CN115261790A - Nanostructured titanium nitride coating with high photo-thermal performance and preparation method thereof - Google Patents

Abstract

The invention discloses a nanostructured titanium nitride coating with high photothermal performance and a preparation method, comprising the following steps: Step 1: using titanium metal as a target material, and arranging a substrate and the target oppositely; the substrate and the target surface The angle between the two surfaces is 45°～80°; Step 2: Step 2: Pour argon and nitrogen gas, and use high-power pulsed magnetron sputtering for deposition, and the discharge power density is 1.0 W/cm ² ～4.5 W/cm ² , the peak power density is 200 W/cm ² -350 W/cm ² , the deposition time is 30 s - 60 s; Step 3: DC magnetron sputtering is used for deposition, and the discharge power density is 3.5 W/cm ² to 5.0 W/cm ² , and the deposition time is 15 min to 25 min; the desired titanium nitride coating can be obtained after cooling after sputtering; the present invention adopts high-power pulse magnetron sputtering and DC magnetron sputtering phase. Combined to obtain a titanium nitride coating with high binding force to the substrate, nanorod structure, close arrangement of nanorods and sharp structure at the top; the coating has continuously adjustable photothermal properties.

Description

A nanostructured titanium nitride coating with high photothermal performance and its preparation method

technical field

The invention relates to the technical field of coating preparation, in particular to a nanostructure titanium nitride coating with high photothermal performance and a preparation method.

Background technique

Coatings with photothermal effects have a wide range of applications in energy, environment, and medical related fields due to their ability to efficiently convert light into heat. Transition metal nitrides have wide absorption wavelengths in the visible and near-infrared regions, good thermal stability, and high strength. They are ideal photothermal materials for high-temperature, corrosion, and wear-and-tear service environments. The preparation methods of transition metal nitride photothermal coatings include physical vapor deposition and chemical vapor deposition. Due to the high-temperature process of chemical vapor deposition, the preparation of transition metal nitride coatings on temperature-sensitive substrates is limited, while physical vapor deposition is more widely applicable. Magnetron sputtering, as a kind of physical vapor deposition, is the preferred technical method for preparing coatings in the industry because of its economy and reliability. However, the transition metal nitride photothermal coating prepared by magnetron sputtering has slow response speed and low photothermal efficiency.

At present, there are transition group metal nitride coatings with nanostructure characteristics such as nanopillars, nanoholes and nanogroove arrays. Structural transition metal nitride coatings exhibit more excellent photothermal effects. However, the preparation of nanostructures such as nanopillars, nanoholes, and nanogroove arrays often requires such functional technologies as ultraviolet lithography and reactive ion etching, and the manufacturing cost is relatively high. Moreover, multi-step processing such as anodic oxidation and subsequent high-temperature ammoniation is required, which is not only complicated in the process, but also faces the difficulty of being unable to manufacture on temperature-sensitive substrates.

When the coating is deposited by magnetron sputtering, when the plasma beam is inclined at a certain angle (OAD) to the substrate, under the action of the "shadow effect", the coating will also have nanostructure features such as nanopillars and nanobelts. However, due to the loose structure of the transition metal nitride coating deposited by OAD, it faces problems such as low coating hardness, poor wear resistance, and low bonding force, and requires subsequent treatment to improve corrosion resistance.

Contents of the invention

Aiming at the problems existing in the prior art, the present invention provides a nano-rod structure titanium nitride coating with compact structure, good bonding, high hardness, wear resistance and corrosion resistance and a preparation method thereof.

The technical scheme adopted in the present invention is:

A method for preparing a nanostructured titanium nitride coating with high photothermal performance, comprising the following steps:

Step 1: Using metal titanium as the target material, set the substrate and the target material oppositely; the angle between the substrate and the two surfaces of the target surface is 45° to 80°;

Step 2: Step 2: Introducing argon and nitrogen, using high-power pulsed magnetron sputtering for deposition, with a discharge power density of 1.0 W/cm ² to 4.5 W/cm ² and a peak power density of 200 W/cm ² to 350 W/cm ² , the deposition time is 30 s ~ 60 s;

Step 3: Deposit by DC magnetron sputtering, the discharge power density is 3.5 W/cm ² to 5.0 W/cm ² , and the deposition time is 15 min to 25 min; the desired titanium nitride can be obtained after cooling after sputtering coating.

Further, the area of the target is 1.5 times larger than the area of the substrate, and the distance between the center of the substrate and the center of the target surface is 80 mm to 120 mm.

Further, the argon gas has a purity greater than 99.9%, a flow rate of 30 sccm-50 sccm, and a partial pressure of 0.3 Pa-0.5 Pa.

Further, the nitrogen purity is greater than 99.9%, the flow rate is 5 sccm-12 sccm, and the partial pressure is 0.05 Pa-0.12 Pa.

Further, in the step 2, target material sputtering cleaning and substrate sputtering cleaning are first carried out;

The argon gas pressure is 0.3 Pa to 0.5 Pa when the target is cleaned, the discharge power density is 2.0 W/cm ² to 3.0 W/cm ² when the target is cleaned, and the target cleaning time is 5 to 15 minutes;

When the substrate is cleaned, the argon gas pressure is 2.0 Pa to 4.0 Pa, the negative substrate bias voltage of the substrate is -1000 to -1500 V, and the substrate cleaning time is 10 to 30 minutes.

Further, the bias voltage of the base substrate during the deposition process in step 2 and step 3 is -50 V to -150 V.

A nanostructured titanium nitride coating, the titanium nitride coating on the surface of the substrate has a nanorod structure, the nanorods are closely packed, and the top is sharp; the diameter of the titanium nitride nanorods is 100 nm to 200 nm, and the titanium nitride nanorods Tilting to one side; the included angle between the titanium nitride nanorod and the vertical line of the substrate is 24°-30°.

The beneficial effects of the present invention are:

(1) The present invention combines high-power pulsed magnetron sputtering and DC magnetron sputtering to obtain a nitriding material with high bonding force with the substrate, nanorod structure, tight arrangement of nanorods, and sharp structure at the top. Titanium coating;

(2) The titanium nitride coating obtained in the present invention has continuously adjustable photothermal properties, and the continuous adjustment of the size of the nanorods can be realized by adjusting the incident angle of the plasma quantity and the adjustment of the deposition time;

(3) After the titanium nitride coating obtained in the present invention is irradiated with a 1.0 W/cm ² 808 nm laser, the surface temperature of the coating can reach up to 100 °C, and its photothermal performance greatly exceeds that of the existing transition metal nitride coating;

(4) The titanium nitride coating obtained in the present invention has a nanorod structure with a sharp tip and has a physical sterilization effect.

Description of drawings

Figure 1 is a schematic diagram of the relative positional relationship between the target and the substrate.

Fig. 2 is the XRD pattern of the titanium nitride nano-coatings obtained in Example 1 and Example 2 of the present invention.

FIG. 3 is an SEM image of the titanium nitride nano-coating obtained in Example 1 and Example 2 of the present invention.

Fig. 4 is a schematic diagram of photothermal performance test curves of titanium nitride nano-coatings obtained in Examples 1-4 of the present invention.

Fig. 5 is a graph showing the mechanical performance test results of the nano-coatings obtained in Examples 1 and 2 of the present invention. a is the hardness test result of the coating, b is the bonding test result of the coating, c is the wear resistance test result of the coating, and d is the corrosion resistance test result of the coating.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

A method for preparing a nanostructured titanium nitride coating with high photothermal performance, comprising the following steps:

Step 1: Using metal titanium as the target, set the substrate and the target oppositely; the angle between the two surfaces of the substrate and the target surface is 45° to 80°; if the angle between the substrate and the target surface is too small, the plasma The inclination angle of the beam is not enough to form nanopillars, and the distance is too large to allow the plasma beam to reach the surface of the substrate for coating deposition. The target area is 1.5 times larger than the substrate area, and this setting can ensure the uniformity of the inclination angle of the plasma beam in front of the entire substrate. The distance between the center of the substrate and the center of the target surface is 80 mm to 120 mm. If the distance is too small, the plasma beam will not be uniform on the substrate surface; if the distance is too large, the beam will be diffracted, making oblique incidence deposition impossible.

Step 2: Infuse argon and nitrogen, and deposit by high-power pulse magnetron sputtering, with a discharge power density of 1.0 W/cm ² to 4.5 W/cm ² and a peak power density of 200 W/cm ² to 350 W/ cm ² , the sputtering power is too low, the Ti ionization rate is low, and there is no sufficient amount of Ti ions implanted into the substrate, and the high power increases the residual compressive stress, which affects the interface bonding. The deposition time is 30 s to 60 s; during the deposition process, the purity of argon gas is greater than 99.9%, the flow rate is 30 sccm to 50 sccm, and the partial pressure is 0.3 Pa to 0.5 Pa. The nitrogen purity is greater than 99.9%, which ensures the formation of 1:1 stoichiometric TiN. The flow rate is 5 sccm~12 sccm, and the partial pressure is 0.05 Pa~0.12 Pa. During the deposition process, the substrate bias voltage is -50 V ~ -150 V. Applying a bias voltage to the substrate is beneficial to increase the hardness of the coating. The higher the bias voltage, the higher the hardness. If the bias voltage is too small, the coating will be loose, and if the bias voltage is too large, the residual compressive stress will be increased and the coating will peel off.

The chamber is evacuated to below 2×10-3 Pa before deposition. If the vacuum degree is insufficient, the coating will be oxidized, which will affect the photothermal effect.

First, target sputtering cleaning and substrate sputtering cleaning are carried out;

The argon gas pressure is 0.3 Pa to 0.5 Pa when the target is cleaned, the discharge power density is 2.0 W/cm ² to 3.0 W/cm ² when the target is cleaned, and the target cleaning time is 5 to 15 minutes;

When the substrate is cleaned, the argon gas pressure is 2.0 Pa to 4.0 Pa, the negative substrate bias voltage of the substrate is -1000 to -1500 V, and the substrate cleaning time is 10 to 30 minutes.

Step 3: Use DC magnetron sputtering for deposition, the discharge power density is 3.5 W/cm ² to 5.0 W/cm ² , and the deposition time is 15 min to 25 min; too small power is not conducive to the formation of wear-resistant and corrosion-resistant (111) Surface-preferential TiN coating, too high power, increases residual compressive stress, and affects the combination of coating and substrate. If the deposition time is too short, the nanorods cannot be formed, and if the deposition time is too long, the nanorods grow into a continuous thin film. After sputtering and cooling, the desired titanium nitride coating can be obtained. During the deposition process, the purity of argon gas is greater than 99.9%, the flow rate is 30 sccm-50 sccm, and the partial pressure is 0.3 Pa-0.5 Pa. The nitrogen purity is greater than 99.9%, the flow rate is 5 sccm~12 sccm, and the partial pressure is 0.05 Pa~0.12 Pa. During the deposition process, the substrate bias voltage is -50 V ~ -150 V.

A nanostructured titanium nitride coating, the titanium nitride coating on the surface of the substrate has a nanorod structure, the nanorods are closely packed, and the top is sharp; the diameter of the titanium nitride nanorods is 100 nm to 200 nm, and the titanium nitride nanorods Tilting to one side; the included angle between the titanium nitride nanorod and the vertical line of the substrate is 24°-30°.

Example 1

Nanostructured titanium nitride coatings with high photothermal properties were prepared as follows:

Step 1: First process the substrate, put the 304 stainless steel disc into acetone, clean it ultrasonically for 15 minutes, then ultrasonically clean it in absolute ethanol for 15 minutes, and finally take it out and dry it with nitrogen for use;

A rectangular metal Ti target with a purity of 99.9% and a size of 170 mm × 130 mm × 5 mm was installed in the vacuum chamber. Fix the processed substrate on the jig, keep the center of the substrate facing the center of the target surface, adjust the distance between the substrate and the target surface to 100 mm, and adjust the angle between the substrate and the target surface to 45°. The installation is shown in Figure 1.

Step 2: Sputter cleaning of the target and substrate first

The intrinsic vacuum is pre-evacuated to 2.00×10 ^-3 Pa, and Ar gas with a purity greater than or equal to 99.9% is introduced into the cavity, the Ar gas flow rate is 40 sccm, and the air pressure is adjusted to 0.4 Pa. Clean the target with a DC power supply of 225 V and 3 A for 10 minutes, adjust the air pressure to 3.0 Pa; apply a negative substrate bias of -1500 V to the substrate; at this time, Ar plasma is generated near the substrate, and Ar ⁺ is in the negative substrate bias. Bombardment of the substrate was continued for 20 minutes under pressure.

Keep the Ar gas flow constant, the flow rate is 40 sccm, and the partial pressure is adjusted to 0.4 Pa; N ₂ gas is introduced, the flow rate is 10 sccm, and the partial pressure is adjusted to 0.1 Pa. Apply a -50 V DC substrate bias to the substrate. Turn on the high-power pulsed magnetron sputtering power supply of -800 V, 150 μm, 200 Hz for the target, keep the average power density of Ti target discharge at 3.0 W/cm ² , and the peak power density is about 275 W/cm ² , Deposit the TiN coating for 30 s.

Step 3: Keep the flow of Ar gas and N gas in step ₂ constant, connect the target with a -350 V, 3A DC magnetron sputtering power supply, and keep the average power density of Ti target discharge at 4.7 W/cm ² , deposit TiN coating for 15 min.

After the coating is deposited, it is cooled to below 30 °C in a vacuum environment, then released to atmospheric pressure, and the cavity is opened to obtain a nanorod structure TiN coating on the surface of the substrate.

Example 2

Nanostructured titanium nitride coatings with high photothermal properties were prepared as follows:

Step 1: First process the substrate, put the 304 stainless steel disc into acetone, clean it ultrasonically for 15 minutes, then ultrasonically clean it in absolute ethanol for 15 minutes, and finally take it out and dry it with nitrogen for use;

A rectangular metal Ti target with a purity of 99.9% and a size of 170 mm × 130 mm × 5 mm was installed in the vacuum chamber. Fix the processed substrate on the jig, keep the center of the substrate facing the center of the target surface, adjust the distance between the substrate and the target surface to 100 mm, and adjust the angle between the substrate and the target surface to 80°. The installation is shown in Figure 1.

Step 2: Sputter cleaning of the target and substrate first

The intrinsic vacuum is pre-evacuated to 2.00×10 ^-3 Pa, and Ar gas with a purity greater than or equal to 99.9% is introduced into the cavity, the Ar gas flow rate is 40 sccm, and the air pressure is adjusted to 0.4 Pa. Clean the target with a DC power supply of 225 V and 3 A for 10 minutes, adjust the air pressure to 3.0 Pa; apply a negative substrate bias of -1500 V to the substrate; at this time, Ar plasma is generated near the substrate, and Ar ⁺ is in the negative substrate bias. Bombardment of the substrate was continued for 20 minutes under pressure.

Keep the Ar gas flow constant, the flow rate is 40 sccm, and the partial pressure is adjusted to 0.4 Pa; N ₂ gas is introduced, the flow rate is 10 sccm, and the partial pressure is adjusted to 0.1 Pa. Apply a -50 V DC substrate bias to the substrate. Turn on the high-power pulsed magnetron sputtering power supply of -800 V, 150 μm, 200 Hz for the target, keep the average power density of Ti target discharge at 3.0 W/cm ² , and the peak power density is about 275 W/cm ² , Deposit the TiN coating for 30 s.

Step 3: Keep the flow of Ar gas and N gas in step ₂ constant, connect the target with a -350 V, 3A DC magnetron sputtering power supply, and keep the average power density of Ti target discharge at 4.7 W/cm ² , deposit TiN coating for 15 min.

After the coating is deposited, it is cooled to below 30 °C in a vacuum environment, then released to atmospheric pressure, and the cavity is opened to obtain a nanorod structure TiN coating on the surface of the substrate.

Example 3

Nanostructured titanium nitride coatings with high photothermal properties were prepared as follows:

Step 1: First process the substrate, put the 304 stainless steel disc into acetone, clean it ultrasonically for 15 minutes, then ultrasonically clean it in absolute ethanol for 15 minutes, and finally take it out and dry it with nitrogen for use;

A rectangular metal Ti target with a purity of 99.9% and a size of 170 mm × 130 mm × 5 mm was installed in the vacuum chamber. Fix the processed substrate on the jig, keep the center of the substrate facing the center of the target surface, adjust the distance between the substrate and the target surface to 100 mm, and adjust the angle between the substrate and the target surface to 80°. The installation is shown in Figure 1.

Step 2: Sputter cleaning of the target and substrate first

The intrinsic vacuum is pre-evacuated to 2.00×10 ^-3 Pa, and Ar gas with a purity greater than or equal to 99.9% is introduced into the cavity, the Ar gas flow rate is 40 sccm, and the air pressure is adjusted to 0.4 Pa. Clean the target with a DC power supply of 225 V and 3 A for 10 minutes, adjust the air pressure to 3.0 Pa; apply a negative substrate bias of -1500 V to the substrate; at this time, Ar plasma is generated near the substrate, and Ar ⁺ is in the negative substrate bias. Bombardment of the substrate was continued for 20 minutes under pressure.

Keep the Ar gas flow constant, the flow rate is 40 sccm, and the partial pressure is adjusted to 0.4 Pa; N ₂ gas is introduced, the flow rate is 10 sccm, and the partial pressure is adjusted to 0.1 Pa. Apply a -50 V DC substrate bias to the substrate. Turn on the high-power pulsed magnetron sputtering power supply of -800 V, 150 μm, 200 Hz for the target, keep the average power density of Ti target discharge at 3.0 W/cm ² , and the peak power density is about 275 W/cm ² , Deposit the TiN coating for 30 s.

Step 3: Keep the flow of Ar gas and N gas in step ₂ constant, connect the target with a -350 V, 3A DC magnetron sputtering power supply, and keep the average power density of Ti target discharge at 4.7 W/cm ² , deposit TiN coating for 25 min.

After the coating is deposited, it is cooled to below 30 °C in a vacuum environment, then released to atmospheric pressure, and the cavity is opened to obtain a nanorod structure TiN coating on the surface of the substrate.

Example 4

Nanostructured titanium nitride coatings with high photothermal properties were prepared as follows:

Step 1: First process the substrate, put the quartz substrate in acetone, clean it ultrasonically for 15 minutes, then ultrasonically clean it in absolute ethanol for 15 minutes, and finally take it out and dry it with nitrogen gas for use;

A rectangular metal Ti target with a purity of 99.9% and a size of 10 mm × 10 mm × 1 mm was installed in the vacuum chamber. Fix the processed substrate on the fixture, keep the center of the substrate facing the center of the target surface, adjust the distance between the substrate and the target surface to 100 mm, and adjust the angle between the substrate and the target surface to 80°. The installation is shown in Figure 1 .

Step 2: Sputter cleaning of the target and substrate first

The intrinsic vacuum is pre-evacuated to 2.00×10 ^-3 Pa, and Ar gas with a purity greater than or equal to 99.9% is introduced into the cavity, the Ar gas flow rate is 40 sccm, and the air pressure is adjusted to 0.4 Pa. Clean the target with a DC power supply of 225 V and 3 A for 10 minutes, adjust the air pressure to 3.0 Pa; apply a negative substrate bias of -1500 V to the substrate; at this time, Ar plasma is generated near the substrate, and Ar ⁺ is in the negative substrate bias. Bombardment of the substrate was continued for 20 minutes under pressure.

Keep the Ar gas flow constant, the flow rate is 40 sccm, and the partial pressure is adjusted to 0.4 Pa; N ₂ gas is introduced, the flow rate is 10 sccm, and the partial pressure is adjusted to 0.1 Pa. Apply a -50 V DC substrate bias to the substrate. Turn on the high-power pulsed magnetron sputtering power supply of -800 V, 150 μm, 200 Hz for the target, keep the average power density of Ti target discharge at 3.0 W/cm ² , and the peak power density is about 275 W/cm ² , Deposit the TiN coating for 30 s.

Step 3: Keep the flow of Ar gas and N gas in step ₂ constant, connect the target with a -350 V, 3A DC magnetron sputtering power supply, and keep the average power density of Ti target discharge at 4.7 W/cm ² , deposit TiN coating for 15 min.

After the coating is deposited, it is cooled to below 30 °C in a vacuum environment, then released to atmospheric pressure, and the cavity is opened to obtain a nanorod structure TiN coating on the surface of the substrate.

Fig. 2 is the XRD pattern of the titanium nitride nano-coatings obtained in Example 1 and Example 2 of the present invention. The crystal structure of the coating was analyzed by X-ray diffractometer. The anode target of the X-ray diffractometer was a Cu target (λ=1.54060 Å), where the X-ray tube voltage was 40 kV and the current was 30 mA; mode to scan the sample, the 2θ angle ranges from 5° to 80°. It can be seen from the figure that the TiN coating is obtained, and the crystallographic (111) surface is preferred. This structure can increase the hardness of the coating, and this feature can also enhance the wear resistance and corrosion resistance of the coating.

Figure 3 is the SEM image (SEM, JSM-700F, JEOL) of the titanium nitride nano-coating obtained in Example 1 and Example 2 of the present invention. The cross-sectional morphology of the coating is observed, and the electron accelerating voltage is 5 kV; It can be seen from the figure that the angle between the substrate and the target increases from 45° to 80°, and the diameter of the TiN nanorods in the coating becomes smaller. When the angle is 80°, the diameter of the TiN nanorods is about 100 nm. The enlargement of Δ increases from about 24° to about 30°. The larger the included angle, the sharper the tip of the nanorod, which is conducive to the improvement of photothermal performance.

Fig. 4 is a schematic diagram of photothermal performance test curves of titanium nitride nano-coatings obtained in Examples 1-4 of the present invention. The TiN coating was continuously irradiated with a 808 nm laser with a power density of 1.0 W/cm ² for 5 min. During the entire test process, the coating surface temperature was measured online with an infrared thermal imager and recorded in real time every 30 s. After irradiating with 1.0 W/cm ² 808nm laser for 5 min, the surface temperature of the coating can reach 57 ℃.

It can be seen from the figure that the TiN coating deposited on the stainless steel surface at an incident angle of 45° for 15 minutes, after 5 minutes of laser irradiation, the temperature reaches about 57 °C. The TiN coating was deposited for 15 minutes at an incident angle of 80°, and the temperature reached about 66 °C after 5 minutes of laser irradiation. The TiN coating was deposited for 25 minutes at an incident angle of 80°, and the temperature exceeded 89 ℃ after 5 minutes of laser irradiation. The TiN coating was deposited on the quartz surface at an incident angle of 45° for 15 minutes. After 5 minutes of laser irradiation, the temperature exceeded 102 ℃.

Fig. 5 is the hardness of the titanium nitride nano-coating that embodiment 1 and embodiment 2 obtain, bonding, wear resistance, corrosion resistance test result. The nano-indentation hardness of the coating was tested using a nano-indenter (Nano Indenter G200, Agilent), with a set load of 1 mN and a loading rate of 0.2 mN/min, as shown in Figure 5. The hardness of the coating obtained in Example 1 reaches above 20 GPa.

The hardness of the coating obtained in Example 2 reaches above 15 GPa.

The coating is scratch tested by a multi-functional material surface performance measuring instrument (MTF-400). The indenter is a Si ₃ N ₄ ball head with a diameter of 6 mm, a scratch length of 5 mm, a maximum load of 100 N, and a loading rate of 100 N/min. , the moving speed of the indenter is 5mm/min. It can be seen from Figure 5 that the coatings obtained in Example 1 and Example 2 are all firmly bonded.

The Swiss CSEM friction and wear testing machine is used to evaluate the wear resistance of the coating, and the method is a ball-on-disk type. In the ball-on-disk test, the "ball" is a Φ6mm Si ₃ N ₄ sphere, the applied normal load is 0.5N, the sample is rotated around the central axis, and the rotation radius is 6mm. It can be seen from Figure 5 that the coefficient of friction of the coating obtained in Example 1 and Example 2 is below 0.4.

The corrosion resistance of the TiN thin film was measured by an IM6 electrochemical workstation. The corrosion solution was NaCl solution with a concentration of 0.9%. The area to be tested was 1.77cm ² . The results are shown in Figure 5, from which it can be seen that the coatings obtained in Example 1 and Example 2 are resistant to salt solution corrosion.

The present invention combines high-power pulse magnetron sputtering and DC magnetron sputtering to obtain a titanium nitride coating with a high bonding force with a base material, a nanorod structure, a tight arrangement of the nanorods, and a sharp structure at the top. High-power pulse magnetron sputtering is used to obtain a bonding layer on the substrate. The high-energy plasma beam generated by high-power pulse magnetron sputtering can be injected into the subsurface layer of the substrate to improve the bonding force between the coating and the substrate, and the obtained The bonding layer structure is relatively dense, which can avoid corrosion of the substrate-coating interface. Due to the special properties of the bonding layer obtained by high-power pulsed magnetron sputtering on the substrate, further applying a DC substrate bias to the substrate enhances the bombardment of ions on the substrate and further improves the density of nanorods in the coating. degree of closeness. Finally, a transition metal nitride photothermal coating with compact structure, high hardness, wear resistance and corrosion resistance can be obtained, which can increase the service reliability of the coating and prolong the service life of the coating.

The titanium nitride coating obtained in the present invention has a nanorod structure, the nanorods are closely packed, and the top is sharp; the diameter of the titanium nitride nanorods is 100 nm to 200 nm, and the titanium nitride nanorods are inclined to one side; the titanium nitride nanorods are The angle between the perpendicular to the substrate is 24° to 30°. By adjusting the incident angle of the plasma quantity and the adjustment of the deposition time, further regulation of the size of the nanorods can be realized, and the purpose of continuous regulation of the photothermal properties of the titanium nitride coating can be achieved. After the coating obtained in the present invention is irradiated with a 1.0W/cm ² 808 nm laser, the surface temperature of the coating can reach up to 100 °C (102 °C in Example 4), and its photothermal performance greatly exceeds that of the existing transition metal nitride coating. Floor. The coating is firmly bonded to the substrate, has high hardness, wear resistance and corrosion resistance, and can serve stably for a long time in seawater desalination and thermal photovoltaic devices. After artificial joints and artificial maxillofacial implants are implanted, they face a huge risk of infection. Regular irradiation of near-infrared lasers on implanted devices deposited with a nanorod structure titanium nitride (TiN) coating can non-invasively kill those that cause local infection. bacterial community.

Claims (7)

1. A preparation method of a nano-structure titanium nitride coating with high photo-thermal performance is characterized by comprising the following steps:

step 1: taking metal titanium as a target material, and arranging the substrate and the target material oppositely; the included angle between the substrate and the two surfaces of the target surface is 45-80 degrees;

step 2: introducing argon and nitrogen, depositing by high-power pulse magnetron sputtering with discharge power density of 1.0W/cm ² ～4.5 W/cm ² The peak power density is 200W/cm ² ～350 W/cm ² The deposition time is 30-60 s;

and step 3: depositing by adopting direct current magnetron sputtering, wherein the discharge power density is 3.5W/cm ² ～5.0 W/cm ² The deposition time is 15 min to 25 min; and after the sputtering is finished and the titanium nitride coating is cooled, the required titanium nitride coating can be obtained.

2. The method of claim 1, wherein the area of the target is 1.5 times larger than the area of the substrate, and the distance between the center of the substrate and the center of the target surface is 80 mm-120 mm.

3. The method of claim 1, wherein the argon gas has a purity of greater than 99.9%, a flow rate of 30 sccm to 50 sccm, and a partial pressure of 0.3 Pa to 0.5 Pa.

4. The method of claim 1, wherein the nitrogen has a purity of greater than 99.9%, a flow rate of 5 sccm to 12 sccm, and a partial pressure of 0.05 Pa to 0.12 Pa.

5. The method for preparing the nano-structure titanium nitride coating with high photothermal properties according to claim 1, wherein in step 2, the target sputtering cleaning and the substrate sputtering cleaning are firstly performed;

the argon pressure is 0.3 Pa-0.5 Pa when the target material is cleaned, and the discharge power density is 2.0W/cm when the target material is cleaned ² ～3.0 W/cm ² The target cleaning time is 5 to 15 minutes;

the argon pressure is 2.0 Pa-4.0 Pa when the substrate is cleaned, the negative substrate bias voltage of the substrate is-1000V-1500V, and the substrate cleaning time is 10-30 minutes.

6. The method for preparing a nano-structured titanium nitride coating with high photothermal properties according to claim 1, wherein the bias voltage of the base substrate during the deposition in step 2 and step 3 is-50V to-150V.

7. The nano-structure titanium nitride coating obtained by the preparation method of any one of claims 1 to 6, wherein the titanium nitride coating on the surface of the base material has a nanorod structure, and nanorods are closely packed and have sharp tops; the diameter of the titanium nitride nanorod is 100 nm-200 nm, and the titanium nitride nanorod inclines to one side; the included angle between the titanium nitride nano rod and the vertical line of the base material is 24-30 degrees.

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