CN108359953A - A kind of Cu-Ni gradient films material and preparation method thereof - Google Patents

Abstract

The invention discloses a Cu-Ni gradient film material and a preparation method thereof. The method uses commercial copper foil or soda-lime glass as the substrate, high-purity copper target material and nickel target material as the sputtering material, and high-vacuum multi-target The magnetron sputtering equipment is a preparation tool. During the process of co-sputtering deposition, the relative content of copper and nickel in the film material can be adjusted by fixing the sputtering power of the copper target position and changing the sputtering power of the nickel target position. Co-sputtering time is used to control the thickness of the prepared film, and finally a Cu-Ni gradient film material with variable thickness is prepared. The method of the invention has the characteristics of short preparation process, simple operation, wide parameter control range, easy realization, optional control of gradient layer thickness, etc., and has good commercialization prospects.

Description

A kind of Cu-Ni gradient film material and preparation method thereof

technical field

The present invention relates to the field of preparation of gradient thin film materials, in particular to a method for preparing binary alloy gradient thin film materials by using magnetron sputtering technology, in particular to a method for preparing Cu-Ni gradient thin film materials by high vacuum double-target magnetron sputtering method.

Background technique

Gradient material is the selection of two (or more) materials with different properties, and the interface disappears by continuously changing the composition and structure of the two (or more) materials, resulting in the change of the properties of the material with the composition and structure of the material. And slowly changing. Since the composition of the gradient material changes continuously in a certain spatial direction and there is no obvious interface, the properties of adjacent layers are similar, and the overall performance of the material changes continuously.

With the rapid development of the global economy, in petroleum, chemical industry, energy, electric power, metallurgy, aerospace and other industries, there are a large number of friction motion pair parts used in harsh environments such as high temperature and corrosion. Not only the materials are required to have good resistance Abrasion resistance, corrosion resistance and oxidation resistance, also need to have excellent toughness. However, a single material with uniform properties is often difficult to meet the above-mentioned fields with multiple application requirements. Cu-based gradient materials are mainly made of copper and another metal material. Cu-Ni gradient materials have good seawater corrosion resistance and high temperature and oxidation resistance, and have broad application prospects in the fields of marine engineering and aerospace. There are many ways to prepare Cu-Ni gradient materials, such as spark plasma sintering, hot pressing sintering, electrodeposition, vapor deposition, and self-propagating high-temperature synthesis. The gradient material is obtained by stacking copper and another material by different methods, so that the material not only has high mechanical strength and good toughness, but also has good electrical conductivity. At the same time, as a gradient material, the bonding surface between the two materials is gradually transitioned, and the composition change between the surfaces is small, which effectively reduces the thermal stress between the two sides and reduces the material due to thermal stress during use. The probability of cracks caused by thermal stress mismatch prolongs the service life of the material.

The magnetron sputtering technology is to place the target material of the material to be deposited into a film on the cathode of the sputtering deposition system. After the sputtering system is evacuated to a high vacuum, it is filled with argon and a specific reaction gas (there may be no reaction gas); the gas The plasma formed by ionization under high pressure is accelerated under the action of electric field and alternating magnetic field, and bombards the surface of the target, causing the atoms on the surface of the target to escape from the original lattice and transfer to the surface of the substrate of the anode sample stage to deposit a film. Magnetron sputtering is characterized by high film formation rate, low substrate temperature, good film adhesion, and large-area coating. By installing targets of different materials at different target positions and using multi-target magnetron sputtering, film materials of different components can be obtained. The relative content of components in the thin film material prepared by this method is related to the deposition rate of different target materials on the substrate. The deposition rate of a certain component depends on the nature of the component itself, the sputtering power of the target position, and the distance between the center of the target plane and the center of the deposition sample stage. In this way, the adjustment of the relative content of the components in the film material can be realized by changing the sputtering power of the target position and the distance between the center of the target plane and the center of the deposition sample stage. These characteristics of multi-target magnetron sputtering technology make it suitable for preparing gradient thin film materials.

Contents of the invention

The technical problem to be solved by the present invention is to provide a Cu-Ni alloy gradient film material; the present invention also provides a low-cost, simple process for preparing Cu-Ni gradient film material by using high vacuum double-target magnetron sputtering technology method.

For realizing above object, the technical scheme that the present invention adopts is as follows:

On copper foil substrate or soda lime glass substrate, magnetron sputtering double target co-deposits Cu-Ni thin film, in situ annealing at 350 ℃ while magnetron sputtering; Under the premise of a fixed distance, the relative content of copper and nickel in the Cu-Ni film is adjusted by changing the sputtering power of the two targets; the inner pure copper layer is in contact with the substrate, and the copper content of the gradient layer gradually decreases from the inside to the outside. The nickel content gradually increased.

The double target is a copper target and a nickel target, the copper content of the copper target is greater than 99.99%, and the nickel content of the nickel target is greater than 99.99%.

The copper substrate is a commercial copper foil with a thickness of 9 μm, and the area can vary between 5 cm × 5 cm ~ 10 cm × 10cm; the soda-lime glass substrate is ordinary soda-lime glass with a thickness of 100 μm, and the area is 5 cm cm × 5 cm.

Preferably, the conditions of the magnetron sputtering are: the distance between the center of the plane where the copper target is located and the center of the deposition sample stage is 8-10 cm, and the distance between the center of the plane where the nickel target is located and the center of the deposition sample stage is 4-6 cm. remain unchanged during shooting.

Preferably, the conditions of the magnetron sputtering are: the sputtering power of the copper target is set between 25 ~ 50 W and remains constant during the co-sputtering process; the initial sputtering power of the nickel target is set at 25 ~ 75 W Between W, the sputtering power of the nickel target can be increased during the co-sputtering process according to the gradient change of Ni content in the Cu-Ni binary alloy film, and the sputtering power adjustment range is 25~175W.

Preferably, the conditions of the magnetron sputtering are: the vacuum degree of the background of the sputtering chamber is not lower than 1.0×10 ^-4 Pa, the working argon pressure of the co-sputtering is about 1.0 Pa, the rotation of the substrate The speed is 15 r/min.

Preferably, the condition of the magnetron sputtering is: after the copper target is sputtered for at least 10 min, the co-sputtering of the copper target and the nickel target is started. Sputtering the copper target for a certain period of time can form an ultra-thin connection layer on the one hand and strengthen the connection force between the co-sputtered film and the substrate; on the other hand, it can form a pure copper layer of Cu-Ni gradient film material.

Preferably, the annealing process of the present invention is: in-situ annealing at 350° C. during the co-sputtering process, so as to eliminate the stress generated during the co-deposition process and prevent the generation of microcracks.

The steps of the present invention are:

(1) Place the polished copper target and nickel target on the two DC sputtering target positions of the high-vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 8-10 cm, The distance between the center of the plane where the nickel target is located and the center of the deposition sample stage is 4-6 cm, which remains unchanged during the co-sputtering process.

(2) Use acetone to ultrasonically clean the copper foil substrate or soda-lime glass substrate for 5 minutes to remove the residual organic matter on the surface, then ultrasonically clean the copper foil substrate with dilute hydrochloric acid for 5 minutes to remove the surface oxide, and finally use absolute ethanol to remove the residual organic matter on the surface. Solution ions and dries quickly.

(3) Transfer the copper foil substrate or soda-lime glass substrate to the center of the substrate sample stage of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set between 25-50 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set between 25-75 W.

(6) After the copper target starts sputtering for at least 10 min, open the nickel target and start the co-sputtering of the copper target and the nickel target. According to the thickness of the Cu-Ni binary alloy film to be prepared and the gradient change requirements of the Cu and Ni content in it, the sputtering power of the nickel target is increased at certain intervals during the co-sputtering process, and the sputtering power adjustment range is 25~175 W.

(7) After the co-sputtering deposition is completed, maintain the air pressure in the sputtering system cavity, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it cools below 50 °C, open the cavity and remove the prepared sample.

The beneficial effects of the present invention are:

(1) The present invention provides a copper-nickel alloy gradient film material with controllable thickness deposited on a bulk substrate by using high-vacuum double-target magnetron sputtering technology. The size of the copper-nickel alloy gradient film material prepared by this method is controllable , thickness controllable, composition adjustable, can meet large-area and large-scale use. The size of the film can be controlled by the size of the substrate; the thickness of the film is 1 μm to 50 μm, which can be adjusted by controlling the time of co-sputtering; the content of Cu in the film varies from 50% to 100%, and can be adjusted by changing the sputtering power of the nickel target adjust.

(2) The present invention selects copper foil or soda-lime glass as the base material, and performs in-situ annealing on the copper-nickel alloy film formed by magnetron sputtering under the protection of inert gas during the magnetron sputtering process, which improves the metal substrate and coating material. adhesion and reduce the occurrence of microcracks.

(3) Copper-nickel alloy gradient thin film material is prepared by magnetron sputtering method, which has simple operation, strong practicability, low cost and strong controllability, and has the application prospect of commercial large-scale production.

Detailed ways

The following are specific examples of the present invention, and further describe the technical solution of the present invention, but the protection scope of the present invention is not limited to these examples. All changes or equivalent substitutions that do not depart from the concept of the present invention are included in the protection scope of the present invention.

Embodiment 1: The preparation method of the present Cu-Ni gradient film material adopts the following specific process.

(1) Place the polished copper target and nickel target on the two DC sputtering target positions of the high-vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 8 cm, and the nickel target The distance between the center of the plane where it is located and the center of the deposition sample stage is 4 cm, which remains unchanged during the co-sputtering process.

(2) The purchased commercial copper foil was cut into a size of 5 cm × 5 cm as the substrate. The copper foil substrate was ultrasonically cleaned with acetone for 5 minutes to remove residual organic matter on the surface, and then ultrasonically cleaned with dilute hydrochloric acid for 5 minutes to remove surface oxides. Finally, Use absolute ethanol to remove residual solution ions on the surface and dry quickly.

(3) Transfer the copper foil substrate to the center of the substrate sample table of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set at 25 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set at 25 W.

(6) After the copper target starts to sputter for 1 h, the nickel target is turned on, and the co-sputtering of the copper target and the nickel target starts. After co-sputtering for 1 h, increase the sputtering power of nickel target to 50 W and continue co-sputtering; after co-sputtering for another 1 h, increase the sputtering power of nickel target to 100 W and continue co-sputtering; After 1 h of sputtering, the sputtering power of the nickel target was increased to 150 W, and co-sputtering was continued; after 1 h of co-sputtering, the sputtering power was turned off.

(7) After the co-sputtering deposition is completed, keep the air pressure in the sputtering system chamber, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it is cooled below 50 °C, open the chamber and remove the prepared sample, that is The Cu-Ni gradient film material can be obtained.

Embodiment 2: The preparation method of the present Cu-Ni gradient film material adopts the following specific process.

(1) Place the polished copper target and the nickel target on the two DC sputtering target positions of the high vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 10 cm, The distance between the center of the plane and the center of the deposition sample stage is 6 cm, which remains unchanged during the co-sputtering process.

(2) The soda-lime glass substrate was ultrasonically cleaned with acetone for 5 min to remove residual organic matter on the surface, and then absolute ethanol was used to remove residual solution ions on the surface and dried quickly.

(3) Transfer the soda-lime glass substrate to the center of the substrate sample stage of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set at 50 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set at 75 W.

(6) After the copper target starts to sputter for 1 h, the nickel target is turned on, and the co-sputtering of the copper target and the nickel target starts. After co-sputtering for 1 h, increase the sputtering power of nickel target to 125 W and continue co-sputtering; after co-sputtering for another 1 h, increase the sputtering power of nickel target to 175 W and continue co-sputtering; co-sputtering After 1 h, the sputtering power was turned off.

(7) After the co-sputtering deposition is completed, keep the air pressure in the sputtering system chamber, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it is cooled below 50 °C, open the chamber and remove the prepared sample, that is The Cu-Ni gradient film material can be obtained.

Embodiment 3: The preparation method of the present Cu-Ni gradient film material adopts the following specific process.

(1) Place the polished copper target and nickel target on the two DC sputtering target positions of the high-vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 8 cm, and the nickel target The distance between the center of the plane and the center of the deposition sample stage is 5 cm, which remains unchanged during the co-sputtering process.

(2) Cut the purchased commercial copper foil into a size of 10 cm × 10 cm as the substrate. The copper foil substrate was ultrasonically cleaned with acetone for 5 minutes to remove residual organic matter on the surface, and then ultrasonically cleaned with dilute hydrochloric acid for 5 minutes to remove surface oxides. Finally, Use absolute ethanol to remove residual solution ions on the surface and dry quickly.

(3) Transfer the copper foil substrate to the center of the substrate sample table of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set at 50 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set at 50 W.

(6) 2 h after the copper target starts sputtering, the nickel target is turned on, and the co-sputtering of the copper target and the nickel target starts. After co-sputtering for 2 h, increase the sputtering power of nickel target to 75 W and continue co-sputtering; after co-sputtering for another 2 h, increase the sputtering power of nickel target to 100 W and continue co-sputtering; After 2 h of sputtering, increase the sputtering power of the nickel target to 125 W and continue co-sputtering; after another 2 h of co-sputtering, increase the sputtering power of the nickel target to 150 W and continue co-sputtering; co-sputtering for 2 h After that, turn off the sputtering power.

(7) After the co-sputtering deposition is completed, keep the air pressure in the sputtering system chamber, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it is cooled below 50 °C, open the chamber and remove the prepared sample, that is The Cu-Ni gradient film material can be obtained.

Embodiment 4: The preparation method of the present Cu-Ni gradient film material adopts the following specific process.

(1) Place the polished copper target and nickel target on the two DC sputtering target positions of the high-vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 8 cm, and the nickel target The distance between the center of the plane where it is located and the center of the deposition sample stage is 4 cm, which remains unchanged during the co-sputtering process.

(2) Cut the purchased commercial copper foil into a size of 8 cm × 8 cm as the substrate. The copper foil substrate was ultrasonically cleaned with acetone for 5 minutes to remove residual organic matter on the surface, and then ultrasonically cleaned with dilute hydrochloric acid for 5 minutes to remove surface oxides. Finally, Use absolute ethanol to remove residual solution ions on the surface and dry quickly.

(3) Transfer the copper foil substrate to the center of the substrate sample table of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set at 40 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set at 50 W.

(6) After the copper target starts to sputter for 1 h, the nickel target is turned on, and the co-sputtering of the copper target and the nickel target starts. After co-sputtering for 1 h, increase the sputtering power of nickel target to 75 W and continue co-sputtering; after co-sputtering for another 1 h, increase the sputtering power of nickel target to 100 W and continue co-sputtering; After sputtering for 1 h, increase the sputtering power of the nickel target to 125 W, and continue co-sputtering; The sputtering power was increased to 175 W, and the co-sputtering was continued; after 1 h of co-sputtering, the sputtering power was turned off.

(7) After the co-sputtering deposition is completed, keep the air pressure in the sputtering system chamber, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it is cooled below 50 °C, open the chamber and remove the prepared sample, that is The Cu-Ni gradient film material can be obtained.

Embodiment 5: The preparation method of the present Cu-Ni gradient film material adopts the following specific process.

(1) Place the polished copper target and nickel target on the two DC sputtering target positions of the high-vacuum magnetron sputtering system; adjust the distance between the center of the plane where the copper target is located and the center of the deposition sample stage to be 8 cm, and the nickel target The distance between the center of the plane and the center of the deposition sample stage is 5 cm, which remains unchanged during the co-sputtering process.

(2) Cut the purchased commercial copper foil into a size of 10 cm × 10 cm as the substrate. The copper foil substrate was ultrasonically cleaned with acetone for 5 minutes to remove residual organic matter on the surface, and then ultrasonically cleaned with dilute hydrochloric acid for 5 minutes to remove surface oxides. Finally, Use absolute ethanol to remove residual solution ions on the surface and dry quickly.

(3) Transfer the copper foil substrate to the center of the substrate sample table of the magnetron sputtering equipment, fix it with double-conducting copper foil tape, close the magnetron sputtering reaction chamber, and perform vacuuming operation.

(4) Evacuate until the background vacuum is 1.0×10 ^-4 Pa, feed argon gas at a preset flow rate of 20 sccm, fine-tune the flow rate of argon gas until the pressure in the sputtering system chamber is about 1.0 Pa, and adjust the speed of the sample stage to 15 r/ min, the sample stage temperature was raised to 350 °C before sputtering started.

(5) The sputtering power of the copper target was set at 50 W and remained constant during the co-sputtering process; the initial sputtering power of the nickel target was set at 50 W.

(6) After the copper target starts to sputter for 10 min, the nickel target is turned on, and the co-sputtering of the copper target and the nickel target starts. After co-sputtering for 10 min, increase the sputtering power of nickel target to 100 W, and continue co-sputtering; after co-sputtering for another 10 min, increase the sputtering power of nickel target to 150 W, and continue co-sputtering; co-sputtering for 10 min After min, turn off the sputtering power.

(7) After the co-sputtering deposition is completed, keep the air pressure in the sputtering system chamber, adjust the sample stage speed to 0, turn off the heating power of the sample stage, and when it is cooled below 50 °C, open the chamber and remove the prepared sample, that is The Cu-Ni gradient film material can be obtained.

Claims (4)

1. A Cu-Ni gradient film material and preparation method thereof, comprising: The invention discloses a Cu-Ni binary alloy thin film material whose content of Cu and Ni elements changes in a gradient, and the material is prepared by a high-vacuum double-target magnetron sputtering method. 2. Cu-Ni binary alloy film material according to claim 1, is characterized in that: The atomic percentage of Cu element in the alloy film can vary between 50% and 100%, and the balance is Ni element. 3. Cu-Ni binary alloy film material according to claim 1, is characterized in that: The thickness of the film can vary from 1 μm to 50 μm, and the area of the film can vary from 5 cm × 5 cm to 10 cm × 10 cm. 4. the method for preparing Cu-Ni binary alloy film material by high vacuum double-target magnetron sputtering method according to claim 1, is characterized in that: Co-deposit Cu-Ni film on copper substrate or soda-lime glass substrate by magnetron sputtering dual targets, the dual targets used are copper target and nickel target, and in-situ annealing at 350 ℃ while magnetron sputtering; The conditions of the magnetron sputtering are: the distance between the center of the plane where the copper target is located and the center of the deposition sample stage is 8-10 cm, and the distance between the center of the plane where the nickel target is located and the center of the deposition sample stage is 4-6 cm. constant; The condition of described magnetron sputtering is: the sputtering power of copper target is set between 25～50 W and remains constant during co-sputtering process; The conditions of the magnetron sputtering are: the initial sputtering power of the nickel target is set between 25 and 75 W, which can be increased during the co-sputtering process according to the gradient change requirements of the Ni content in the Cu-Ni binary alloy film. The sputtering power of the nickel target, the sputtering power adjustment range is 25~175 W.