A gallium antimonide surface cleaning liquid and a gallium antimonide substrate cleaning method

Abstract

The present invention belongs to the technical field of semiconductor materials, and specifically relates to a gallium antimonide surface cleaning liquid and a method for cleaning a gallium antimonide substrate using the cleaning liquid. The gallium antimonide surface cleaning liquid is obtained by mixing a detergent and water, the mass ratio of the detergent to water is (8-15):8, and the detergent is selected from one or more of ammonium hydroxide, ethanol, alcohol ether, acetone and isopropanol. The gallium antimonide surface cleaning liquid has high stability, no hydrophobic phenomenon occurs during the gallium antimonide cleaning process, and has a good effect on removing dirt and particle residues on the gallium antimonide surface without color difference. In addition, the cleaning method is simple, the cleaning time is short, the cleaning efficiency is high, and it has good application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor materials, and in particular relates to a gallium antimonide surface cleaning liquid and a gallium antimonide substrate cleaning method. Background Art

[0002] GaSb is a III-V compound semiconductor, belonging to zinc blende, direct bandgap material, with a bandgap width of 0.725eV (300K) and a lattice constant of 0.60959nm. GaSb has excellent physical and chemical properties and is often used as a substrate material, such as infrared detectors and lasers with a diameter of 8 to 14 mm and larger than 14 mm. In addition, Te-doped GaSb can be used to prepare thermophotovoltaic devices with high photoelectric conversion efficiency, laminated solar cells and microwave devices.

[0003] The main methods for preparing GaSb include the liquid-sealed Czochralski method (LEC method), hydrogen reduction method and other improved Czochralski methods, vertical gradient solidification method and vertical Bridgman method. The liquid-sealed Czochralski method and vertical Bridgman method are prone to cause an oxide film to appear on the surface of GaSb. To solve this problem, the double crucible method, liquid sealant method and gas protection method have been proposed in the literature. The most widely used growth method is the LEC method.

[0004] The surface of the gallium antimonide substrate is active and easily oxidized. A few nanometers of oxide layer can be quickly formed on the surface of the gallium antimonide that has just been treated in the air. Antimony oxide has disadvantages such as passivation and limited solubility. At the same time, the chemical reaction of gallium antimonide is difficult and the pH balance is extremely difficult. In the process of cleaning with acid and alkaline solutions, it is very easy for the substrate surface to be hydrophobic, dirty, have residual particles, and have surface color difference, thus failing to meet production requirements. Therefore, a gallium antimonide substrate surface cleaning solution and cleaning technology are needed to solve the above problems. Summary of the invention

[0005] Based on the above technical background, the present invention provides a gallium antimonide surface cleaning liquid and a method for cleaning a gallium antimonide substrate using the cleaning liquid. The gallium antimonide surface cleaning liquid is obtained by mixing one or more of ammonium hydroxide, ethanol, alcohol ether, acetone and isopropanol with water, wherein the mass ratio of one or more of ammonium hydroxide, ethanol, alcohol ether, acetone and isopropanol to water is (8-15):8. The gallium antimonide surface cleaning liquid obtained by mixing the above solvents with water according to the mass ratio has the advantage of high stability, and no hydrophobic phenomenon occurs during the cleaning process, which effectively solves the defects of dirt, particle residue and surface color difference during the gallium antimonide surface cleaning process, thereby completing the present invention.

[0006] The first aspect of the present invention is to provide a gallium antimonide surface cleaning solution, wherein the gallium antimonide surface cleaning solution is obtained by mixing a detergent and water, wherein the mass ratio of the detergent to water is (8-15):8,

[0007] The detergent is selected from one or more of ammonium hydroxide, ethanol, alcohol ether, acetone and isopropanol.

[0008] Preferably, the detergent is a mixture of a main detergent and a secondary detergent, the main detergent is one of ethanol, alcohol ether, acetone, and isopropanol, and the secondary detergent is ammonium hydroxide.

[0009] More preferably, the mass ratio of the main detergent to the secondary detergent is (5-10):3.

[0010] More preferably, the gallium antimonide surface cleaning solution is obtained by mixing ammonium hydroxide, ethanol and water in a mass ratio of 3:8:8.

[0011] A second aspect of the present invention is to provide a method for cleaning a gallium antimonide substrate using the gallium antimonide surface cleaning solution, the cleaning method comprising the following steps:

[0012] Step 1, fix the GaSb wafer to be cleaned, and then place it in a GaSb surface cleaning solution for cleaning;

[0013] Step 2: After cleaning, the surface of the GaSb wafer is sprayed with water and then the GaSb wafer is dried.

[0014] In step 1, the surface of the substrate is placed in a gallium antimonide surface cleaning solution and cleaned at 3 to 6° C. for 15 to 30 seconds.

[0015] In step 2, the spray flushing time is 30s to 90s.

[0016] The drying speed is 4000-5000 r / min, and the drying time is 45-90 s.

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

[0018] (1) The gallium antimonide surface cleaning solution of the present invention has simple ingredients, is non-toxic, and will not have adverse effects on the human body and the environment during use;

[0019] (2) The gallium antimonide surface cleaning liquid of the present invention has no hydrophobicity, can effectively remove dirt and particle residues on the surface of gallium antimonide, and will not have surface color difference. In addition, the gallium antimonide surface cleaning liquid has good stability and a service life of more than 8 hours;

[0020] (3) The cleaning method of the gallium antimonide substrate of the present invention is simple, and a good cleaning effect can be achieved through simple cleaning, and the cleaning time is short and the efficiency is high. DETAILED DESCRIPTION

[0021] 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.

[0022] The first aspect of the present invention is to provide a gallium antimonide surface cleaning solution, which is obtained by mixing a detergent and water, wherein the mass ratio of the detergent to water is (8-15):8, and preferably the mass ratio is (9-12):8.

[0023] The detergent is selected from one or more of ammonium hydroxide, ethanol, alcohol ether, acetone and isopropanol.

[0024] The surface cleaning liquid obtained by mixing the above detergent with water effectively solves the defects such as hydrophobicity, dirtiness, particle residue and surface color difference in the gallium antimonide cleaning process. The gallium antimonide cleaning liquid has high stability and a service life of more than 8 hours.

[0025] Preferably, the detergent is a mixture of a main detergent and a secondary detergent, the main detergent is one of ethanol, alcohol ether, acetone, and isopropanol, and the secondary detergent is ammonium hydroxide.

[0026] More preferably, the mass ratio of the main detergent to the secondary detergent is (5-10):3, and the preferred mass ratio is (6-9):3.

[0027] More preferably, the gallium antimonide surface cleaning solution is obtained by mixing ammonium hydroxide, ethanol and water in a mass ratio of 3:8:8.

[0028] The present invention adopts the mixed solvent in the above-mentioned mass ratio to effectively improve the cleanliness of the surface of gallium antimonide, and has high stability and a service life of more than 8 hours.

[0029] The second aspect of the present invention is to provide a method for cleaning a gallium antimonide substrate using the gallium antimonide surface cleaning solution described in the first aspect of the present invention, the cleaning method comprising the following steps:

[0030] Step 1, fix the GaSb wafer to be cleaned, and then place it in a GaSb surface cleaning solution for cleaning;

[0031] Step 2: After cleaning, the surface of the GaSb wafer is sprayed with water and then the GaSb wafer is dried.

[0032] In step 1, one of ethanol, alcohol ether, acetone and isopropanol is mixed with ammonium hydroxide and water to obtain a gallium antimonide surface cleaning solution.

[0033] The surface of the substrate is placed in a gallium antimonide surface cleaning solution at 3 to 6° C. for cleaning for 15 to 30 seconds. Preferably, the surface of the substrate is placed in a gallium oxide surface cleaning solution at 5° C. for cleaning for 30 seconds.

[0034] It is found through experiments that the cleaning solution for the surface of gallium antimonide of the present invention is used for cleaning at 5° C. for 30 seconds, which has a higher cleanliness degree for the surface of gallium antimonide.

[0035] In step 2, the spray flushing time is 30s to 90s, preferably 60s.

[0036] The drying is preferably carried out in a drying machine, and the drying speed is 4000-5000 r / min, preferably 4500-5000 r / min.

[0037] The spin drying time is 45 to 90 seconds, preferably 50 to 60 seconds.

[0038] Example

[0039] 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.

[0040] The raw materials used in the embodiments of the present invention are all purchased.

[0041] Example 1

[0042] Ammonium hydroxide, anhydrous ethanol and water are mixed in a mass ratio of 3:8:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after the fixation is completed, it is placed in a beaker filled with a gallium antimonide surface cleaning solution for cleaning. The cleaning time is 30 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0043] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0044] Example 2

[0045] Ammonium hydroxide, anhydrous ethanol and water are mixed in a mass ratio of 3:8:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after the fixation is completed, it is placed in a beaker filled with a gallium antimonide surface cleaning solution for cleaning. The cleaning time is 15 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0046] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0047] Example 3

[0048] Ammonium hydroxide, anhydrous ethanol and water are mixed in a mass ratio of 3:8:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after the fixation is completed, it is placed in a beaker filled with a gallium antimonide surface cleaning solution for cleaning. The cleaning time is 20 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0049] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0050] Example 4

[0051] Ammonium hydroxide, alcohol ether and water are mixed in a mass ratio of 3:7:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after the fixation is completed, it is placed in a beaker filled with a gallium antimonide surface cleaning solution for cleaning. The cleaning time is 30 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0052] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0053] Example 5

[0054] Ammonium hydroxide, acetone and water are mixed in a mass ratio of 3:6:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after fixing, it is placed in a beaker filled with gallium antimonide surface cleaning solution for cleaning. The cleaning time is 30 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0055] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0056] Example 6

[0057] Ammonium hydroxide, isopropanol and water are mixed in a mass ratio of 3:9:8 to obtain a gallium antimonide surface cleaning solution. The gallium antimonide wafer to be cleaned is fixed with a special fixture, and after the fixation is completed, it is placed in a beaker filled with a gallium antimonide surface cleaning solution for cleaning. The cleaning time is 30 seconds and the cleaning temperature is 5°C. During the cleaning process, the fixture is shaken evenly to allow the gallium antimonide surface to be evenly cleaned by the gallium antimonide surface cleaning solution.

[0058] After cleaning, the surface of the gallium antimonide wafer was quickly cleaned by spraying with deionized water for 60 seconds. During the spray cleaning process, the deionized water was ensured to evenly rinse the surface of the gallium antimonide wafer. After the spray cleaning was completed, the clamp was removed and the gallium antimonide wafer was placed in a single-chip spin dryer for spin drying. The spin drying speed was 4500r / min and the spin drying time was 50s.

[0059] Comparative Example

[0060] Comparative Example 1

[0061] The surface of gallium antimonide was cleaned in a manner similar to that of Example 1, except that hydrochloric acid, ammonium hydroxide, hydrogen peroxide and water were mixed in a mass ratio of 3:1:1:5 to obtain a cleaning solution.

[0062] Comparative Example 2

[0063] The surface of gallium antimonide was cleaned in a manner similar to that of Example 1, except that ammonium hydroxide, hydrogen peroxide and water were mixed in a mass ratio of 1:1:7 to obtain a cleaning solution.

[0064] Comparative Example 3

[0065] The surface of gallium antimonide was cleaned in a manner similar to that of Example 1, except that hydrofluoric acid, hydrochloric acid, hydrogen peroxide and water were mixed in a mass ratio of 1:3:0.5:6 to obtain a cleaning solution.

[0066] Experimental example

[0067] Experimental Example 1 Surface Detection

[0068] A 400,000 LUX strong light lamp was used to perform preliminary surface inspection on the gallium antimonide wafers after cleaning in Examples 1-6 and Comparative Examples 1-3, and finally the surface inspection was completed by metallographic microscope. The inspection results are shown in Table 1.

[0069] Table 1

[0070]

[0071] As can be seen from Table 1, the gallium antimonide surface cleaning solution used in Examples 1-6 has no hydrophobic phenomenon during the cleaning process, and there is no dirt, particle residue and color difference on the gallium antimonide surface after cleaning, while the cleaning solution used in Comparative Examples 1-3 is severely hydrophobic, has heavy particle residue and dirt, and has slight color difference on the surface. This shows that the gallium antimonide surface cleaning solution and cleaning method used in the present invention have good cleaning ability for the gallium antimonide surface, and can effectively solve the defects such as hydrophobicity, dirt, particle residue and surface color difference that occur during the cleaning process of the gallium antimonide surface.

[0072] 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 method for cleaning a gallium antimonide substrate using a gallium antimonide surface cleaning solution, characterized in that: The gallium antimonide surface cleaning solution is obtained by mixing a detergent and water, wherein the mass ratio of the detergent to water is (9-12):

8. The detergent is a mixture of a main detergent and a secondary detergent, the main detergent is one of anhydrous ethanol, alcohol ether, acetone, and isopropanol, and the secondary detergent is ammonium hydroxide; The mass ratio of the main detergent to the secondary detergent is (6-9):3; The cleaning method comprises the following steps: Step 1, fix the GaSb wafer to be cleaned, and then place it in a GaSb surface cleaning solution and clean it at 3-6°C for 15-30s; Step 2: After cleaning, the surface of the gallium antimonide wafer is sprayed with water for 30s to 90s, and then the gallium antimonide wafer is dried.

2. The cleaning method according to claim 1, characterized in that: The gallium antimonide surface cleaning solution is obtained by mixing ammonium hydroxide, anhydrous ethanol and water in a mass ratio of 3:8:

8.

3. The cleaning method according to claim 1, characterized in that: In step 2, The drying speed is 4000-5000 r / min, and the drying time is 45-90 s.

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