Silicon wafer degumming agent and preparation method thereof

Abstract

The invention belongs to the technical field of silicon wafer processing, and discloses a silicon wafer degumming agent and a preparation method thereof. The silicon wafer degumming agent comprises the following components in parts by weight: 50-70 parts of lactic acid, 6-12 parts of citric acid, 10-15 parts of tartaric acid, 1-5 parts of a penetrant, 1-5 parts of an antibacterial agent, 1-8 parts of an organic solvent and 5-20 parts of water, the penetrating agent comprises nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether; the antibacterial agent comprises a phenol antibacterial agent and a quaternary ammonium salt antibacterial agent. The silicon wafer degumming agent provided by the invention can reduce the influence of reuse water with poor water quality stability on the degumming effect, inhibit the growth of microorganisms, improve the degumming effect and reduce the consumption of the silicon wafer degumming agent. Compared with a traditional degumming agent, the silicon wafer degumming agent provided by the invention can better meet the requirements of actual production and processing of silicon wafers.

Description

Technical Field

[0001] The invention belongs to the technical field of silicon wafer processing, and in particular relates to a silicon wafer degumming agent and a preparation method thereof. Background Art

[0002] Silicon wafer debonding agents are chemicals used to help separate silicon wafers (wafers) from their supporting frames or substrates during the semiconductor manufacturing process. The debonding agent needs to be able to effectively remove the adhesive between the silicon wafer and the frame without damaging the surface or internal microstructure of the silicon wafer. The selection and use of the debonding agent depends on many factors, including the material of the silicon wafer, the type of adhesive, the processing temperature, and the required debonding speed and efficiency. In the semiconductor industry, the selection and use of debonding agents is a delicate process step that needs to take into account environmental impact, cost-effectiveness, and the impact on product quality.

[0003] At present, the debonding process of solar silicon wafers is generally as follows: control the reasonable spraying pressure and time to remove impurities such as silicon powder, metal impurities, cutting fluid, etc. attached to the surface of the silicon wafer through physical spraying, and then soak the silicon wafer in a solution of a debonding agent of a certain concentration and temperature mixed with pure water or recycled water to soften and destroy the adhesive, and finally remove the residual adhesive impurities, silicon powder, and debonding agent on the surface of the silicon wafer through rinsing for a certain period of time, thereby achieving the debonding of the silicon wafer.

[0004] The cost of using pure water to mix silicon wafer degumming agent is very high, so in the actual production process, recycled water is often used to mix it. The recycled water used (such as the filter water of slicing wastewater) will contain trace metal ions, and its water quality stability is poorer than that of pure water, which will have a certain impact on the degumming effect of the degumming agent; and the recycled water has a high content of microorganisms. If it is recycled all the time, the solution discharged after the degumming agent solution is completed will contain a large number of microorganisms, which will bring great difficulties to subsequent recycling and reuse, and is not conducive to degumming.

[0005] Therefore, there is an urgent need to provide a silicon wafer degumming agent that can adapt to the water quality of recycled water, inhibit the growth of microorganisms, and reduce the impact of recycled water on the degumming effect. Summary of the invention

[0006] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a silicon wafer degumming agent and a preparation method thereof. The silicon wafer degumming agent provided by the present invention can adapt to the water quality of recycled water, inhibit the growth of microorganisms, and reduce the influence of recycled water on the degumming effect.

[0007] The invention provides a silicon wafer degumming agent.

[0008] Specifically, a silicon wafer degumming agent comprises the following components by weight: 50-70 parts of lactic acid, 6-12 parts of citric acid, 10-15 parts of tartaric acid, 1-5 parts of penetrant, 1-5 parts of antibacterial agent, 1-8 parts of organic solvent, and 5-20 parts of water; the penetrant comprises nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether; the antibacterial agent comprises phenolic antibacterial agent and quaternary ammonium salt antibacterial agent.

[0009] In some embodiments of the present invention, the silicon wafer degumming agent includes the following components by weight: 50-65 parts of lactic acid, 8-12 parts of citric acid, 10-15 parts of tartaric acid, 3-5 parts of penetrant, 1-5 parts of antibacterial agent, 1-8 parts of organic solvent and 5-15 parts of water.

[0010] In some embodiments of the present invention, the phenolic antimicrobial agent includes p-hydroxybenzoic acid esters and / or pentachlorophenol; the quaternary ammonium antimicrobial agent includes benzalkonium chloride and / or cetylpyridinium chloride.

[0011] In some embodiments of the present invention, the mass ratio of the phenolic antibacterial agent to the quaternary ammonium salt antibacterial agent is (0.3-3):1; preferably, the mass ratio of the phenolic antibacterial agent to the quaternary ammonium salt antibacterial agent is (0.5-2):1; further preferably, the mass ratio of the phenolic antibacterial agent to the quaternary ammonium salt antibacterial agent is (0.8-1.5):1.

[0012] In some embodiments of the present invention, the penetrant includes nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether. Preferably, the mass ratio of the nonylphenol polyoxyethylene ether to the octylphenol polyoxyethylene ether is (0.5-2):1.

[0013] In some embodiments of the present invention, the organic solvent is an alcohol, ester or ether solvent. Preferably, the organic solvent is selected from at least one of ethanol, isopropanol, ethyl acetate and diethyl ether.

[0014] In some embodiments of the present invention, the silicon wafer degumming agent further comprises 1-5 parts of a wetting agent by weight, wherein the wetting agent is one or more combinations of polyoxyethylene alcohol, polyoxyethylene stearate, and sodium lauryl acid.

[0015] In some embodiments of the present invention, the silicon wafer degumming agent further comprises 1-5 parts of a lubricant by weight.

[0016] In some embodiments of the present invention, the lubricant is a polyol polyether. Preferably, the lubricant is selected from polyethylene glycol and / or polypropylene glycol.

[0017] In some embodiments of the present invention, the pH value of the silicon wafer degumming agent ranges from 0.5 to 3.0, and the density ranges from 1.0 to 2.0 g / cm 3Preferably, the pH value of the silicon wafer degumming agent is in the range of 0.5-2.0, and the density is in the range of 1.0-1.5 g / cm 3 .

[0018] The invention also provides a method for preparing the silicon wafer degumming agent.

[0019] Specifically, a method for preparing a silicon wafer degumming agent comprises the following steps:

[0020] Lactic acid, tartaric acid, citric acid and water are mixed and dispersed; then the remaining components are added and dispersed to prepare a silicon wafer degumming agent.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The silicon wafer degumming agent provided by the present invention uses lactic acid, tartaric acid, and citric acid to construct an acidic system, and is used in combination with components such as penetrants, antibacterial agents, and organic solvents; and uses nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether as penetrants, and uses phenolic antibacterial agents and quaternary ammonium salt antibacterial agents as antibacterial agents to form a degumming agent system. The degumming system combines the antibacterial properties of phenolic antibacterial agents, quaternary ammonium salt antibacterial agents, and the properties of surfactants with the properties of acid solutions such as tartaric acid, and can reduce the influence of recycled water with poor water stability on the degumming effect, inhibit microbial growth, improve the degumming effect, and reduce the consumption of silicon wafer degumming agent. Compared with traditional degumming agents, the silicon wafer degumming agent provided by the present invention can better meet the needs of actual production and processing of silicon wafers.

[0023] (2) The silicon wafer degumming agent provided by the present invention can maximize the utilization rate of the degumming agent and is suitable for a variety of glue systems and degumming conditions. It has strong adaptability and a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a diagram showing the antibacterial effects of the silicon wafer degumming agents provided in Example 1, Example 2 and Comparative Example 3. DETAILED DESCRIPTION

[0025] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be noted that the following embodiments do not limit the protection scope of the present invention.

[0026] Unless otherwise specified, the raw materials, reagents or devices used in the following examples and comparative examples can be obtained from conventional commercial sources or by existing known methods.

[0027] Example 1

[0028] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0029] 54 parts of lactic acid, 10 parts of citric acid, 10 parts of tartaric acid, 2 parts of polyoxyethylene alcohol, 1.5 parts of nonylphenol polyoxyethylene ether, 1.5 parts of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 2 parts of pentachlorophenol, 3 parts of benzalkonium chloride, and 8 parts of deionized water.

[0030] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0031] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water are weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600r / min using a high-speed disperser, and then polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol, pentachlorophenol and benzalkonium chloride are added, and the dispersion is continued for 15 minutes until they are completely mixed to obtain a silicon wafer degumming agent.

[0032] Example 2

[0033] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0034] 58 parts of lactic acid, 9 parts of citric acid, 13 parts of tartaric acid, 2 parts of polyoxyethylene stearate, 1 part of nonylphenol polyoxyethylene ether, 2-octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 2 parts of parabens, 2 parts of cetylpyridinium chloride, and 8 parts of deionized water.

[0035] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0036] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water are weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600r / min using a high-speed disperser, and then polyoxyethylene stearate, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol, p-hydroxybenzoate and cetylpyridinium chloride are added, and the dispersion is continued for 15 minutes until the mixture is completely mixed to obtain a silicon wafer degumming agent.

[0037] Example 3

[0038] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0039] 70 parts of lactic acid, 6 parts of citric acid, 10 parts of tartaric acid, 2 parts of polyoxyethylene alcohol, 1 part of nonylphenol polyoxyethylene ether, 1 part of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 2 parts of pentachlorophenol, 3 parts of benzalkonium chloride, and 8 parts of deionized water.

[0040] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0041] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water are weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600r / min using a high-speed disperser, and then polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol, pentachlorophenol and benzalkonium chloride are added, and the dispersion is continued for 15 minutes until they are completely mixed to obtain a silicon wafer degumming agent.

[0042] Example 4

[0043] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0044] 54 parts of lactic acid, 10 parts of citric acid, 10 parts of tartaric acid, 2 parts of polyoxyethylene alcohol, 1.5 parts of nonylphenol polyoxyethylene ether, 1.5 parts of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 0.8 parts of pentachlorophenol, 4.2 parts of benzalkonium chloride, and 8 parts of deionized water.

[0045] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0046] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water are weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600r / min using a high-speed disperser, and then polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol, pentachlorophenol and benzalkonium chloride are added, and the dispersion is continued for 15 minutes until they are completely mixed to obtain a silicon wafer degumming agent.

[0047] Comparative Example 1

[0048] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0049] 54 parts of lactic acid, 10 parts of citric acid, 10 parts of oxalic acid, 2 parts of polyoxyethylene alcohol, 1.5 parts of nonylphenol polyoxyethylene ether, 1.5 parts of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 2 parts of pentachlorophenol, 3 parts of benzalkonium chloride, and 8 parts of deionized water.

[0050] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0051] The above-mentioned lactic acid, citric acid, oxalic acid and deionized water were weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600 r / min using a high-speed disperser. Then, polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol, pentachlorophenol and benzalkonium chloride were added and dispersed for 15 minutes until they were completely mixed to obtain a silicon wafer degumming agent.

[0052] Comparative Example 2

[0053] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0054] 54 parts of lactic acid, 10 parts of citric acid, 10 parts of tartaric acid, 2 parts of polyoxyethylene alcohol, 1.5 parts of nonylphenol polyoxyethylene ether, 1.5 parts of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 5 parts of benzalkonium chloride, and 8 parts of deionized water.

[0055] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0056] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water are weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600r / min using a high-speed disperser, and then polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropyl alcohol and benzalkonium chloride are added, and the dispersion is continued for 15 minutes until the mixture is completely mixed to obtain a silicon wafer degumming agent.

[0057] Comparative Example 3

[0058] A silicon wafer degumming agent, comprising the following components in parts by weight:

[0059] 54 parts of lactic acid, 10 parts of citric acid, 10 parts of tartaric acid, 2 parts of polyoxyethylene alcohol, 1.5 parts of nonylphenol polyoxyethylene ether, 1.5 parts of octylphenol polyoxyethylene ether, 3 parts of polyethylene glycol, 5 parts of isopropanol, 5 parts of pentachlorophenol, and 8 parts of deionized water.

[0060] A method for preparing a silicon wafer degumming agent comprises the following steps:

[0061] The above-mentioned lactic acid, citric acid, tartaric acid and deionized water were weighed and mixed, and dispersed for 30 minutes at room temperature and a speed of 600 r / min using a high-speed disperser, and then polyoxyethylene alcohol, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, polyethylene glycol, isopropanol and pentachlorophenol were added and dispersed for 15 minutes until they were completely mixed to obtain a silicon wafer degumming agent.

[0062] Product effect testing

[0063] 1. The silicon wafer degumming agent prepared in the embodiment and the comparative example was applied to silicon wafer degumming, and the degumming effect of the silicon wafer degumming agent mixed with recycled water (filtered water of slicing wastewater) was tested. After testing, the pH of the recycled water (filtered water of slicing wastewater) was 6.42, the COD value was 40 mg / L, and the Ni content was 0.12 mg / L.

[0064] 30L of the silicon wafer degumming agent prepared in the embodiment and the comparative example were measured respectively, and the working solution was prepared by mixing and diluting with recycled water at a volume ratio of 1:6. The pH value of the working solution ranged from 1.0 to 2.5. The working solution was added to the degumming tank of the degumming machine, and the working temperature was set to 55°C. According to the test results under the same test conditions, the test silicon wafer specification was 182mm in size and 130μm in thickness. When two consecutive knives failed to be removed, it was determined to be the degumming limit value.

[0065] The test results are shown in Table 1.

[0066] Table 1

[0067]

[0068]

[0069] As shown in Table 1, the silicon wafer degumming agent provided by the embodiment of the present invention has excellent degumming effect, can adapt to the degumming conditions with poor stability of recycled water quality, inhibit microbial growth, and reduce the impact of recycled water on the degumming effect; and can reduce the consumption of silicon wafer degumming agent, and the single-blade consumption is as low as 0.275 liters / blade. The silicon wafer degumming agent provided by the comparative example will be significantly affected by metal ions and microorganisms in the recycled water, not only the degumming effect is significantly deteriorated, but also the risk of microbial contamination is brought to the silicon wafer. Specifically, in comparative example 1, tartaric acid is not used, but oxalic acid is used instead. The system composed of oxalic acid, lactic acid, citric acid, phenolic antibacterial agent and quaternary ammonium salt antibacterial agent cannot effectively reduce the impact of recycled water quality on the degumming effect, and the single-blade consumption increases significantly. Comparative example 2 and comparative example 3 only use one of phenolic antibacterial agent or quaternary ammonium salt antibacterial agent, which cannot effectively reduce the impact of recycled water quality on the degumming effect. This is because the phenolic antibacterial agent and the quaternary ammonium salt antibacterial agent selected in the present invention have both antibacterial properties and surfactant characteristics. The combination of the two can achieve an effective antibacterial effect and a stabilizing effect on the degumming system.

[0070] 2. Take the above recycled water, as well as the working solution prepared by the silicon wafer degumming agent and recycled water in Example 1, Example 2, and Comparative Example 3, and conduct antibacterial test. After constant temperature culture for 48 hours, the growth of the colonies in each group is as follows: Figure 1 As shown, Figure 1 A in the middle is a plate where the recycled water is directly used for cultivation; Figure 1 B is a plate in which the working solution prepared by the silicon wafer degumming agent and recycled water in Comparative Example 3 is inoculated and cultured; Figure 1 C in the middle is a plate inoculated with the working solution prepared with the silicon wafer degumming agent and recycled water in Example 1 and then cultured; Figure 1 D in the middle is a plate inoculated with the working solution prepared with the silicon wafer degumming agent and recycled water in Example 2 and then cultured.

[0071] Depend on Figure 1 It can be seen that there are many microorganisms in the recycled water. The silicon wafer degumming agent provided by Examples 1 and 2 of the present invention can significantly inhibit the microorganisms in the recycled water, while the silicon wafer degumming agent provided by Comparative Example 3 has a certain antibacterial effect, but not as good as Examples 1 and 2 of the present invention.

[0072] From the above experiments, it can be seen that the silicon wafer degumming agent provided by the embodiment of the present invention has an excellent degumming effect, can adapt to the water quality of recycled water, inhibit the growth of microorganisms, and reduce the impact of recycled water on the degumming effect. Compared with traditional degumming agents, the silicon wafer degumming agent provided by the present invention can better meet the needs of actual production and processing of silicon wafers.

[0073] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A silicon wafer degumming agent, characterized in that: The invention comprises the following components by weight: 50-70 parts of lactic acid, 6-12 parts of citric acid, 10-15 parts of tartaric acid, 1-5 parts of penetrant, 1-5 parts of antibacterial agent, 1-8 parts of organic solvent and 5-20 parts of water; the penetrant comprises nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether; the antibacterial agent comprises phenolic antibacterial agent and quaternary ammonium salt antibacterial agent.

2. The silicon wafer degumming agent according to claim 1, characterized in that: The composition comprises the following components by weight: 50-65 parts of lactic acid, 8-12 parts of citric acid, 10-15 parts of tartaric acid, 3-5 parts of penetrant, 1-5 parts of antibacterial agent, 1-8 parts of organic solvent and 5-15 parts of water.

3. The silicon wafer degumming agent according to claim 1 or 2, characterized in that: The phenolic antibacterial agent includes p-hydroxybenzoic acid ester and / or pentachlorophenol; the quaternary ammonium salt antibacterial agent includes benzalkonium chloride and / or cetylpyridinium chloride.

4. The silicon wafer degumming agent according to claim 3, characterized in that: The mass ratio of the phenolic antibacterial agent to the quaternary ammonium salt antibacterial agent is (0.3-3):

1.

5. The silicon wafer degumming agent according to claim 4, characterized in that: The mass ratio of the phenolic antibacterial agent to the quaternary ammonium salt antibacterial agent is (0.5-2):

1.

6. The silicon wafer degumming agent according to claim 3 or 4, characterized in that: The penetrant comprises nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether; the mass ratio of the nonylphenol polyoxyethylene ether to the octylphenol polyoxyethylene ether is (0.5-2):

1.

7. The silicon wafer debonding agent according to claim 1 or 2, characterized in that: In terms of weight, the silicon wafer degumming agent also includes 1-5 parts of a wetting agent; the wetting agent is one or more combinations of polyoxyethylene alcohol, polyoxyethylene stearate, and sodium lauryl acid.

8. The silicon wafer degumming agent according to claim 1 or 2, characterized in that: The silicon wafer degumming agent further comprises 1-5 parts of lubricant by weight; the lubricant is polyol polyether.

9. The silicon wafer degumming agent according to claim 6, characterized in that: The pH value of the silicon wafer degumming agent ranges from 0.5 to 3.0, and the density ranges from 1.0 to 2.0 g / cm 3 .

10. The method for preparing a silicon wafer degumming agent according to any one of claims 1 to 9, characterized in that: The following steps are involved: Mix and disperse lactic acid, tartaric acid, citric acid and water; Then, the remaining components are added and dispersed to obtain the silicon wafer degumming agent.

Images