Method for preparing copper-gallium alloy film layer through electro-deposition method

Abstract

The invention relates to a method for preparing a copper-gallium alloy film layer through an electro-deposition method, and belongs to the technical field of copper-gallium alloy film layers. The method comprises the following steps: adding metal gallium into a sodium hydroxide solution, and carrying out ultrasonic treatment to completely react and dissolve the metal gallium into the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; a copper sheet serves as a working electrode, a platinum sheet serves as a counter electrode, electro-deposition is conducted for 0.5-12 h in an alkaline gallium ion electrolyte through a constant-current charging method at the room temperature, and the copper-gallium alloy film layer is prepared on the surface of the working electrode through in-situ deposition. According to the method, the copper-gallium alloy film CuGa2 is prepared in the alkaline sodium hydroxide solution through one-step electro-deposition alloying with the metal gallium as the raw material, oxidation of the metal gallium can be effectively avoided, a high-temperature environment is not needed, the thickness of the alloy film is easy to control, the process is simple and easy to operate, and the synthesis rate is high.

Description

Technical Field

[0001] The invention relates to a method for preparing a copper-gallium alloy film layer by an electrodeposition method, belonging to the technical field of copper-gallium alloys. Background Art

[0002] Liquid gallium-based alloy films have developed rapidly due to their excellent performance. Combining the advantages of gallium and copper metals to make alloy films has become the goal pursued by researchers. Copper gallium alloy (CuGa2) films have very excellent performance. Compared with pure gallium, copper gallium alloy films have significantly increased thermal conductivity and electrical conductivity, and their adhesion and formability are also greatly improved. This makes copper gallium alloy films an excellent choice for making high-conductivity circuits, and they are gaining more and more attention.

[0003] However, the traditional method for preparing copper-gallium alloy film layers requires the use of a high-temperature environment to coat gallium on a copper substrate and slowly alloy it to form an alloy film layer. This method requires a high-temperature environment, is time-consuming to prepare, and is costly and inconvenient, so the application of this method is greatly limited. In particular, directly coating gallium on the copper surface not only has a poor fusion effect, but also causes a large amount of oxidation of the liquid metal. The thickness of the alloy film layer is also difficult to control, which greatly affects the effect of forming the alloy film layer. Summary of the invention

[0004] In view of the problems of poor fusion effect, large-scale oxidation of liquid metal gallium, uncontrollable film thickness, etc. in the existing copper-gallium alloy film preparation process, the present invention proposes a method for preparing a copper-gallium alloy film by electrodeposition, that is, using copper as a working electrode and platinum as a counter electrode, and utilizing the effect of an electric field to promote the rapid reduction of gallium ions in an alkaline gallium ion electrolyte on the working electrode copper and realize the rapid alloying of copper-gallium metal.

[0005] A method for preparing a copper-gallium alloy film layer by electrodeposition, the specific steps are as follows:

[0006] (1) adding metallic gallium to a sodium hydroxide solution, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte;

[0007] (2) Using a copper sheet as the working electrode and a platinum sheet as the counter electrode, a copper-gallium alloy film is prepared by in-situ deposition on the surface of the working electrode by constant current electrodeposition in an alkaline gallium ion electrolyte at room temperature for 0.5 to 12 hours.

[0008] Preferably, the mass concentration of the sodium hydroxide solution in step (1) is 5-20%.

[0009] Preferably, the concentration of gallium ions in the alkaline gallium ion electrolyte in step (1) is 0.5 to 5 g / L.

[0010] Preferably, the current density of the constant current electrodeposition in step (2) is 0.01 to 0.5 A / cm 2 .

[0011] The beneficial effects of the present invention are:

[0012] (1) Compared with the traditional copper-gallium alloy film preparation method, liquid gallium is coated on the copper substrate by coating, and high temperature is applied to gradually form an alloy film. This method requires a high-temperature environment, has poor fusion effect, will cause a large amount of oxidation of the liquid metal, and the thickness of the alloy film layer is uneven and uncontrollable, which greatly affects the effect of forming the alloy; the present invention adopts the electrodeposition method to utilize the effect of the electric field to promote the rapid reduction of gallium ions in the alkaline gallium ion electrolyte on the working electrode copper and realize the rapid alloying of copper-gallium metal, which can effectively avoid the oxidation of metallic gallium, the alloy film layer is easy to control, and the process is simple and easy to operate; and it greatly improves the alloying speed of the copper-gallium alloy and the preparation efficiency of the copper-gallium alloy film layer; BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 The XRD diagram of the copper-gallium alloy film layer at different electrodeposition times in Example 1;

[0014] Figure 2 The SEM image and EDS image of the copper-gallium alloy film layer after electrodeposition for 0.5 h in Example 1;

[0015] Figure 3 The SEM image and EDS image of the copper-gallium alloy film layer after electrodeposition for 1 h in Example 2;

[0016] Figure 4 The SEM image and EDS image of the copper-gallium alloy film layer after electrodeposition for 4 hours in Example 3;

[0017] Figure 5 These are the SEM and EDS images of the copper-gallium alloy film layer in Example 4 after electrodeposition for 8 hours. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with specific implementation modes, but the protection scope of the present invention is not limited to the described contents.

[0019] Example 1: A method for preparing a copper-gallium alloy film layer by electrodeposition, the specific steps are as follows:

[0020] (1) adding metallic gallium to a sodium hydroxide solution having a mass concentration of 10%, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; wherein the concentration of gallium ions in the alkaline gallium ion electrolyte is 1 g / L;

[0021] (2) A copper sheet was used as a working electrode and a platinum sheet was used as a counter electrode. Constant current electrodeposition was performed in an alkaline gallium ion electrolyte at room temperature for 0.5 h, 1 h, 4 h, and 8 h, respectively, to prepare a copper-gallium alloy film layer by in-situ deposition on the surface of the working electrode. The current density of the constant current electrodeposition was 0.1 A / cm 2 ;

[0022] The XRD patterns of the copper-gallium alloy films at different electrodeposition times in this embodiment are shown in FIG. Figure 1 ,from Figure 1 It can be seen that the sample after electrodeposition is a phase of copper-gallium alloy (CuGa2) and a phase of substrate copper, indicating that a layer of copper-gallium alloy film is formed on the surface of copper during the electrodeposition process.

[0023] The SEM and EDS images of the copper-gallium alloy film layer with an electrodeposition time of 0.5 h in this embodiment are shown in Figure 2 ,from Figure 2 It can be seen that the thickness of the copper-gallium alloy film layer prepared by electrodeposition on the sample surface is about 10 μm.

[0024] Example 2: A method for preparing a copper-gallium alloy by electrodeposition, the specific steps are as follows:

[0025] (1) adding metallic gallium to a sodium hydroxide solution having a mass concentration of 5%, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; wherein the concentration of gallium ions in the alkaline gallium ion electrolyte is 0.5 g / L;

[0026] (2) A copper sheet was used as a working electrode and a platinum sheet was used as a counter electrode. Constant current electrodeposition was performed in an alkaline gallium ion electrolyte at room temperature for 1 h, and a copper-gallium alloy film layer was prepared by in-situ deposition on the surface of the working electrode. The current density of the constant current electrodeposition was 0.02 A / cm 2 ;

[0027] The SEM and EDS images of the copper-gallium alloy film layer after electrodeposition for 1 h in this embodiment are shown in Figure 3 ,from Figure 3 It can be seen that the thickness of the copper-gallium alloy film layer prepared by electrodeposition on the sample surface is about 5 μm.

[0028] Embodiment 3: A method for preparing a copper-gallium alloy film layer by electrodeposition, the specific steps are as follows:

[0029] (1) adding metallic gallium to a sodium hydroxide solution having a mass concentration of 15%, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; wherein the concentration of gallium ions in the alkaline gallium ion electrolyte is 3 g / L;

[0030] (2) A copper sheet was used as a working electrode and a platinum sheet was used as a counter electrode. Constant current electrodeposition was performed in an alkaline gallium ion electrolyte at room temperature for 4 h, and a copper-gallium alloy film layer was prepared by in-situ deposition on the surface of the working electrode. The current density of the constant current electrodeposition was 0.2 A / cm 2 ;

[0031] The SEM and EDS images of the copper-gallium alloy electrodeposited for 4 h in this embodiment are shown in Figure 4 ,from Figure 4 It can be seen that the thickness of the copper-gallium alloy film layer prepared by electrodeposition on the sample surface is about 15 μm.

[0032] Example 4: A method for preparing a copper-gallium alloy film layer by electrodeposition, the specific steps are as follows:

[0033] (1) adding metallic gallium to a sodium hydroxide solution having a mass concentration of 20%, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; wherein the concentration of gallium ions in the alkaline gallium ion electrolyte is 5 g / L;

[0034] (2) A copper sheet was used as a working electrode and a platinum sheet was used as a counter electrode. Constant current electrodeposition was performed in an alkaline gallium ion electrolyte at room temperature for 8 h, and a copper-gallium alloy film layer was prepared by in-situ deposition on the surface of the working electrode. The current density of the constant current charging method was 0.5 A / cm 2 ;

[0035] The SEM and EDS images of the copper-gallium alloy electrodeposited for 8 h in this embodiment are shown in Figure 5 ,from Figure 5 It can be seen that the thickness of the copper-gallium alloy film layer prepared by electrodeposition on the sample surface is about 20 μm.

[0036] The specific implementation modes of the present invention are described in detail above, but the present invention is not limited to the above implementation modes, and various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. A method for preparing a copper-gallium alloy film layer by electrodeposition, characterized in that: The specific steps are as follows: (1) adding metallic gallium to a sodium hydroxide solution, and subjecting the metallic gallium to ultrasonic treatment so that the metallic gallium is completely reacted and dissolved in the sodium hydroxide solution to obtain an alkaline gallium ion electrolyte; (2) Using a copper sheet as the working electrode and a platinum sheet as the counter electrode, a copper-gallium alloy film is prepared by in-situ deposition on the surface of the working electrode by constant current electrodeposition in an alkaline gallium ion electrolyte at room temperature for 0.5 to 12 hours.

2. The method for preparing a copper-gallium alloy film layer by electrodeposition according to claim 1, characterized in that: The mass concentration of the sodium hydroxide solution in step (1) is 5-20%.

3. The method for preparing a copper-gallium alloy film layer by electrodeposition according to claim 2, characterized in that: The concentration of gallium ions in the alkaline gallium ion electrolyte in step (1) is 0.5 to 5 g / L.

4. The method for preparing a copper-gallium alloy film layer by electrodeposition according to claim 1, characterized in that: The current density of step (2) constant current electrodeposition is 0.01 to 0.5 A / cm 2 .

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