CN106835011A - A kind of structural member with Diamond-like Carbon array and preparation method thereof - Google Patents

Abstract

The invention provides a structure with a diamond-like nanoneedle array, including a substrate and a diamond-like nanoneedle array with a tip structure arranged on the substrate, and the diamond-like nanoneedle array is formed on the substrate by pairing etched on a class of diamond coatings. The structural member with the diamond-like array can generate pressure on the cell wall of the bacteria, pierce the cell wall of the bacteria to stretch and eventually dissolve, leading to the death of the bacteria, effectively destroying the formation of biofilm, and endowing the structural member with significant antibacterial properties. The invention also provides a preparation method of the structural member with the diamond-like matrix.

Description

A structural member with a diamond-like matrix and its preparation method

technical field

The invention relates to the field of superhydrophobic materials, in particular to a structural member with a diamond-like array and a preparation method thereof.

Background technique

Biomaterials, especially biomaterials used in medical implants (such as automatic implantable cardiac defibrillators, urinary catheters, etc.) and surgical instruments, must meet various requirements for clinical use due to their direct contact with human tissues. In addition to having good physical, chemical and mechanical properties of general materials, they must also have antimicrobial properties to avoid bacterial colonization, which can lead to the formation of biofilms on the surface of equipment and bacterial infection. Biofilm is a colony aggregate formed by the extracellular polymers secreted by microorganisms in response to changes in the external environment and aggregated on the surface of the medium. The formation of biofilm will increase the drug resistance of bacteria and increase the difficulty of clinical treatment. Therefore, it is generally necessary to modify the surface of medical metal and ceramic materials to provide their antibacterial properties.

Diamond-like carbon (DLC) is an amorphous carbon material containing sp ² and sp ³ bonding characteristics, which has high hardness, low friction, high thermal conductivity, high light transmittance, strong chemical inertness and good With excellent properties such as biocompatibility, DLC films have broad application prospects in optical windows, cutting tools, molds and other parts, biomedical devices and other fields. DLC coating is used as a surface modification layer of medical implant materials, and its main advantages are as follows: ①The adaptability of DLC coating mechanical strength and implant materials not only ensures the firm combination of coatings and medical implant materials , and enhance the support strength of the loading part of the implant; ②The excellent wear and corrosion resistance of the high-density DLC coating not only improves the corrosion and wear resistance of the implant material in the bio-mechanical interactive environment, but also effectively Shield the diffusion of metal ions to surrounding tissues and blood, thereby inhibiting the dissolution of harmful metal ions into biological tissues and preventing tissue damage caused by their toxic reactions to biological tissues, prolonging the service life of medical materials; ③Low toxicity and high chemical stability Due to its adjustable surface and interface properties, the DLC coating can adapt to the implant service environment, reduce the human body's rejection of medical implant materials and improve its compatibility with biological tissues. However, there is no report that a single DLC coating can have antibacterial properties.

Contents of the invention

In view of this, the first aspect of the present invention provides a structural member with a diamond-like array, which first deposits a layer of diamond-like coating on the substrate, and then etches it to form a needle-like Diamond-like nanoneedle arrays with tip structures. The structural member with the diamond-like array has good antibacterial performance, and is used to solve the problem of weak or almost no antibacterial performance of the diamond-like coating in the prior art.

In a first aspect, the present invention provides a structure with a diamond-like nanoneedle array, including a substrate and a diamond-like nanoneedle array with a tip structure arranged on the substrate, and the diamond-like nanoneedle array is formed by pairing A type of diamond coating is etched on the substrate.

Preferably, a residual diamond-like coating is further provided between the substrate and the array of diamond-like nanoneedles, and the array of diamond-like nano-needles 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 thickness of the residual diamond-like coating is 100 nm-3 μm. The existence of the residual diamond-like coating is more conducive to improving the bonding force between the substrate and the diamond-like nanoneedle array.

Preferably, the diamond-like nanoneedles in the diamond nanoneedle array have a cone-shaped structure, the aspect ratio of the diamond-like nanoneedles is 20-80, the diameter of the tip is 10-100 nm, and the diameter of the bottom is 30 nm-2 μm. The needle density is 10 ⁴ to 10 ⁹ ·cm ^-2 .

Wherein, the aspect ratio refers to the ratio of the height of the nanoneedle to the diameter corresponding to half the height of the nanoneedle. Obviously, the base diameter should not be smaller than the tip diameter.

In the present application, in the diamond nanoneedle array, the diamond-like nanoneedles may have a uniform height, or may be nanoneedles with different heights, the height of which varies between 10 nm and 10 μm. For example, nanoneedles with a height of less than 100 nm and nanoneedles with a height of 0.8-9 μm may exist at the same time.

Further, the diamond-like nanoneedles have a height of 400 nm-10 μm. The height of the diamond-like nanoneedles is distributed in a gradient.

In the present application, the size of the diamond-like nanoneedles is similar to that of bacteria, and the aspect ratio is high. The size of the diamond-like nanoneedles can be completely the same or not, and there are certain height changes. The aspect ratio of the diamond-like nanoneedle is 30-60 (preferably 35-55, 40-50); the diameter of the tip is 10-50nm or 60-100nm; the diameter of the bottom is 800nm-2μm or 200-700nm or 30 ~200nm. The needle density may be 10 ⁵ to 10 ⁹ ·cm ^-2 , for example, 10 ⁶ to ×10 ⁹ ·cm ^-2 , 10 ⁸ ·cm ^-2 . The antibacterial performance and mammalian biocytocompatibility of the antibacterial diamond-like array material can be optimized by adjusting the size and density of the diamond-like nanoneedles.

Preferably, the substrate is one or more of metal, metal alloy, hard alloy, stainless steel, polymer, glass and silicon, but not limited thereto. Especially commonly used implant materials, such as titanium alloy TC4 and so on.

Wherein, the metal may be selected from any one of titanium Ti, nickel Ni, molybdenum Mo, niobium Nb, tantalum Ta, ruthenium Ru, and platinum Pt. The metal alloy can be a titanium-based alloy, a cobalt-based alloy (such as a cobalt-chromium alloy), a Ni-Ti alloy, a nickel-based alloy; the hard alloy can be a tungsten carbide-based hard alloy, a titanium carbide-based hard alloy, One of titanium carbonitride-based cemented carbide and chromium carbide-based cemented carbide.

Preferably, when the material of the substrate is medical stainless steel, polymer, cobalt-based metal alloy, hard alloy, glass and silicon, the antibacterial diamond array material also includes a transition metal layer, and the transition metal A layer is located between the substrate and the residual diamond-like coating.

Further, the thickness of the transition metal layer is 50-500 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, and Pt.

In the present application, if the material of the substrate itself is a transition metal or a metal alloy with a small difference in coefficient of thermal expansion (such as titanium Ti, nickel Ni, niobium Nb, tantalum Ta; when titanium-based alloys, Ni-Ti alloys, and nickel-based alloys), Directly depositing a diamond-like coating on the surface of the substrate can make it firmly bonded to the surface of the substrate, and then etch to obtain the array. If the substrate is not a transition metal, it is necessary to deposit a transition metal layer on the substrate first, and then deposit a diamond-like coating on the basis of the transition metal layer to improve the firm bonding of the diamond-like coating to the substrate. .

The structural member with a diamond-like nanoneedle array provided by the first aspect of the present invention includes a substrate and a diamond-like nanoneedle array with a tip structure arranged on the surface of the substrate, and the diamond-like nanoneedle array is formed on the surface of the substrate layer by pairing The diamond-like carbon coating is obtained by etching. The diamond-like nanoneedle array can not only generate pressure on the cell wall of the bacteria, but also pierce the cell wall of the bacteria to stretch and finally dissolve, leading to the death of the bacteria, effectively destroying the formation of biofilm, and endowing the diamond-like coating with remarkable antibacterial properties. 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, beneficial to human health.

In a second aspect, the present invention provides a method for preparing a structural member with a diamond-like array, comprising the following steps:

providing a substrate, and pretreating the substrate;

The pretreated substrate is placed in a vacuum chamber of a coating device, and a diamond-like coating is deposited on the pretreated substrate;

The diamond-like coating is etched to obtain a diamond-like nanoneedle array with a pointed structure.

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

In one embodiment of the present invention, ultrasonic cleaning may be performed first, and then the ultrasonically cleaned substrate is placed in a vacuum chamber of a deposition device for glow cleaning and then ion etching cleaning. This can better ensure the cleanliness of the workpiece surface to be treated.

Wherein, the ultrasonic cleaning is performed in deionized water, acetone, and ethanol in sequence for 5-30 minutes. After ultrasonic cleaning, the substrate needs to be blown dry before other pretreatments.

Wherein, both the glow cleaning and the ion etching cleaning need to be performed at a vacuum degree below 5.0×10 ⁻³ Pa.

Specifically, the conditions of the glow cleaning are as follows: argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is 300-500 sccm, the working pressure is 1.0-1.7Pa, and the substrate bias voltage is -500--800V. The time is 10-30 minutes.

Specifically, the conditions for ion etching and cleaning are: turn on the ion source, the ion source voltage is 50-90V; the argon gas flow rate is 70-300 sccm, the working pressure is 0.5-1.2Pa, and the substrate bias voltage is -100--800V ; The ion etching cleaning time is 10-30 minutes.

Preferably, when the material of the substrate is medical stainless steel, polymer, cobalt-based alloy, cemented carbide, glass and silicon, after the pretreatment and before depositing the diamond-like coating, a transition process is also included. metal layer.

Further, the step of depositing the transition metal layer includes: introducing argon gas into the vacuum chamber, adjusting the pressure of the vacuum chamber to 0.2-1.3 Pa, turning on the transition metal arc target, performing arc deposition of the metal transition layer, and controlling the target current 80~200A, substrate bias voltage is -100~-300V, deposition time is 2~10min.

Further, the thickness of the transition metal layer is 50-500 nm.

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

Wherein, the method for depositing the diamond-like coating includes magnetron sputtering, hot wire chemical vapor deposition (HFCVD), plasma-enhanced chemical vapor deposition, or other conventional methods for preparing the diamond-like coating.

In one embodiment of the present invention, the diamond-like carbon coating is deposited by means of magnetron sputtering, specifically, including: passing argon gas into the vacuum chamber and opening the carbon target for deposition, so that the pressure in the vacuum chamber is 0.5-1.0Pa, the target power of the carbon target is 1-5kW, the substrate negative bias is -50--200V, and the deposition time is 30-600min.

In one embodiment of the present invention, the diamond-like carbon coating is deposited by means of plasma-enhanced chemical vapor deposition, specifically, including: feeding a gaseous carbon source into a vacuum chamber for deposition, so that the pressure in the vacuum chamber is 0.5 ~1.0Pa, the ion source voltage is 50~100V, the substrate negative bias voltage is -50~-200V, and the deposition time is 30~600min. Gaseous carbon sources include methane, acetylene, acetone and the like. At this time, the thickness of the diamond-like coating is 500 nm-10 μm.

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

Further, the conditions of the ICP etching are: the substrate deposited with the diamond-like coating is placed in an inductively coupled plasma etching (ICP) chamber, and hydrogen, argon, oxygen, helium, nitrogen, gaseous One or more of carbon source, CF ₄ , C ₄ F ₈ and SF ₆ is the reaction gas, the flow rate of the reaction gas is 5-200sccm, the reaction pressure is 0.1-10Pa, and the power supply P _ICP of the ICP is 500-3000W , the radio frequency power P _rf on the substrate table is 50-300W, and the etching time is 10-600min. At this time, the thickness of the etched diamond-like carbon coating is 400 nm˜10 μm.

In the present application, the power supply 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 (substrate), and P _rf determines the etching process The proportion of physical bombardment plays a key role in the etching orientation selectivity and rate. The control of the morphology of the final etched structure can be realized mainly by controlling P _ICP and P _rf .

Further, the step of ECR-MWPCVD etching includes: placing the substrate deposited with the diamond-like coating in an electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MWPCVD) device, feeding hydrogen, gaseous carbon source and One or more of argon gas is used as the reaction gas, the gas pressure is 5-8mTorr, the DC negative bias voltage is 75-230V, the bias current is 40-120mA, and the etching time is 30 minutes-6 hours. Wherein, the gaseous carbon source may be a gaseous carbon source such as methane, acetylene, acetone, etc., preferably methane. At this time, at this time, the thickness of the etched away diamond-like coating is 400 nm˜10 μm.

Preferably, during the ECR-MWPCVD etching, the gas fed is hydrogen alone, or a mixed gas of hydrogen and gaseous carbon source, or a mixed gas of hydrogen and argon, or hydrogen, gaseous carbon source and hydrogen formed gas mixture.

In addition, the diamond-like carbon coating can also be etched by a double-bias assisted HFCVD etching method to form a diamond-like nano-needle array.

The second aspect of the present invention provides a method for preparing a structural member with a diamond-like array, by first depositing a layer of diamond-like coating on the substrate, and then etching it to form a needle-like tip structure The diamond-like nanoneedle array has better anti-bacterial adhesion and killing bacteria functions. The preparation method is simple and easy to operate, can form a large-area diamond-like nanoneedle array with sharp tips, and is convenient for commercial application.

The advantages of the present invention will be partly clarified in the following description, and part of them will be obvious from the description, or can be known through the implementation of the embodiments of the present invention.

Description of drawings

Fig. 1 is the structural representation of the structure member that has diamond-like array that the embodiment of the present invention 1, 2 makes;

Fig. 2 is the schematic structural view of the structural member with diamond-like arrays obtained in Example 3-5 of the present invention;

FIG. 3 shows the antibacterial performance test results of the structural members with diamond-like arrays prepared in Examples 4 and 5 of the present invention and Comparative Example 1. FIG.

detailed description

The following description is a preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications are also considered Be the protection scope of the present invention.

Example 1:

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

(1) Substrate pretreatment:

Cobalt-chromium alloy is provided as the substrate. First, the substrate is ultrasonically cleaned with distilled water for 10 minutes, then ultrasonically cleaned with acetone and absolute ethanol for 20 minutes, and then the substrate is dried with nitrogen and placed in a blast drying oven at 100 ° C. ;

Place the above substrate in the vacuum chamber of the multifunctional ion coating equipment (V-Tech MF610/610), first evacuate the vacuum chamber to a background vacuum of 5.0×10 ^-3 Pa, and open the main valve of the argon gas cylinder , pressure reducing valve, ion source valve, arc valve and target valve and mass flowmeter feed argon into vacuum chamber to carry out glow cleaning to substrate, wherein, the condition of glow cleaning is: argon gas flow rate 300sccm, working pressure is 1.0 Pa, the substrate bias is -800V, the substrate is glow-cleaned, and the cleaning time is 10min; after the glow cleaning is completed, the ion source is turned on to perform ion bombardment cleaning on the sample. The flow rate of argon gas is 300sccm, the working pressure of argon gas is 1.2Pa, the base bias voltage is -800V; the cleaning time is 10min;

(2) Deposition of the transition metal layer: After the above-mentioned ion etching cleaning is completed, argon gas is introduced into the vacuum chamber, the flow rate of the argon gas is adjusted so that the pressure of the vacuum chamber is 1.3Pa, the transition metal arc target is turned on, the target current is 100A, the substrate The bias voltage was -300V, and the metal transition layer was deposited by arc ion plating, and the deposition time was 3 minutes; wherein, pure Ti was used as the arc target in this embodiment, and the thickness of the obtained Ti layer was 80 nm.

(3) Diamond-like layer (DLC) deposition: On the transition metal layer obtained in the previous step, DLC is deposited by magnetron sputtering, argon gas is introduced into the vacuum chamber and a carbon target (specifically, a pure graphite target) is turned on. , adjust the argon flow to make the pressure in the vacuum chamber 0.6Pa, the carbon target power 5kW, the substrate negative bias voltage -30V, and the deposition time 1.5h; wherein, the thickness of the DLC layer is 2.5μm;

(4) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, turn off the multifunctional ion coating equipment (V-TechMF610/610), and wait until the temperature of the substrate drops to room temperature, place the substrate in electron cyclotron resonance microwave plasma chemical vapor deposition In the system (ECR-MWPCVD), vacuumize to 10 ^-5 Pa, then refill hydrogen to 7mTorr, turn on the ECR microwave plasma mode, and the magnetic field provided by the external electromagnetic coil has a strength of 875 gauss in the ECR area, and the reaction is carried out under the following conditions Ion etching: feed hydrogen and methane, methane/hydrogen volume ratio: 3%/97%, total gas flow: 20sccm, make the gas pressure 6.6mTorr, the DC negative bias loaded on the substrate table is -220V, and the bias current is 80mA, the etching time is 2 hours, after the etching is completed, turn off the bias voltage, microwave power supply, electromagnetic coil power supply, and turn off the gas to obtain the diamond-like nanoneedle array; wherein, the thickness of the etched DLC layer (that is, the diamond-like nanometer The needle height) is 2 μm, the thickness of the remaining DLC layer is 500 nm; the diamond-like nanoneedles have an aspect ratio of 50, a tip diameter of 50 nm, a base diameter of 200 nm, and a needle density of ~10 ⁸ cm ^-2 .

Example 2:

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

(1) Substrate pretreatment:

Provide a polyetheretherketone (PEEK) substrate as a substrate. First, use distilled water to ultrasonically clean the substrate for 10 minutes, then use acetone and absolute ethanol to ultrasonically clean it for 20 minutes, and then blow dry the substrate with nitrogen, and put it in the air to dry. Dry in oven at 80°C;

Put the above substrate in the multifunctional ion coating equipment (V-Tech MF610/610), vacuumize 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 flowmeter feeds argon gas into the vacuum chamber to perform glow cleaning on the substrate. The conditions for glow cleaning are to feed argon gas into the vacuum chamber, the flow rate of argon gas is 400 sccm, the working pressure is 1.4Pa, and the substrate bias voltage is -500V. , perform glow cleaning on the substrate, and the cleaning time is 30min; after the glow cleaning is completed, turn on the ion source to perform ion bombardment cleaning on the sample, and the ion etching cleaning conditions are: the ion source voltage is 50V, the flow rate of argon gas is 70 sccm, The working air pressure is 0.5Pa, the base bias voltage is -100V; the cleaning time is 30min;

(2) Deposition of transition metal layer: After the above-mentioned ion etching cleaning is completed, argon gas is introduced into the vacuum chamber, the flow rate of argon gas is adjusted (the flow rate is 50-400 sccm) so that the pressure of the vacuum chamber is 1.0 Pa, and the transition metal arc target is turned on , the target current is 150A, the substrate bias is -200V, the metal transition layer is deposited by arc ion plating, and the deposition time is 10min; wherein, in this embodiment, pure Ti is used as the arc target, and the thickness of the obtained Ti layer is 500nm.

(3) Diamond-like layer (DLC) deposition: on the transition metal layer obtained in the previous step, the deposition of DLC is carried out by means of plasma enhanced chemical vapor deposition (PECVD), and acetylene and argon are introduced into the vacuum chamber to adjust the vacuum The pressure in the chamber is 1.0Pa, the ion source voltage is 100V, the substrate negative bias is -50V, and the deposition time is 10h; the thickness of the DLC layer is 10μm;

(4) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, turn off the multifunctional ion coating equipment (V-TechMF610/610), and wait for the temperature of the substrate to drop to room temperature, and place the substrate in inductively coupled plasma etching (ICP ) In the cavity of the equipment, plasma etching is performed on the substrate. The conditions for ICP etching are as follows: oxygen is introduced as the reaction gas, the flow rate of the reaction gas is 20sccm, the working pressure is 10Pa, the frequency of ICP is 13.56MHz, and the frequency of ICP is 13.56MHz. The power supply P _ICP is 1000W, the radio frequency power P _rf on the substrate table 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 the diamond-like nanoneedle array is obtained; wherein, the etched The thickness of the DLC layer (that is, the height of the diamond-like nanoneedle) is ~ 9 μm, and the thickness of the remaining DLC layer is 1 μm; the aspect ratio of the diamond-like nanoneedle is ~ 20, the tip diameter is 60 ~ 100nm, and the bottom diameter It is 800nm～1μm, and the needle density is ～10 ⁴ cm ^-2 .

FIG. 1 is a schematic structural view of the antibacterial diamond array material prepared in Examples 1 and 2 of the present invention. In Fig. 1, 101 is a substrate, 102 is a transition metal layer, 1031 is a residual diamond-like layer, 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:

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

(1) Substrate pretreatment:

Provide a Ni-Ti alloy as a substrate. First, use distilled water to ultrasonically clean the substrate for 10 minutes, then use acetone and absolute ethanol to ultrasonically clean it for 20 minutes, then dry the substrate with nitrogen, and put it in a blast drying oven at 120 ° C. drying;

Put the above substrate in the multifunctional ion coating equipment (V-Tech MF610/610), under the condition that the background vacuum degree is 5.0×10 ^-3 Pa, open the main valve of the argon cylinder, the pressure reducing valve and the ion source valve , arc valve, target valve and mass flowmeter feed argon gas into the vacuum chamber to carry out glow cleaning to the substrate, wherein the conditions of glow cleaning are: feed argon gas into the vacuum chamber, the flow rate of argon gas is 500 sccm, and the working pressure is 1.5 Pa, substrate bias -600V, glow cleaning the substrate for 20min; after the glow cleaning, turn on the ion source to perform ion bombardment cleaning on the sample, the ion etching cleaning conditions are: the ion source voltage is 70V, the argon flow rate is 150sccm, The working pressure of argon is 0.9Pa, the substrate bias is -550V; the cleaning time is 20min;

(2) Transition metal deposition: After the above-mentioned ion etching cleaning is completed, argon gas is introduced into the vacuum chamber, and the flow rate of argon gas (50-400 sccm) is adjusted so that the pressure of the vacuum chamber is 1.0 Pa. The transition metal arc target is turned on, and the target current 100A, the substrate bias is -300V, the metal transition layer is deposited by arc ion plating, and the deposition time is 4min; wherein, in this embodiment, pure Ti is used as the arc target, and the thickness of the obtained Ti layer is 100nm.

(3) Diamond-like carbon layer (DLC) deposition: After the above-mentioned ion etching and cleaning, the substrate is placed in a multi-functional ion coating equipment (V-Tech MF610/610), and plasma-enhanced chemical vapor deposition (PECVD) is used. The method is to deposit DLC on the surface of the substrate, pass acetylene and argon into the vacuum chamber, adjust the pressure in the vacuum chamber to 0.9Pa, the ion source voltage to 80V, the substrate negative bias to -100V, and the deposition time to 60min; among them, The thickness of the DLC layer is 0.5 μm;

(4) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, turn off the multifunctional ion coating equipment (V-TechMF610/610), and wait for the temperature of the substrate to drop to room temperature, and place the substrate in inductively coupled plasma etching (ICP ) In the cavity of the equipment, the substrate is etched by plasma. The conditions for ICP etching are as follows: CF ₄ or SF ₆ is introduced 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 power supply P _ICP of ICP is 2000W, the radio frequency power P _rf on the substrate stage is 150W, and the etching time is 50min, after the etching is completed, turn off the ICP source, turn off the gas, and obtain the diamond-like nanoneedle array; wherein, The thickness of the etched DLC layer (i.e. the height of the diamond-like nanoneedle) is 450nm, and the thickness of the remaining DLC layer is 50nm; the aspect ratio of the diamond-like nanoneedle is ~ 10, the tip diameter is 20nm, and the bottom The diameter is 100 nm and the needle density is ~10 ⁹ cm ⁻² .

Example 4:

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

(1) Substrate pretreatment:

Titanium alloy TC4 is provided as the substrate. First, the substrate is ultrasonically cleaned with distilled water for 10 minutes, then ultrasonically cleaned with acetone and absolute ethanol for 20 minutes, and then the substrate is blown dry with nitrogen, and dried in a blast drying oven at 150°C. ;

Put the above substrate in the multifunctional ion coating equipment (V-Tech MF610/610), under the condition that the background vacuum degree is 5.0×10 ^-3 Pa, open the main valve of the argon cylinder, the pressure reducing valve and the ion source valve , arc valve, target valve and mass flowmeter feed argon gas into the vacuum chamber to carry out glow cleaning to the substrate, wherein the conditions of glow cleaning are: feed argon gas into the vacuum chamber, the flow rate of argon gas is 450 sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V; the cleaning time is 20min;

(2) Deposition of diamond-like carbon layer (DLC): After the above-mentioned ion etching cleaning is completed, DLC is deposited on the surface of the substrate by magnetron sputtering, argon gas is introduced into the vacuum chamber and the carbon target (specifically graphite target), adjust the flow of argon gas so that the pressure in the vacuum chamber is 0.8Pa, the power of the carbon target is 1kW, the negative bias voltage of the substrate 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-mentioned DLC layer is completed, turn off the multifunctional ion coating equipment (V-TechMF610/610), and wait until the temperature of the substrate drops to room temperature, and place the substrate in the electron cyclotron resonance microwave plasma chemical vapor phase In the deposition system (ECR-MWPCVD), evacuate to 10 ^-5 Pa, then refill hydrogen to 7mTorr, turn on the ECR microwave plasma mode, and the magnetic field provided by the external electromagnetic coil has a strength of 875 gauss in the ECR area, using the following conditions Reactive ion etching: feed hydrogen gas, gas flow rate: 20sccm, make the gas pressure 8mTorr, the DC negative bias voltage loaded on the substrate table is -150V, the bias current is 40-60mA, the etching time is 120min, after the etching is completed Turn off the bias voltage, microwave power supply, and electromagnetic coil power supply, and turn off the gas to obtain a diamond-like nanoneedle array; wherein, the thickness of the etched DLC layer (that is, the height of the tapered diamond-like nanoneedle) is 800nm to 2.5μm, and the remaining The thickness of the DLC layer is 2.5 μm. The diamond-like nanoneedles obtained in this example have a tip diameter of 10-40 nm, a bottom diameter of 350-750 μm, and a needle density of ~4×10 ⁸ cm ^-2 .

Example 5:

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

(1) Substrate pretreatment:

Titanium alloy TC4 is provided as the substrate. First, the substrate is ultrasonically cleaned with distilled water for 10 minutes, then ultrasonically cleaned with acetone and absolute ethanol for 20 minutes, and then the substrate is blown dry with nitrogen, and dried in a blast drying oven at 150°C. ;

Put the above substrate in the multifunctional ion coating equipment (V-Tech MF610/610), under the condition that the background vacuum degree is 5.0×10 ^-3 Pa, open the main valve of the argon cylinder, the pressure reducing valve and the ion source valve , arc valve, target valve and mass flowmeter feed argon gas into the vacuum chamber to carry out glow cleaning to the substrate, wherein the conditions of glow cleaning are: feed argon gas into the vacuum chamber, the flow rate of argon gas is 450 sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V; the cleaning time is 20min;

(2) Deposition of diamond-like carbon layer (DLC): After the above-mentioned ion etching cleaning is completed, DLC is deposited on the surface of the substrate by magnetron sputtering, argon gas is introduced into the vacuum chamber and the carbon target (specifically graphite target), adjust the flow of argon gas so that the pressure in the vacuum chamber is 0.8Pa, the power of the carbon target is 1kW, the negative bias voltage of the substrate 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-mentioned DLC layer is completed, turn off the multifunctional ion coating equipment (V-TechMF610/610), and wait until the temperature of the substrate drops to room temperature, and place the substrate in the electron cyclotron resonance microwave plasma chemical vapor phase In the deposition system (ECR-MWPCVD), evacuate to 10 ^-5 Pa, then refill hydrogen to 7mTorr, turn on the ECR microwave plasma mode, and the magnetic field provided by the external electromagnetic coil has a strength of 875 gauss in the ECR area, using the following conditions Reactive ion etching: feed hydrogen and argon, argon/hydrogen volume ratio: 45%/55%, total gas flow: 20sccm, make the gas pressure 5mTorr, and the DC negative bias on the substrate table is -200V, The bias current is 40-60mA, and the etching time is 240min. After the etching is completed, turn off the bias voltage, microwave power supply, and electromagnetic coil power supply, and turn off the gas to obtain a diamond-like nanoneedle array; wherein, the thickness of the remaining DLC layer is 500nm. The needle density of the obtained diamond-like nanoneedles is about 1.7×10 ⁸ cm ^-2 , which is divided into two parts, of which a small part of diamond-like nanocones is very small, with a height of less than 100nm, a tip diameter of 10-40nm, and a bottom diameter of The height of most nanocones is 3-4.5 μm, the diameter of the bottom is 100 nm-2 μm, and the diameter of the tip is 10-40 nm.

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

Comparative Example 1

(1) Substrate pretreatment:

Titanium alloy TC4 is provided as the substrate. First, the substrate is ultrasonically cleaned with distilled water for 10 minutes, then ultrasonically cleaned with acetone and absolute ethanol for 20 minutes, and then the substrate is blown dry with nitrogen, and dried in a blast drying oven at 150°C. ;

Put the above substrate in the multifunctional ion coating equipment (V-Tech MF610/610), under the condition that the background vacuum degree is 5.0×10 ^-3 Pa, open the main valve of the argon cylinder, the pressure reducing valve and the ion source valve , arc valve, target valve and mass flowmeter feed argon gas into the vacuum chamber to carry out glow cleaning to the substrate, wherein the conditions of glow cleaning are: feed argon gas into the vacuum chamber, the flow rate of argon gas is 450 sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; The flow rate is 200sccm, the working pressure of argon is 1.0Pa, the substrate bias is -450V; the cleaning time is 20min;

(2) Deposition of diamond-like carbon layer (DLC): After the above-mentioned ion etching cleaning is completed, DLC is deposited on the surface of the substrate by magnetron sputtering, argon gas is introduced into the vacuum chamber and the carbon target (specifically graphite target), adjust the flow of argon gas so that the pressure in the vacuum chamber is 0.8Pa, the power of the carbon target is 1kW, the negative bias voltage of the substrate is -100V, and the deposition time is 5 hours; wherein, the thickness of the DLC layer is 5 μm;

Effect example

In order to verify that the material prepared by the present invention has antibacterial properties, the present invention also provides effect examples. The antibacterial diamond array materials prepared in Examples 4 and 5 of the present invention were tested for antibacterial performance respectively, and a complete DLC layer with a thickness of 5 μm was deposited on the titanium alloy TC4 as Comparative Example 1, and the results are shown in Figure 3 , Pseudomonas aeruginosa is respectively acted on comparative example 1 (titanium alloy TC4+ complete DLC layer), and on the diamond-like nanoarrays obtained in Example 4 and Example 5, (a) is the Pseudomonas aeruginosa attached to substrates with different surface morphology The total number of bacillus bacteria; (b) is the percentage of dead Pseudomonas aeruginosa after 1 hour. From (b) in Fig. 3, it can be seen that the complete diamond-like coating (comparative example 1) and the obtained diamond-like nanoneedles of Examples 4 and 5 have certain antibacterial effects, but the obtained diamond-like needles of Examples 4 and 5 have certain antibacterial effects. The bactericidal effect of the diamond nanoneedle array is obviously much better than that of the ordinary complete diamond-like coating without etching. Comparing the etched nanoneedle arrays under different conditions, it can be seen that the diamond-like nanoneedle array (nanoneedles with different heights) prepared in Example 5 has a better bactericidal effect.

The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. A structure with a diamond-like nano-needle array, characterized in that it includes a substrate and a diamond-like nano-needle array with a tip structure arranged on the substrate, and the diamond-like nano-needle array is formed on the It is obtained by etching a kind of diamond coating on the above-mentioned substrate. 2. The structural member with diamond-like arrays as claimed in claim 1, characterized in that, a residual diamond-like coating is also arranged between the substrate and the diamond-like nanoneedle array, and the diamond-like nanometer The needle array is formed on the surface of the residual diamond-like coating; the thickness of the residual diamond-like coating is 100nm-3μm. 3. as claimed in claim 1, there is the structure of diamond-like nanoneedle array, it is characterized in that, the diamond-like nanoneedle in described diamond nanoneedle array is a cone structure, and the aspect ratio of described diamond-like nanoneedle 20-80, tip diameter 10-100nm, base diameter 30nm-2μm, needle density 10 ⁴ -10 ⁹ ·piece·cm ^-2 . 4 . The structural member with a diamond-like carbon array according to claim 3 , wherein the height of the diamond-like nanoneedles is between 10 nm and 10 μm. 5. The structural member with a diamond-like matrix as claimed in claim 1, wherein the substrate is one or more of metal, metal alloy, hard alloy, stainless steel, polymer, glass and silicon . 6. The structural member with a diamond-like array as claimed in claim 5, wherein when the material of the substrate is stainless steel, polymer, cobalt-based metal alloy, cemented carbide, glass and silicon, the The antibacterial diamond-like array material also includes a transition metal layer, the transition metal layer is located between the substrate and the residual diamond-like coating; the thickness of the transition metal layer is 50-500nm. 7. A method for preparing a structural member with a diamond-like array, comprising the following steps: providing a structural member matrix, and performing pretreatment on the matrix; The pretreated substrate is placed in a vacuum chamber of a coating device, and a diamond-like coating is deposited on the pretreated substrate; The diamond-like coating is etched to obtain a diamond-like nanoneedle array with a pointed structure. 8. preparation method as claimed in claim 7 is characterized in that, the method for described deposition described diamond-like coating comprises magnetron sputtering or plasma enhanced chemical vapor deposition; Wherein, the step of magnetron sputtering includes: feeding argon gas into the vacuum chamber and turning on the carbon target for deposition, so that the pressure in the vacuum chamber is 0.5-1.0 Pa, and the target power of the carbon target is 1-1.0 Pa. 5kW, substrate negative bias voltage is -50~-200V, deposition time is 30~600min; Wherein, the step of plasma-enhanced chemical vapor deposition includes: feeding a gaseous carbon source into the vacuum chamber for deposition, making the pressure in the vacuum chamber 0.5-1.0 Pa, the ion source voltage 50-100V, and the substrate negatively biased The voltage is -50~-200V, and the deposition time is 30~600min. 9. The preparation method according to claim 7, wherein the etching of the diamond-like coating adopts inductively coupled plasma etching or electron cyclotron resonance microwave plasma chemical vapor deposition etching; Wherein, the step of inductively coupled plasma etching includes: placing the substrate deposited with the diamond-like coating in the cavity of inductively coupled plasma etching, using hydrogen, argon, oxygen, helium, nitrogen, gaseous One or more of the carbon source, CF ₄ , C ₄ F ₈ and SF ₆ is the reaction gas, the flow rate of the reaction gas is 5-200sccm, the reaction pressure is 0.1-10Pa, and the power of the plasma is 500-3000W. The RF power on the substrate table is 50-300W, and the etching time is 10-600min; Wherein, the step of electron cyclotron resonance microwave plasma chemical vapor deposition etching includes: placing the substrate deposited with the diamond-like coating in the electron cyclotron resonance microwave plasma chemical vapor deposition equipment, feeding hydrogen or feeding mixed Hydrogen gas, gaseous carbon source and argon gas, the gas pressure is 5-8mTorr, the DC negative bias voltage is 75-230V, the bias current is 40-120mA, and the etching time is 30 minutes-6 hours. 10. The preparation method according to any one of claims 7-9, further comprising depositing a transition metal layer after the pretreatment and before depositing the diamond-like coating; Wherein, the step of depositing the transition metal layer comprises: feeding argon gas 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, base bias voltage is -100~-300V, deposition time is 2~10min.