V, the substrate is polished by glow, the cleaning time is 10min; after the glow cleaning is finished, the ion source is turned on to ion bombard the sample. 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;

(2) 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 μm;

(3) Etching of DLC: After the deposition of the above DLC layer is finished, the multi-function ion plating equipment (V-Tech MF610/610) is turned off, and the substrate is placed at the temperature of the room temperature, and the substrate is placed in an electron cyclotron resonance microwave plasma chemistry. system vapor deposition (ECR-MWPCVD), and then evacuated to 10 ^-5 Pa, and then refilled with hydrogen to 7mTorr, ECR microwave plasma open mode, magnetic field intensity of the electromagnetic coil provided in the ECR zone is 875 gauss, using the following conditions Perform reactive ion etching: pass hydrogen gas, the gas flow rate is: 20sccm, the gas pressure is 8mTorr, the DC negative bias voltage applied to the substrate is -150V, the bias current is 40-60mA, the etching time is 120min, and the etching is completed. After turning off the bias voltage, the microwave power supply, the electromagnetic coil power supply, and turning off the gas, 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 μm. The thickness of the residual DLC layer was 2.5 μm. 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 μm, and a needle density of ～4×10 ⁸ cm ^-2 .

Example 5:

(1) Matrix pretreatment:

(2) Diamond-like layer (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 μm;

(3) Etching of DLC: After the deposition of the above DLC layer is finished, the multi-function ion plating equipment (V-Tech MF610/610) is turned off, and the substrate is placed at the temperature of the room temperature, and the substrate is placed in an electron cyclotron resonance microwave plasma chemistry. In the vapor deposition system (ECR-MWPCVD), evacuate to 10 ^-5 Pa, then recharge the hydrogen to 7 mTorr, turn on the ECR microwave plasma mode, and the magnetic field provided by the electromagnetic coil is 875 Gauss in the ECR region, using the following conditions. Perform reactive ion etching: pass hydrogen and argon, argon/hydrogen volume ratio: 45%/55%, total gas flow rate: 20sccm, gas pressure is 5mTorr, and the DC negative bias voltage applied to the substrate is -200V The bias current is 40-60 mA, and the etching time is 240 min. After the etching is completed, the bias voltage, the microwave power supply, the electromagnetic coil power supply are turned off, and the gas is turned off to obtain a diamond-like nanoneedle array; wherein the residual DLC layer has a thickness of 500 nm. 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 μm, a bottom diameter of 100 nm to 2 μm, and a tip diameter of 10 to 40 nm.

2 is a schematic structural view of an antibacterial diamond-like array material prepared in Example 3-5 of the present invention. In Fig. 1, 201 is a matrix, 2021 is a residual diamond-like layer, and 2022 is a diamond-like nanoneedle array, and no transition metal layer is disposed between the residual diamond-like layer and the substrate.

Comparative Example 1

(1) Matrix pretreatment:

In order to verify that the material produced by the present invention has antibacterial properties, 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 μm 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. It can be seen from Figure (b) that the complete diamond-like coating (Comparative Example 1) and the diamond-like nanoneedle arrays obtained in Examples 4 and 5 have certain antibacterial effects, but the diamond-like nanoneedles obtained in Examples 4 and 5 The bactericidal effect of the column is significantly better than that of the conventional diamond-free coating without etching. Comparing the nanoneedle arrays etched under different conditions, it can be seen that the diamond-like nanoneedle arrays (nano needles of different heights) prepared in Example 5 have better bactericidal effects.

The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

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 on the substrate by a pair A type of diamond coating is obtained by etching.
The structural member with a diamond-like array according to claim 1, wherein 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 in the Residual diamond-like coating surface; the residual diamond-like coating has a thickness of 100 nm to 3 μm.
The structural member with a diamond-like array according to claim 1, wherein 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. The diameter of the tip is 10 to 100 nm, the diameter of the bottom is 30 nm to 2 μm, and the density of the needle is 10 4 to 10 9 ·cm· 2 .
The structural member having a diamond-like array according to claim 3, wherein the diamond-like nanoneedle has a height of between 10 nm and 10 μm.
The structural member with a diamond-like array according to claim 4, wherein the diamond nanoneedle array has different heights of diamond-like nanoneedles.
A structural member having a diamond-like array according to claim 1, wherein said base The body is one or more of a metal, a metal alloy, a cemented carbide, stainless steel, a polymer, glass, and silicon.
The structural member with a diamond-like array according to claim 6, wherein when the material of the substrate is stainless steel, polymer, cobalt-based metal alloy, cemented carbide, glass and silicon, the antibacterial diamond-like material The array material further includes a transition metal layer between the substrate and the residual diamond-like coating; the transition metal layer has a thickness of 50 to 500 nm.
A method for preparing a structural member having a diamond-like array, comprising the steps of:

Providing a structural member substrate, and pretreating the substrate;

Depositing the pretreated substrate in a vacuum chamber of a coating apparatus, depositing a diamond-like coating on the pretreated substrate;

The diamond-like carbon coating is etched to obtain a diamond-like nanoneedle array having a tip structure.
The method according to claim 8, wherein the depositing the diamond-like carbon coating is by magnetron sputtering; wherein the step of magnetron sputtering comprises:

Argon gas is introduced into the vacuum chamber and the carbon target is opened for deposition, so that the pressure in the vacuum chamber is 0.5-1.0 Pa, the target power of the carbon target is 1 to 5 kW, and the substrate negative bias is -50 to -200 V. The deposition time is 30 to 600 min.
The preparation method according to claim 8, wherein said depositing said diamond-like diamond The coating is in the form of plasma enhanced chemical vapor deposition; wherein the step of plasma enhanced chemical vapor deposition comprises:

A gaseous carbon source is introduced into the vacuum chamber for deposition, such that the pressure in the vacuum chamber is 0.5-1.0 Pa, the ion source voltage is 50-100 V, the substrate negative bias is -50 to -200 V, and the deposition time is 30-600 min. .
The method according to claim 8, wherein the etching of the diamond-like coating is performed by inductively coupled plasma etching; and the following steps are included:

The diamond-deposited substrate is placed in a cavity of inductively coupled plasma etching using hydrogen, argon, oxygen, helium, nitrogen, gaseous carbon sources, CF 4 , C 4 F 8 and SF 6 One or more of them 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, the power of the plasma is 500 to 3000 W, and the RF power on the substrate stage is 50 to 300 W. The time is 10 to 600 minutes.
The method according to claim 8, wherein the etching of the diamond-like coating is performed by electron cyclotron resonance microwave plasma chemical vapor deposition etching, comprising the following steps:

The substrate deposited with the diamond-like coating is placed in an electron cyclotron resonance microwave plasma chemical vapor deposition apparatus, and hydrogen or a mixed hydrogen gas, a gaseous carbon source, and argon gas are introduced, and the gas pressure is 5-8 mTorr, and the DC negative bias is applied. The pressure is 75 to 230 V, the bias current is 40 to 120 mA, and the etching time is 30 minutes to 6 hours.
The preparation method according to claim 8, wherein the pretreatment comprises solvent ultrasonic cleaning, glow cleaning, and ion etching cleaning.
The preparation method according to claim 13, wherein the ultrasonic cleaning of the solvent is performed in deionized water, acetone, ethanol in sequence for 5-30 min;

The conditions of the glow cleaning are as follows: the substrate after ultrasonic cleaning of the solvent is placed in a vacuum chamber of a deposition apparatus, and argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is 300-500 sccm, and the working pressure is 1.0-1.7 Pa. Pressing -500 ~ -800V, the time of the glow cleaning is 10 ~ 30min;

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 preparation method according to any one of claims 8 to 14, wherein after the pretreatment and before depositing the diamond-like coating, a method further comprises depositing a transition metal layer;

Wherein, 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 to 80 ~ 200A, the substrate bias is -100 ~ -300V, deposition time is 2 ~ 10min.
The method according to claim 15, wherein the transition metal in the transition metal layer is one of Cr, Ti, Ni, Zr, W, Mo, Nb, Ta, Ru, and Pt.