CN106835011B - A kind of structural member and preparation method thereof with diamond-like array - Google Patents

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

A kind of structural member with diamond-like carbon array and preparation method thereof

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 those used in medical implants (such as automatic implantable cardiac defibrillators, urinary catheters, etc.) and surgical instruments, need to meet various requirements for clinical use due to their direct contact with human tissue. In addition to the good physical, chemical and mechanical properties of general materials, they must also be antibacterial to prevent bacterial colonization, which can lead to the formation of biofilms on equipment surfaces and bacterial infection. Biofilms are colony aggregates formed by the extracellular polymers secreted by microorganisms themselves in response to changes in the external environment on the surface of the medium. The formation of biofilms will increase the drug resistance of bacteria and increase the difficulty of clinical treatment. Therefore, surface modification of medical metals and ceramic materials is generally required to provide their antibacterial properties.

Diamond-like carbon (DLC) is an amorphous carbon material containing sp ² and sp ³ bonding features, with high hardness, low friction, high thermal conductivity, high light transmittance, strong chemical inertness and good Due to its excellent properties such as biocompatibility, DLC films have broad application prospects in optical windows, tools, molds and other parts, biomedical devices and other fields. As a surface modification layer of medical implant materials, DLC coating has the main advantages as follows: ① The adaptability of DLC coating mechanical strength and implant material not only ensures the firm combination of coating and medical implant material , and enhances the support strength of the implant load part; ② The 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 interaction 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, extending the service life of medical materials; ③ Low toxicity and high chemical stability Because of its tunable surface 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.

SUMMARY OF THE INVENTION

In view of this, the first aspect of the present invention provides a structural member with a diamond-like carbon array, which is formed by depositing a layer of diamond-like carbon coating on a substrate and then etching it to form a diamond-like carbon-like structure Array of diamond nanoneedles. The structural member with the diamond-like carbon array has good antibacterial properties, and is used to solve the problem that the diamond-like carbon coating has weak bactericidal properties or almost no antibacterial properties in the prior art.

In a first aspect, the present invention provides a structural member having a diamond-like carbon array, comprising a substrate and a diamond-like nanoneedle array with a tip structure disposed on the substrate, wherein the diamond-like nanoneedle array is formed on the A type of diamond coating on the substrate is obtained by etching.

Preferably, a residual diamond-like carbon coating is further disposed between the matrix and the diamond-like nano-needle array, and the diamond-like carbon nano-needle array is formed on the surface of the residual diamond-like carbon coating. The residual DLC coating is a complete coating without DLC nanoneedles. Further, the thickness of the residual diamond-like carbon coating is 100 nm˜3 μm. The existence of the residual diamond-like carbon coating is more conducive to improving the bonding force between the matrix and the diamond-like nano-needle array.

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

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

In the present application, in the diamond-like nano-needle array, the height of the diamond-like nano-needles may be a uniform height, or may be nano-needles with different heights, and the heights may vary from 10 nm to 10 μm. For example, nanoneedles with a height of less than 100 nm and nanoneedles with a height of 0.8-9 μm may coexist.

Further, the height of the diamond-like nanoneedles is 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 nano-needles may be exactly the same, or may not be exactly the same, with certain height changes. The aspect ratio of the diamond-like nanoneedles is 30-60 (preferably 35-55, 40-50); the diameter of the tip is 10-50 nm or 60-100 nm; the diameter of the bottom is 800-2 μm or 200-700 nm 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 properties and mammalian biocompatibility of the antibacterial diamond-like carbon array material can be optimized by adjusting the size and density of the diamond-like nano-needles.

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

Wherein, the metal can 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 titanium-based alloy, cobalt-based alloy (such as cobalt-chromium alloy), Ni-Ti alloy, nickel-based alloy; the cemented carbide can be tungsten carbide-based cemented carbide, titanium carbide-based cemented carbide, 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, cemented carbide, glass and silicon, the structural member with the diamond-like carbon array further comprises a transition metal layer, 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 this application, if the material of the substrate itself is a transition metal or a metal alloy with 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), By depositing a diamond-like coating directly on the surface of the substrate, it can be firmly bonded to the surface of the substrate, and then etched to obtain an array. If the substrate is not a transition metal, a transition metal layer needs to be deposited on the substrate first, and then a diamond-like carbon coating is deposited on the basis of the transition metal layer, so as to improve the firm bonding of the diamond-like carbon coating to the substrate.

The first aspect of the present invention provides a structural member with a diamond-like carbon array including a substrate and a diamond-like nanoneedle array with a tip structure disposed on the surface of the substrate. The diamond-like nanoneedle array The diamond coating is etched. The diamond-like nanoneedle array can not only generate pressure on the cell wall of bacteria, but also puncture the cell wall of bacteria to stretch and eventually dissolve, leading to bacterial death, effectively destroying the formation of biofilm, and endowing the diamond-like carbon coating with significant 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, preventing Bacterial infection is good for human health.

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

providing a substrate, and pre-processing the substrate;

placing the pretreated substrate in a vacuum chamber of the coating equipment, and depositing a diamond-like coating on the pretreated substrate;

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

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

In an 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 apparatus, and glow cleaning is performed first, followed by 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 min. After ultrasonic cleaning, the substrate needs to be dried before other pretreatments.

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

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

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

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, it also includes depositing a transition metal layer.

Further, the step of depositing the transition metal layer includes: 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 is 80-200A, the substrate bias is -100--300V, and the 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 filament 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 method of magnetron sputtering is used to deposit the diamond-like carbon coating, which specifically 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 0.5～1.0Pa, the target power of the carbon target is 1～5kW, the negative bias voltage of the substrate is -50～-200V, and the deposition time is 30～600min.

In an embodiment of the present invention, the plasma-enhanced chemical vapor deposition method is used to deposit the diamond-like carbon coating. Specifically, the method includes: 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 negative bias voltage of the substrate is -50～-200V, and the deposition time is 30～600min. The gaseous carbon source may 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 is 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: placing the substrate on which the diamond-like carbon coating is deposited in an inductively coupled plasma etching (ICP) cavity, using hydrogen, argon, oxygen, helium, nitrogen, gaseous One or more of the carbon source, CF ₄ , C ₄ F ₈ and SF ₆ is a reaction gas, the flow rate of the reaction gas is 5～200sccm, the reaction gas pressure is 0.1～10Pa, and the power P _ICP of the ICP is 500～3000W , the radio frequency power P _rf on the substrate stage 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 this application, the 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 (substrate), and P _rf determines the etching process The proportion of physical bombardment in the medium plays a key role in the selectivity and rate of etching orientation. The control of the morphology of the final etched structure can be achieved mainly by controlling P _ICP and P _rf .

Further, the step of the ECR-MWPCVD etching includes: placing the substrate on which the diamond-like carbon coating is deposited into an electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MWPCVD) equipment, feeding hydrogen, a gaseous carbon source and One or more of the argon gases are used as reactive gases, 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-6 hours. Wherein, the gaseous carbon source may be a gaseous carbon source such as methane, acetylene, acetone, etc., preferably methane. At this time, the thickness of the diamond-like carbon coating layer etched away is 400 nm to 10 μm.

Preferably, during the ECR-MWPCVD etching, the gas introduced 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 composed of mixed gases.

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

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

Advantages of the present invention will be set forth in part in the description which follows, in part will be apparent from the description, or may be learned by practice of embodiments of the invention.

Description of drawings

1 is a schematic structural diagram of a structural member with a diamond-like carbon array prepared in Embodiments 1 and 2 of the present invention;

2 is a schematic structural diagram of a structural member with a diamond-like carbon array prepared in Example 3-5 of the present invention;

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

Detailed ways

The following description is the 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, several improvements and modifications can also be made, and these improvements and modifications are also regarded as It is the protection scope of the present invention.

Example 1:

A preparation method of a structural member with a diamond-like carbon array, comprising:

(1) Matrix pretreatment:

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

The above-mentioned substrate was placed in the vacuum chamber of the multi-functional ion coating equipment (V-Tech MF610/610), the vacuum chamber was first evacuated to a background vacuum of 5.0×10 ^-3 Pa, and the main valve of the argon cylinder was opened. , the pressure reducing valve, the ion source valve, the arc valve and the target valve and the mass flow meter pass argon into the vacuum chamber to perform glow cleaning on the substrate, wherein, the conditions of the glow cleaning are: the argon flow rate is 300sccm, and the working pressure is 1.0 Pa, the substrate bias voltage is -800V, the substrate is subjected to glow cleaning, 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, and the ion etching cleaning conditions are: the ion source voltage is 90V, The flow rate of argon gas is 300sccm, the working pressure of argon gas is 1.2Pa, the substrate bias voltage is -800V; the cleaning time is 10min;

(2) transition metal layer deposition: after the above-mentioned ion etching and cleaning finishes, feed argon into the vacuum chamber, adjust the argon flow so that the pressure of the vacuum chamber is 1.3Pa, open the transition metal arc target, 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; in this example, pure Ti was used as the arc target, and the thickness of the obtained Ti layer was 80 nm.

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

(4) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, the multifunctional ion coating equipment (V-TechMF610/610) is turned off, and when the temperature of the substrate is lowered to room temperature, the substrate is placed in electron cyclotron resonance microwave plasma chemical vapor deposition In the system (ECR-MWPCVD), the vacuum was evacuated to 10 ^-5 Pa, and then the hydrogen gas was recharged to 7mTorr, the ECR microwave plasma mode was turned on, and the magnetic field provided by the external electromagnetic coil had a strength of 875 Gauss in the ECR region, and the reaction was carried out under the following conditions Ion etching: hydrogen and methane were introduced, the volume ratio of methane/hydrogen: 3%/97%, the total gas flow: 20sccm, the gas pressure was 6.6mTorr, the negative DC bias loaded on the substrate table was -220V, and the bias current was 80mA, the etching time is 2 hours, turn off the bias voltage, the microwave power supply, the electromagnetic coil power supply after the etching is completed, and turn off the gas to obtain the diamond-like nano-needle array; The height of the needles) was 2 μm, the thickness of the residual DLC layer was 500 nm; the diamond-like nanoneedles had an aspect ratio of 50, a tip diameter of 50 nm, a bottom diameter of 200 nm, and a needle density of ~10 ⁸ cm ⁻² .

Example 2:

A preparation method of a structural member with a diamond-like carbon array, comprising:

(1) Matrix pretreatment:

Provide a polyetheretherketone (PEEK) substrate as the substrate, first ultrasonically clean the substrate with distilled water for 10 min, then ultrasonically clean it with acetone and absolute ethanol for 20 min, and then dry the substrate with nitrogen, and put it into blast drying Dry at 80℃ in the box;

The above-mentioned substrate was placed in a multifunctional ion coating equipment (V-Tech MF610/610), evacuated to 5.0×10 ^{- 3} Pa, and the main valve of the argon cylinder, pressure reducing valve, ion source valve, arc valve and target valve were opened. And the mass flow meter feeds argon gas into the vacuum chamber to perform glow cleaning on the substrate, wherein the conditions for glow cleaning are to feed argon gas into the vacuum chamber, the argon gas flow rate is 400sccm, 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, turn on the ion source to clean the sample by ion bombardment. The working air pressure is 0.5Pa, the substrate bias is -100V; the cleaning time is 30min;

(2) Deposition of transition metal layer: after the above-mentioned ion etching and cleaning is completed, argon gas is introduced into the vacuum chamber, the flow rate of argon gas is adjusted (the flow rate is 50～400sccm) so that the pressure of the vacuum chamber is 1.0Pa, and the transition metal arc target is turned on. , the target current is 150A, the substrate bias is -200V, and 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 carbon layer (DLC) deposition: On the transition metal layer obtained in the previous step, the DLC is deposited by means of plasma enhanced chemical vapor deposition (PECVD), and acetylene and argon are fed into the vacuum chamber to adjust the vacuum The pressure in the chamber is 1.0Pa, the voltage of the ion source is 100V, the negative bias voltage of the substrate 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, the multifunctional ion coating equipment (V-TechMF610/610) is turned off, and the substrate is placed in inductively coupled plasma etching (ICP) when the temperature of the substrate drops to room temperature. ) in the cavity of the equipment, plasma etching is performed on the substrate, and the conditions for using 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 the ICP is 13.56MHz, the ICP The power supply power P _ICP is 1000W, the radio frequency 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, and the gas is turned off to obtain a diamond-like nanoneedle array; The thickness of the DLC layer (that is, the height of the diamond-like nanoneedles) is ~9 μm, and the thickness of the residual DLC layer is 1 μm; the aspect ratio of the diamond-like nanoneedles is ~20, the diameter of the tip is 60 to 100 nm, and the diameter of the bottom is 60 to 100 nm. is 800 nm to 1 μm, and the pin density is ~10 ⁴ cm ^-2 .

FIG. 1 is a schematic structural diagram of the antibacterial diamond-like carbon array materials prepared in Examples 1 and 2 of the present invention. In FIG. 1 , 101 is the substrate, 102 is the transition metal layer, 1031 is the residual diamond-like carbon layer, 1031 is the diamond-like carbon nanoneedle array, and the sum of the thicknesses of 1031 and 1032 is the thickness of the initially deposited DLC layer.

Example 3:

A preparation method of a structural member with a diamond-like carbon array, comprising:

(1) Matrix pretreatment:

The Ni-Ti alloy was provided as the substrate. First, the substrate was ultrasonically cleaned with distilled water for 10 min, followed by ultrasonic cleaning with acetone and absolute ethanol for 20 min. Then the substrate was blown dry with nitrogen and placed in a blast drying oven at 120 °C. drying;

The above-mentioned substrate was placed in a multifunctional ion coating equipment (V-Tech MF610/610), and the main valve of the argon 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. , arc valve and target valve and mass flow meter into the vacuum chamber to pass argon to the substrate to carry out glow cleaning, wherein, the conditions of glow cleaning are: enter argon into the vacuum chamber, the argon flow rate is 500sccm, and the working pressure is 1.5 Pa, the substrate bias voltage is -600V, and the substrate is subjected to glow cleaning for 20 minutes; after the glow cleaning is completed, the ion source is turned on to clean the sample by ion bombardment. 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 and cleaning is finished, pass argon gas into the vacuum chamber, adjust the argon gas flow (50～400sccm) to make the pressure of the vacuum chamber be 1.0Pa, open the transition metal arc target, the target current is 100A, the substrate bias is -300V, the metal transition layer is deposited by arc ion plating, and the deposition time is 4min; in this embodiment, pure Ti is used as the arc target, and the thickness of the obtained Ti layer is 100nm.

(3) Deposition of diamond-like carbon layer (DLC): After the above-mentioned ion etching and cleaning, the substrate is placed in a multifunctional ion coating equipment (V-Tech MF610/610), and a plasma-enhanced chemical vapor deposition (PECVD) is used. The DLC deposition was carried out on the surface of the substrate, acetylene and argon were introduced into the vacuum chamber, the pressure in the vacuum chamber was adjusted to 0.9Pa, the voltage of the ion source was 80V, the negative bias voltage of the substrate was -100V, and the deposition time was 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, the multifunctional ion coating equipment (V-TechMF610/610) is turned off, and the substrate is placed in inductively coupled plasma etching (ICP) when the temperature of the substrate drops to room temperature. ) in the cavity of the equipment, the substrate is subjected to plasma etching, and the conditions for using ICP etching are as follows: _CF4 or _SF6 is introduced as the reaction gas, the flow rate of the reaction gas is 40sccm, the working pressure is 10Pa, and the frequency of ICP is 13.56MHz, the power P _ICP of the ICP is 2000W, the radio frequency power P _rf on the substrate stage is 150W, the etching time is 50min, after the etching is completed, the ICP source is turned off, and the gas is turned off to obtain a diamond-like nanoneedle array; wherein, The thickness of the etched DLC layer (that is, the height of the diamond-like nanoneedles) is 450 nm, and the thickness of the remaining DLC layer is 50 nm; the aspect ratio of the diamond-like nanoneedles is ~10, the diameter of the tip is 20 nm, and the bottom of the The diameter is 100 nm and the pin density is ~ ¹⁰⁹ cm ^-2 .

Example 4:

A preparation method of a structural member with a diamond-like carbon array, comprising:

(1) Matrix pretreatment:

Titanium alloy TC4 was provided as the substrate. First, the substrate was ultrasonically cleaned with distilled water for 10 min, followed by ultrasonic cleaning with acetone and absolute ethanol for 20 min. Then the substrate was blown dry with nitrogen, and dried at 150 °C in a blast drying oven. ;

The above-mentioned substrate was placed in a multifunctional ion coating equipment (V-Tech MF610/610), and the main valve of the argon 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. , arc valve and target valve and mass flow meter into the vacuum chamber to pass argon to the substrate to carry out glow cleaning, wherein, the conditions of the glow cleaning are: enter argon into the vacuum chamber, the argon flow rate is 450sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; after glow cleaning, turn on the ion source to clean the sample by ion bombardment, ion etching cleaning conditions are: 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; the cleaning time is 20min;

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

(3) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, the multifunctional ion coating equipment (V-TechMF610/610) is turned off, and the substrate temperature is lowered to room temperature, and the substrate is placed in the electron cyclotron resonance microwave plasma chemical vapor phase In the deposition system (ECR-MWPCVD), the vacuum was evacuated to 10 ^-5 Pa, and then the hydrogen gas was recharged to 7 mTorr, the ECR microwave plasma mode was turned on, and the intensity of the magnetic field provided by the external electromagnetic coil in the ECR region was 875 Gauss, and the following conditions were used to carry out Reactive ion etching: Pass in hydrogen, the gas flow is: 20sccm, the gas pressure is 8mTorr, the negative DC bias 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, 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 nanoneedles) is 800nm～2.5μm, and the residual The thickness of the DLC layer is 2.5 μm. The diameter of the tip of the diamond-like nanoneedles obtained in this example is 10-40 nm, the diameter of the bottom is 350-750 μm, and the needle density is ˜4×10 ⁸ cm ⁻² .

Example 5:

A preparation method of a structural member with a diamond-like carbon array, comprising:

(1) Matrix pretreatment:

Titanium alloy TC4 was provided as the substrate. First, the substrate was ultrasonically cleaned with distilled water for 10 min, followed by ultrasonic cleaning with acetone and absolute ethanol for 20 min. Then the substrate was blown dry with nitrogen, and dried at 150 °C in a blast drying oven. ;

The above-mentioned substrate was placed in a multifunctional ion coating equipment (V-Tech MF610/610), and the main valve of the argon 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. , arc valve and target valve and mass flow meter into the vacuum chamber to pass argon to the substrate to carry out glow cleaning, wherein, the conditions of the glow cleaning are: enter argon into the vacuum chamber, the argon flow rate is 450sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; after glow cleaning, turn on the ion source to clean the sample by ion bombardment, ion etching cleaning conditions are: 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; the cleaning time is 20min;

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

(3) Etching of DLC: After the deposition of the above-mentioned DLC layer is completed, the multifunctional ion coating equipment (V-TechMF610/610) is turned off, and the substrate temperature is lowered to room temperature, and the substrate is placed in the electron cyclotron resonance microwave plasma chemical vapor phase In the deposition system (ECR-MWPCVD), the vacuum was evacuated to 10 ^-5 Pa, and then the hydrogen gas was recharged to 7 mTorr, the ECR microwave plasma mode was turned on, and the intensity of the magnetic field provided by the external electromagnetic coil in the ECR region was 875 Gauss, and the following conditions were used to carry out Reactive ion etching: pass hydrogen and argon, argon/hydrogen volume ratio: 45%/55%, total gas flow: 20sccm, make the gas pressure 5mTorr, and the DC negative bias loaded on the substrate table is -200V, The bias current is 40-60mA, and the etching time is 240min. After the etching is completed, the bias voltage, microwave power supply, and electromagnetic coil power supply are turned off, and the gas is turned off to obtain a diamond-like nanoneedle array; wherein, the thickness of the residual DLC layer is 500nm, so 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 the diamond-like nanocones is very small, the height is less than 100 nm, the diameter of the tip is 10-40 nm, and the diameter of the bottom is 10-40 nm. less than 100 nm; while most nanocones have a height of 3-4.5 μm, a bottom diameter of 100 nm to 2 μm, and a tip diameter of 10 to 40 nm.

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

Comparative Example 1

(1) Matrix pretreatment:

Titanium alloy TC4 was provided as the substrate. First, the substrate was ultrasonically cleaned with distilled water for 10 min, followed by ultrasonic cleaning with acetone and absolute ethanol for 20 min. Then the substrate was blown dry with nitrogen, and dried at 150 °C in a blast drying oven. ;

The above-mentioned substrate was placed in a multifunctional ion coating equipment (V-Tech MF610/610), and the main valve of the argon 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. , arc valve and target valve and mass flow meter into the vacuum chamber to pass argon to the substrate to carry out glow cleaning, wherein, the conditions of the glow cleaning are: enter argon into the vacuum chamber, the argon flow rate is 450sccm, and the working pressure is 1.7 Pa, substrate bias voltage -800V, glow cleaning the substrate, cleaning time 10min; after glow cleaning, turn on the ion source to clean the sample by ion bombardment, ion etching cleaning conditions are: 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; the cleaning time is 20min;

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

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-like carbon array materials prepared in Examples 4 and 5 of the present invention were respectively tested for antibacterial performance, and a complete DLC layer with a thickness of 5 μm was deposited on titanium alloy TC4 as Comparative Example 1. The results are shown in Figure 3. Pseudomonas aeruginosa acted on comparative example 1 (titanium alloy TC4+ complete DLC layer), and diamond-like nanoarrays obtained in examples 4 and 5, respectively, (a) Pseudomonas aeruginosa bacteria attached to substrates with different surface topography The total number; (b) is the percentage of Pseudomonas aeruginosa that died after 1 h. It can be seen from (b) in FIG. 3 that the complete diamond-like carbon coating (Comparative Example 1) and the diamond-like nano-needle arrays obtained in Examples 4 and 5 have a certain antibacterial effect, but the The bactericidal effect of diamond nano-needle array is obviously much better than that of ordinary complete diamond-like carbon coating without etching. By comparing the nanoneedle arrays etched under different conditions, it can be seen that the sterilization effect of the diamond-like nanoneedle arrays (nanoneedles with different heights) prepared in Example 5 is better.

The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the appended claims.

Claims (9)

1. A structural member with a diamond-like carbon array, characterized in that it comprises a matrix and a diamond-like nano-needle array with a tip structure disposed on the matrix, the diamond-like nano-needle array being formed on the matrix by pairing The diamond-like nano-needles in the diamond-like nano-needle array have a tapered structure, the aspect ratio of the diamond-like nano-needles is 20-80, and the diameter of the tip is 10 ~100 nm, the bottom diameter is 30 nm to 2 μm, and the pin density is 10 ⁸ to 10 ⁹ ·cm ⁻² . 2. The structural member with a diamond-like carbon array according to claim 1, wherein a residual diamond-like carbon coating is further provided between the matrix and the diamond-like carbon nano-needle array, and the diamond-like carbon nano-needle array is formed on the The surface of the residual diamond-like carbon coating; the thickness of the residual diamond-like carbon coating is 100 nm˜3 μm. 3 . The structural member having a diamond-like carbon array according to claim 2 , wherein the height of the diamond-like nano-needles is between 10 nm and 10 μm. 4 . 4. The structure having a diamond-like carbon array according to claim 2, wherein the substrate is one or more of metal, metal alloy, cemented carbide, polymer, glass and silicon. 5 . The structure with diamond-like carbon array according to claim 4 , wherein when the material of the substrate is stainless steel, polymer, cobalt-based metal alloy, cemented carbide, glass and silicon, the The structural member of the diamond-like carbon array further includes a transition metal layer, and the transition metal layer is located between the substrate and the residual diamond-like carbon coating; the thickness of the transition metal layer is 50-500 nm. 6. a preparation method of a structural member with a diamond-like array, is characterized in that, comprises the following steps: providing a structural member base, and pre-processing the base; placing the pretreated substrate in a vacuum chamber of the coating equipment, and depositing a diamond-like coating on the pretreated substrate; The diamond-like carbon coating is etched to obtain a diamond-like nano-needle array with a tip structure, wherein the diamond-like nano-needles in the diamond-like nano-needle array are tapered structures, and the length of the diamond-like nano-needles is The diameter ratio is 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 needle density is 10 ⁸ to 10 ⁹ ·cm ⁻² . 7. The preparation method of claim 6, wherein the method for depositing the diamond-like carbon 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. 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, so that the pressure in the vacuum chamber is 0.5-1.0 Pa, the voltage of the ion source is 50-100 V, and the substrate is negatively biased The pressure is -50～-200V, and the deposition time is 30～600min. 8. preparation method as claimed in claim 6 is characterized in that, the etching of described diamond-like coating is to adopt 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 on which the diamond-like carbon coating is deposited in the cavity of inductively coupled plasma etching, using hydrogen, argon, oxygen, helium, nitrogen, gaseous One or more of the carbon source and SF ₆ is a reactive gas, the flow rate of the reactive gas is 5～200sccm, the reactive gas pressure is 0.1～10Pa, the power of the plasma is 500～3000W, and the radio frequency power on the substrate stage is 50～300W, the etching time is 10～600min; Wherein, the step of the electron cyclotron resonance microwave plasma chemical vapor deposition and etching includes: placing the substrate on which the diamond-like coating is deposited into the electron cyclotron resonance microwave plasma chemical vapor deposition equipment, and feeding hydrogen or mixed Hydrogen, gaseous carbon source and argon, the gas pressure is 5-8mTorr, the DC negative bias is 75-230V, the bias current is 40-120mA, and the etching time is 30 minutes-6 hours. 9. The preparation method according to any one of claims 6-8, characterized in that, after the pretreatment and before depositing the diamond-like coating, further comprising depositing a transition metal layer; Wherein, the step of depositing the transition metal layer includes: feeding 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 to be 80～200A, the substrate bias voltage is -100～-300V, and the deposition time is 2～10min.