A gallium antimonide reduction protective agent and an oxidation prevention method

Abstract

The present invention belongs to the field of semiconductor materials, and specifically relates to a gallium antimonide reduction protective agent and an oxidation prevention method. The gallium antimonide reduction protective agent is prepared from a reducing agent and a solvent, the reducing agent is selected from one or more of sodium thiosulfate pentahydrate, sodium pyrosulfite, sodium bisulfite and sodium disulfite, and the solvent is water; the reducing agent accounts for 26-34% of the total weight of the gallium antimonide reduction protective agent, and the rest is water. The gallium antimonide reduction protective agent can be used as an immersion liquid to effectively remove the oxide layer on the surface of gallium antimonide in a short time, and add a protective layer on the surface of the gallium antimonide substrate, thereby achieving the protection of the gallium antimonide surface, solving the oxidation defects on the surface of gallium antimonide, and making gallium antimonide meet the production requirements without affecting subsequent processing.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductors, and in particular relates to a gallium antimonide reduction protective agent and an oxidation prevention method. Background Art

[0002] Gallium antimonide is a III-V compound semiconductor material composed of antimony and gallium. As it has a low dissociation pressure at the melting point, single crystals could be grown from chemical melts as early as the 1950s.

[0003] Gallium antimonide is widely used because of its excellent physical and chemical properties. Gallium antimonide heterojunction is a typical heterojunction structure composed of gallium antimonide and other III-V compound solid solutions. This heterojunction can be used to make optoelectronic devices with a spectral range of 2 to 5 μm. Such optoelectronic devices can be used in various engineering fields such as optical fiber communication, laser ranging, and photosensitive detection. Gallium antimonide-based avalanche photodiode (APD) has an independent absorption region (GaInAsSb) with a bandgap of 0.52 eV. This type of APD also has an avalanche multiplication region (PN junction). At room temperature, the multiplication factor of gallium antimonide-based APD is as high as 30 to 50, and the response time is less than 0.5ns. When the multiplication factor is 10, the limit noise coefficient of gallium antimonide-based APD is only 5 decibels. Gallium antimonide-based APD has great potential in manufacturing ultra-low noise optoelectronic devices and can be used in optical fiber communication systems or laser ranging systems.

[0004] Gallium antimonide is a narrow bandgap semiconductor material that can be used to prepare thermophotovoltaic cells that absorb infrared light (780nm~4000nm) and convert it into electrical energy. Compared with ordinary solar cells, the advantage of thermophotovoltaic cells is that they can get rid of the dependence of ordinary photovoltaic cells on sunlight and use infrared light emitted by fossil fuels, isotopes and nuclear energy to perform photovoltaic effects. The unit power generation of thermophotovoltaic cells is smaller in size, lighter in weight, and has higher performance. The thermophotovoltaic stacked cell made of overlapping GaAs and GaSb developed by Boeing in the United States has a photoelectric conversion efficiency of 36%, which will catch up with the efficiency of coal-fired power generation.

[0005] However, the surface of the GaSb substrate is chemically active, and oxidation will cause the oxide layer to be unable to be removed later. In the prior art, after physical grinding, the GaSb substrate will oxidize when placed in deionized water or in the air, resulting in failure to meet production requirements, so a process is needed to prevent oxidation of the surface of the GaSb substrate. Summary of the invention

[0006] Based on the above technical background, the present invention provides a gallium antimonide reduction protective agent and a method for preventing surface oxidation of gallium antimonide using the reduction protective agent. The gallium antimonide reduction protective agent is obtained by mixing one or more of sodium thiosulfate pentahydrate, sodium pyrosulfite, sodium bisulfite and sodium disulfite with water. The gallium antimonide reduction protective agent has simple components and can form a protective layer on the surface of a gallium antimonide substrate by immersion, isolating external oxidation factors, solving oxidation defects on the surface of the gallium antimonide substrate, and will not affect the subsequent production process of gallium antimonide. The anti-oxidation method is simple and efficient, thereby completing the present invention.

[0007] The first aspect of the present invention is to provide a gallium antimonide reduction protective agent, the gallium antimonide reduction protective agent is prepared from a reducing agent and a solvent, the reducing agent is selected from one or more of sodium thiosulfate pentahydrate, sodium pyrosulfite, sodium bisulfite and sodium disulfite, and the solvent is water;

[0008] The reducing agent accounts for 26-34% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

[0009] Preferably, the reducing agent is sodium thiosulfate pentahydrate.

[0010] Preferably, the reducing agent accounts for 30% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

[0011] The second aspect of the present invention is to provide a method for preventing surface oxidation of gallium antimonide by using the above-mentioned gallium antimonide reduction protective agent, the method comprising the following steps:

[0012] S1. Physically grinding the GaSb substrate to remove scratches on the GaSb surface, and then immersing it in a GaSb reduction protective agent;

[0013] S2. After soaking, the gallium antimonide substrate is rinsed with water, an acidic reagent, and water in sequence, and then dried.

[0014] In step S1, the soaking temperature is room temperature, and the soaking time is 2 to 8 hours.

[0015] In step S2, the acidic reagent is selected from one of hydrochloric acid, phosphoric acid, acetic acid and oxalic acid. Preferably, the acidic reagent is hydrochloric acid.

[0016] The drying speed is 500-2000 r / min, and the drying time is 120-240 s.

[0017] The beneficial effects of the present invention are:

[0018] (1) The gallium antimonide reduction protective agent of the present invention has simple ingredients, is non-toxic and harmless, and will not have adverse effects on humans and the environment during the gallium antimonide treatment process; and the gallium antimonide reduction protective agent has a good removal effect on the oxide layer on the surface of gallium antimonide. After physical grinding, a protective layer is formed on the surface of gallium antimonide through the reduction protection effect of the reduction protective agent. The protective layer can isolate external oxidizing factors. During subsequent processing, the protective layer is very easy to wash away and does not affect the subsequent processing of gallium antimonide. Therefore, while protecting the surface of gallium antimonide and preventing oxidation, it will not affect the subsequent production process of gallium antimonide;

[0019] (2) The gallium antimonide reduction protective agent and anti-oxidation method of the present invention can form a protective layer on the surface of gallium antimonide in a relatively short time, thereby solving the oxidation defects on the surface of the gallium antimonide substrate and achieving good anti-oxidation effect. DETAILED DESCRIPTION

[0020] The present invention will be described in detail below, and the characteristics and advantages of the present invention will become clearer and more distinct with the description.

[0021] The first aspect of the present invention is to provide a gallium antimonide reduction protective agent, which is prepared from a reducing agent and a solvent, wherein the reducing agent is selected from one or more of sodium thiosulfate pentahydrate, sodium pyrosulfite, sodium bisulfite and sodium disulfite, and the solvent is water.

[0022] Preferably, the reducing agent is sodium thiosulfate pentahydrate. When the reducing agent is sodium thiosulfate pentahydrate, the oxidation defects on the surface of gallium antimonide can be resolved in a shorter time.

[0023] According to a preferred embodiment of the present invention, the reducing agent accounts for 26-34% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

[0024] Preferably, the reducing agent accounts for 30% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

[0025] The proportion of reducing agent has a great influence on the reduction protection effect of the gallium antimonide surface. Experiments have found that when the reducing agent accounts for less than 25% or more than 35% of the total weight of the gallium antimonide reduction protection agent, the surface of gallium antimonide is severely oxidized. When the reducing agent accounts for the total weight of the reduction protection agent within the above range, no oxidation occurs on the surface of gallium antimonide.

[0026] The second aspect of the present invention is to provide a method for preventing surface oxidation of gallium antimonide using the gallium antimonide reduction protective agent described in the first aspect of the present invention, the method comprising the following steps:

[0027] S1. Physically grinding the GaSb substrate to remove scratches on the GaSb surface, and then immersing it in a GaSb reduction protective agent;

[0028] S2. After soaking, the gallium antimonide substrate is rinsed with water, an acidic reagent, and water in sequence, and then dried.

[0029] In step S1, the soaking temperature is room temperature, and the soaking time is 2 to 8 hours, preferably 3 to 6 hours.

[0030] The gallium antimonide reduction protective agent of the present invention can effectively treat the surface of gallium antimonide in a relatively short time, and effectively solve the oxidation defects on the surface of gallium antimonide.

[0031] In step S2, the acidic reagent is selected from one of hydrochloric acid, phosphoric acid, acetic acid and oxalic acid. Preferably, the acidic reagent is hydrochloric acid.

[0032] The spin-drying speed is 500-2000 r / min, preferably 1500 r / min.

[0033] The spin drying time is 120 to 240 seconds, preferably 180 seconds.

[0034] Example

[0035] The present invention is further described below by means of specific examples. These embodiments are only intended to illustrate the present invention but are not intended to limit the scope of the present invention.

[0036] The raw materials used in the embodiments of the present invention are all purchased.

[0037] Example 1

[0038] Mix 300g of sodium thiosulfate pentahydrate with 700mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 3 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0039] Example 2

[0040] Mix 260g of sodium thiosulfate pentahydrate with 750mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 3 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0041] Example 3

[0042] Mix 340g of sodium thiosulfate pentahydrate with 650mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 3 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0043] Example 4

[0044] Mix 300g of sodium disulfite with 700mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 5 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0045] Example 5

[0046] Mix 300g of sodium bisulfite with 700mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0047] Example 6

[0048] Mix 300g of sodium pyrosulfite with 700mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 4 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0049] Comparative Example

[0050] Comparative Example 1

[0051] Mix 100g of sodium thiosulfate pentahydrate with 900mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0052] Comparative Example 2

[0053] Mix 150g of sodium thiosulfate pentahydrate with 850mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0054] Comparative Example 3

[0055] Mix 200g of sodium thiosulfate pentahydrate with 800mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0056] Comparative Example 4

[0057] Mix 250g of sodium thiosulfate pentahydrate with 750mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0058] Comparative Example 5

[0059] Mix 350g of sodium thiosulfate pentahydrate with 650mL of water to obtain a gallium antimonide reduction protective agent. Physically grind the gallium antimonide substrate to remove the cutting line damage layer, place the ground substrate in the gallium antimonide reduction protective agent and soak it at room temperature for 6 hours, rinse the soaked gallium antimonide substrate with deionized water, and then clean it with hydrochloric acid. After cleaning, rinse the acidic reagent on the surface of gallium antimonide with deionized water in time. Finally, spin dry the cleaned gallium antimonide substrate at a speed of 1500r / min for 180s.

[0060] Experimental example

[0061] Experimental Example 1 GaSb Surface Test

[0062] The color difference of the gallium antimonide surface after oxidation protection of Example 1-6 and Comparative Example 1-5 was observed under the irradiation of fluorescent lamps. The surface without color difference is a qualified product. The observation results are shown in Table 1:

[0063] Table 1

[0064]

[0065] As can be seen from Table 1, after being treated by Examples 1-6 of the present invention, no oxidation occurs on the surface of gallium antimonide, while Comparative Examples 1-5 have different degrees of oxidation, indicating that the amount of sodium thiosulfate pentahydrate added has a greater impact on the oxidation of the surface of gallium antimonide. As the proportion of sodium thiosulfate pentahydrate in the reduction protective agent gradually increases, the defect of surface oxidation of gallium antimonide can be solved, but when it increases to a certain proportion, the balance between the reducing agent and water will be destroyed, resulting in re-oxidation of the surface of the gallium antimonide substrate. It also shows that the use of the reduction protective agent and treatment method described in the present invention can prevent oxidation of the surface of gallium antimonide, meeting the next production needs.

[0066] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

Claims

1. A gallium antimonide reduction protective agent, characterized in that: The gallium antimonide reduction protective agent is prepared from a reducing agent and a solvent, the reducing agent is selected from one or more of sodium thiosulfate pentahydrate, sodium pyrosulfite, sodium bisulfite and sodium disulfite, and the solvent is water; The reducing agent accounts for 26-34% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

2. The gallium antimonide reduction protective agent according to claim 1, characterized in that: The reducing agent is sodium thiosulfate pentahydrate.

3. The gallium antimonide reducing protective agent according to claim 1, characterized in that: The reducing agent accounts for 30% of the total weight of the gallium antimonide reducing protective agent, and the rest is water.

4. A method for preventing surface oxidation of gallium antimonide by using the gallium antimonide reduction protective agent according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: S1. Physically grinding the GaSb substrate to remove scratches on the GaSb surface, and then immersing it in a GaSb reduction protective agent; S2. After soaking, the gallium antimonide substrate is rinsed with water, an acidic reagent, and water in sequence, and then dried.

5. The method according to claim 4, characterized in that In step S1, The soaking temperature is room temperature, and the soaking time is 2 to 8 hours.

6. The method according to claim 4, characterized in that In step S2, The acidic agent is selected from one of hydrochloric acid, phosphoric acid, acetic acid and oxalic acid.

7. The method according to claim 6, characterized in that The acidic reagent is hydrochloric acid.

8. The method according to claim 4, characterized in that In step S2, The drying speed is 500-2000 r / min, and the drying time is 120-240 s.

Images