Semiconductor electronic chip cleaning agent, preparation method and application

Abstract

The invention provides a semiconductor electronic chip cleaning agent which is prepared from the following components in parts by weight: 30-45 parts of an alcohol ether solvent, 10-20 parts of an anionic surfactant, 3-8 parts of triethanolamine, 1-6 parts of a corrosion inhibitor, 5-15 parts of polyoxyethylene fatty acid ester and 40-60 parts of deionized water. The semiconductor electronic chip cleaning agent can remarkably improve the cleanliness of the surface of a chip and effectively remove various pollutants and small particles which are difficult to remove, meanwhile, a formed protective film has excellent anti-rust performance, the service life of the chip can be greatly prolonged, and the reliability and stability of electronic equipment are improved. In addition, the preparation method is simple and easy to implement, the used raw materials are low in cost and environmentally friendly, and the preparation method has good application prospects and economic value.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor material cleaning, specifically relating to a method for preparing and applying a semiconductor electronic chip cleaning agent. Background Technology

[0002] In the manufacturing process of semiconductor electronic chips, the cleanliness and rust prevention of the chip surface have a crucial impact on the overall performance and lifespan of the chip. Traditional cleaning methods, such as physical wiping or chemical solvent immersion, often fail to completely remove organic contaminants and tiny particulate impurities adhering to the chip surface. These residues can severely affect the chip's electrical performance and stability. Furthermore, during subsequent storage and use, the chip surface is prone to oxidation and corrosion due to exposure to oxygen and moisture in the air. This not only reduces the chip's operating efficiency but may also lead to premature chip failure, thereby affecting the reliability and lifespan of the entire electronic device.

[0003] Chinese patent CN116496851A discloses a semiconductor chip cleaning agent and its preparation method, comprising the following raw materials in the indicated mass percentages: 3-6% sulfonic acid-based fluorinated surfactant, 6-10% nonionic surfactant, 0.2-1% complexing agent, 0-3% ethanol, 3-8% diethylene glycol monobutyl ether, and the balance being deionized water. The preparation involves adding the sulfonic acid-based fluorinated surfactant and nonionic surfactant to deionized water and stirring; then adding ethanol and diethylene glycol monobutyl ether and stirring; finally adding the complexing agent and stirring again. The cleaning agent described in this invention primarily targets flux residues and other contaminants on semiconductor chips, which differ from photoresist residues. However, this invention is ineffective at cleaning certain specific organic contaminants (photoresist residues) and fine particulate impurities (SiO2, Al2O3, etc.). Furthermore, the sulfonic acid-based fluorinated surfactant is expensive, and the fluorine it contains can damage the ozone layer, which is detrimental to environmental protection.

[0004] Chinese patent CN112592769A discloses a low-VOC semiconductor chip cleaning agent and its preparation method. The cleaning agent has a pH value of 7.2-8.5 and a VOC content ≤100g / L. Its composition and weight percentages are: 3-80 parts alcohol ether solvent, 2-10 parts N-hydroxyethyl-2-pyrrolidone, 0.6-5 parts nonionic surfactant, 0.1-0.8 parts corrosion inhibitor, and 30-100 parts deionized water. It can effectively remove solder paste, flux, and solder paste residue from various semiconductor electronic devices, and also has a significant cleaning effect on flip chips and PCBAs. Although this invention can effectively remove various residues on semiconductor electronic chips, its rust prevention performance is poor, and its composition is relatively complex, with a cumbersome preparation process. Summary of the Invention

[0005] The purpose of this invention is to provide a semiconductor electronic chip cleaning agent that solves the problems of incomplete surface cleaning and insufficient rust protection of semiconductor electronic chips in the prior art by using specific solvents and preparation processes.

[0006] The semiconductor electronic chip cleaning agent prepared by this invention can significantly improve the cleanliness of the chip surface, effectively remove various difficult-to-remove contaminants and microparticles, and the protective film formed has excellent anti-rust properties, which can greatly extend the service life of the chip and improve the reliability and stability of electronic devices. Furthermore, the preparation method of this invention is simple and easy to implement, uses low-cost raw materials, and is environmentally friendly, showing good application prospects and economic value.

[0007] The technical solution of this invention is as follows: a semiconductor electronic chip cleaning agent, which is made of the following components by weight: 30-45 parts of alcohol ether solvent, 10-20 parts of anionic surfactant, 3-8 parts of triethanolamine, 1-6 parts of corrosion inhibitor, 5-15 parts of polyoxyethylene fatty acid ester, and 40-60 parts of deionized water.

[0008] Preferably, the alcohol ether solvent is a mixture of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of (1-4):(2-5). Propylene glycol ether solvent is characterized by strong dissolving power and slow evaporation rate, which is beneficial for improving the leveling properties of the film. If diethylene glycol monobutyl ether is used alone, the removal effect on photoresist and other residues is not significant; while propylene glycol ethyl ether, although having strong dissolving power, is insufficient in its synergistic effect with other components, failing to achieve the best comprehensive cleaning and rust prevention effect. This invention mixes diethylene glycol monobutyl ether and propylene glycol ethyl ether in a specific mass ratio, which can fully utilize the advantages of both, ensuring both strong dissolving power and effective removal of various contaminants on the chip surface. Furthermore, when combined with other components such as anionic surfactants, it can form a more uniform and stable cleaning system, laying the foundation for the subsequent formation of an excellent rust-preventive protective film on the chip surface.

[0009] More preferably, the diethylene glycol monobutyl ether and propylene glycol ethyl ether are in a mass ratio of 1:(1-2). Propylene glycol ethyl ether plays a dominant role in "dissolving contaminants", while diethylene glycol monobutyl ether assists in "system stability and film formation". When the ratio is unbalanced, insufficient propylene glycol ethyl ether leads to a lack of dissolving power, while excessive diethylene glycol monobutyl ether damages compatibility and film formation conditions, ultimately resulting in incomplete cleaning, system instability, and rust prevention failure. If the amount of diethylene glycol monobutyl ether is greater than that of propylene glycol ethyl ether, the following adverse results will occur: (1) The ability to dissolve and remove stubborn contaminants will be significantly reduced: The core function of propylene glycol ethyl ether is to provide strong dissolving power to effectively remove stubborn contaminants such as photoresist, flux residue, and organic polymers from the chip surface. When the amount of diethylene glycol monobutyl ether exceeds that of propylene glycol ethyl ether, the relative content of propylene glycol ethyl ether decreases, resulting in insufficient overall dissolving power of the mixed solvent, which cannot fully dissolve the above-mentioned contaminants. After cleaning, contaminants are easily left on the chip surface, affecting the performance of the semiconductor electronic chip. (2) Decreased stability of the cleaning system, prone to stratification or uneven dispersion: An imbalance in the ratio of diethylene glycol monobutyl ether to propylene glycol ethyl ether can disrupt the synergistic compatibility of the solvent with other components (such as anionic surfactants). The molecular structure of propylene glycol ethyl ether (containing ether bonds and hydroxyl groups) is well-matched with the hydrophilic and lipophilic groups of surfactants, which can help the surfactants disperse evenly; while diethylene glycol monobutyl ether is more lipophilic, and an excess will lead to uneven dispersion of surfactants in the solvent, which cannot effectively reduce the surface tension of the cleaning solution, thereby affecting the wettability of the cleaning solution on the chip surface and the ability of the cleaning solution to remove contaminants. At the same time, decreased system stability may cause stratification, precipitation or abnormal viscosity, resulting in local concentration fluctuations during the cleaning process and uneven cleaning effect.

[0010] Preferably, the anionic surfactant is sodium N-oleoyl-N-methyltaurate, which can effectively reduce the surface tension of the liquid, enhance the cleaning effect, and make it easier to remove contaminants and particles from the surface of semiconductor electronic chips.

[0011] The triethanolamine, as a pH adjuster, can effectively prevent the corrosion and oxidation of metals, thereby enhancing the rust-preventive properties of the cleaning agent.

[0012] Preferably, the corrosion inhibitor is citric acid, which can form a dense chelated protective film on the chip surface, blocking the contact path between corrosive media such as oxygen and moisture and the metal substrate, effectively inhibiting the corrosion reaction on the metal surface, and significantly improving the long-term rust prevention performance of the chip.

[0013] The polyoxyethylene fatty acid ester, acting as a dispersant, enables other components to be more uniformly dispersed in the solvent, preventing agglomeration and thus further improving the cleaning effect and the density of the film.

[0014] This invention achieves a dual effect of cleaning and rust prevention by optimizing the solvent ratio and adding specific functional additives. In particular, the synergistic effect of the anionic surfactant and triethanolamine significantly enhances the rust-preventive capabilities of the cleaning agent while improving cleaning efficiency. The anionic surfactant reduces surface tension, making it easier for contaminants to detach from the chip surface, while triethanolamine rapidly forms a protective film on the metal surface, isolating oxygen and moisture and preventing oxidation and corrosion. The two complement each other, ensuring both highly efficient cleaning and long-lasting rust protection. This synergistic effect not only improves cleaning effectiveness but also enhances rust prevention, overcoming the problems of incomplete cleaning and insufficient rust prevention in existing semiconductor electronic chip technologies.

[0015] A method for preparing a semiconductor electronic chip cleaning agent includes the following steps:

[0016] Add alcohol ether solvent to the reaction vessel and pre-stir at 200-400 r / min for 2-5 min at 30-40℃. Then add anionic surfactant and 50-90% water, and centrifuge at 500-700 r / min for 3-5 min to form a microemulsion system. Continue to add triethanolamine and corrosion inhibitor, stir evenly, and finally add polyoxyethylene fatty acid ester and the remaining water. Transfer to an ultrasonic disperser for 5-10 min, filter through a filter membrane, and let stand to obtain the desired semiconductor electronic chip cleaning agent.

[0017] This invention employs a high-speed centrifugation process to prepare microemulsions, breaking through conventional emulsification methods. This method promotes the directional alignment of surfactants to form stable micelles, thereby efficiently forming a microemulsion system with uniform particle size and thermodynamic stability. Compared with stirring, this "centrifugal emulsification" mode more easily avoids the problem of particle size distribution broadening caused by local shear unevenness, laying the foundation for the uniform dispersion of subsequent functional components.

[0018] A multi-stage synergistic dispersion mechanism combining anionic and nonionic surfactants with ultrasonic dispersion is employed. The system achieves functional synergy through the stepwise addition of different types of surfactants: first, anionic surfactant (sodium N-oleoyl N-methyltaurate) is centrifuged to form a microemulsion framework, providing initial emulsification and cleaning capabilities; subsequently, polyoxyethylene fatty acid ester (a nonionic surfactant) is added, and the HLB values ​​of the ionic and nonionic surfactants are combined to adjust the hydrophilic-lipophilic balance of the system, enhancing the penetration and removal of oil contaminants on the chip surface (cleaning function). After compounding, ultrasonic dispersion for 5 minutes further breaks down any potential agglomerates using the ultrasonic cavitation effect, allowing corrosion inhibitors and other components to be uniformly embedded in the microemulsion micelles, forming a "microemulsion-functional molecule" composite dispersion system, ensuring the uniformity of the film material formation on the chip surface.

[0019] High-speed centrifugation optimizes the particle size, distribution, and stability of microemulsions, improving the efficiency of alcohol-ether solvents and rust inhibitors, thereby enhancing cleaning and rust prevention. During high-speed centrifugation, the synergistic effect of centrifugal force and shear force significantly reduces the oil-water interfacial tension, promoting a tighter arrangement of N-oleoyl-N-methyltaurate sodium at the oil-water interface and dispersing the alcohol-ether solvent into smaller droplets. Compared to ordinary emulsions formed without centrifugal stirring (which have larger and unevenly distributed particles), microemulsions have a larger specific surface area and stronger penetration ability, enabling more thorough contact with tiny gaps and uneven areas on the chip surface. Through adsorption and dissolution, they efficiently remove organic contaminants and microparticles, reducing residue. High-speed centrifugation also promotes uniform distribution of rust inhibitors and strengthens the density of the rust-preventive film. The microemulsion system formed by high-speed centrifugation has higher stability (less prone to stratification or aggregation), allowing rust inhibitor molecules to be evenly distributed throughout the system with the tiny droplets. After cleaning, the rust inhibitor can adhere evenly to the chip surface and form a more complete monomolecular / multimolecular protective film through coordination bonds or physical adsorption, effectively blocking corrosive media such as water and oxygen from contacting the metal surface; while ordinary emulsions, due to their large particle size and uneven distribution, are prone to local insufficient concentration of rust inhibitor, resulting in defects in the film layer and an increased risk of rust.

[0020] This invention introduces a specific ratio of alcohol-ether solvent, triethanolamine organic base, and chelating corrosion inhibitor to form a dual dissolution system for both polar and non-polar contaminants. Triethanolamine disrupts the ester and ether bonds in photoresist molecules, causing them to peel off from the chip surface. The chelating corrosion inhibitor forms stable complexes with metal ions, enhancing the removal of metal oxide particles and forming a monomolecular protective film on the chip surface, effectively inhibiting subsequent oxidation reactions. Environmentally, this invention uses a fluorine-free surfactant, ensuring that the cleaning wastewater complies with the EU RoHS directive.

[0021] This invention also provides an application of a semiconductor electronic chip cleaning agent, wherein the semiconductor electronic chip comprises photoresist, comprising the following steps:

[0022] S1: Place the semiconductor electronic chip to be processed into a dual-frequency ultrasonic cleaning tank containing semiconductor electronic chip cleaning agent, and use alternating low frequency (25kHz) and high frequency (60kHz) ultrasonic cleaning (2min cycle each), cleaning time 5-10min;

[0023] S2: Perform a three-stage gradient rinse with deionized water (water temperatures of 35℃, 30℃, and 25℃, 1 minute for each stage), and then place it in a vacuum drying oven.

[0024] The beneficial effects of the present invention are as follows: (1) The method for preparing cleaning and anti-rust functional film materials provided by the present invention can effectively remove organic pollutants and microparticles on the surface of semiconductor electronic chips, thereby improving the cleanliness of the chips; (2) A layer of anti-rust film is formed on the surface of the chip, which can effectively prevent the chips from oxidizing and corroding during subsequent storage and use, thereby improving the performance and reliability of the chips; (3) The method of the present invention is simple and easy to implement, low in cost, environmentally friendly and pollution-free, and has good application prospects. The environmental protection is specifically manifested in the following ways: (a) The raw material components are degradable: The main components of the cleaning agent are alcohol ether solvents (low toxicity, good biodegradability), biodegradable taurine surfactants (anionic surfactants) and polyoxyethylene fatty acid esters (nonionic surfactants, biodegradability is usually >90%), which do not contain heavy metals, fluorides, highly volatile toxic solvents (such as benzene series) or difficult-to-degrade organic pollutants. The main components are water and easily biodegradable organic matter, which can be decomposed by microorganisms into CO2 and H2O, without long-term residual toxicity. (b) The preparation process has no harmful emissions: the cleaning process only uses deionized water to rinse, avoiding the introduction of heavy metal salts and phosphorus / nitrogen pollutants; the vacuum plasma activation uses inert argon gas, and there are no emissions of toxic gases (such as Cl2 and HF); the wastewater contains degradable components, is easy to treat, and does not produce recalcitrant organic deposits or heavy metal pollution, thus meeting the requirements of environmental protection and pollution-free. Detailed Implementation

[0025] To better understand the technical content of this invention, specific embodiments are provided below to further illustrate the invention.

[0026] Example 1

[0027] A semiconductor electronic chip cleaning agent is prepared as follows: 35 parts of an alcohol ether solvent composed of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of 5:5 are added to a reaction vessel. The mixture is pre-stirred at 200 r / min for 2 min under a water bath at 35°C. Then, 10 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water (total deionized water is 50 parts, with the initial addition accounting for 80%) are added. The mixture is then centrifuged at 500 r / min for 3 min to form a microemulsion system. 4 parts of triethanolamine and 3 parts of citric acid are added and stirred evenly. Finally, 5 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added. The mixture is then transferred to an ultrasonic disperser for 5 min, filtered through a 0.22 μm filter membrane, and allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0028] Comparative Example 1

[0029] A semiconductor electronic chip cleaning agent is prepared as follows: 35 parts of an alcohol ether solvent composed of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of 5:5 are added to a reaction vessel. The mixture is pre-stirred at 200 r / min for 2 min under a water bath at 35°C. Then, 10 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the mixture is stirred at 500 r / min for 3 min to form an emulsion system (non-centrifugal method). 4 parts of triethanolamine and 3 parts of citric acid are added and stirred evenly. Finally, 5 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added. The mixture is then transferred to an ultrasonic disperser for 5 min, filtered through a 0.22 μm filter membrane, and allowed to stand to obtain the semiconductor electronic chip cleaning agent.

[0030] Test Results: The semiconductor electronic chip cleaning agents prepared in Example 1 and Comparative Example 1 were applied to clean semiconductor electronic chips of the same size and with the same degree of contamination. After cleaning, the cleanliness of the chip surface was detected using a surface particle analyzer. It was found that the residual amount of organic contaminants and microparticles on the chip surface after cleaning in Example 1 was significantly lower than that in Comparative Example 1. Simultaneously, the rust prevention performance of the cleaned chips was tested. After placing the chips in a constant temperature and humidity chamber (temperature 40±1℃, relative humidity 95±3%) for 48 hours, the rust on the chip surface was observed. The results showed that the rust-preventive film formed in Example 1 resulted in a much less rusty chip than that in Comparative Example 1. These findings indicate that the semiconductor electronic chip cleaning agent prepared using a high-speed centrifugal process is superior to the cleaning agent obtained without centrifugal stirring in both cleaning effect and rust prevention performance.

[0031] Example 2

[0032] A semiconductor electronic chip cleaning agent is prepared as follows: 40 parts of an alcohol ether solvent composed of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of (5:5) are added to a reaction vessel. The mixture is pre-stirred at 200 r / min for 2 min under a water bath at 35°C. Then, 12 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the mixture is centrifuged at 500 r / min for 3 min to form a microemulsion system. 6 parts of triethanolamine and 4 parts of citric acid are added and stirred evenly. Finally, 8 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added. The mixture is then transferred to an ultrasonic disperser for 5 min, filtered through a 0.22 μm filter membrane, and allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0033] Example 3

[0034] A semiconductor electronic chip cleaning agent is prepared as follows: 45 parts of an alcohol ether solvent composed of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of (5:5) are added to a reaction vessel. The mixture is pre-stirred at 200 r / min for 2 min under a water bath at 35°C. Then, 15 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the mixture is centrifuged at 500 r / min for 3 min to form a microemulsion system. 5 parts of triethanolamine and 5 parts of citric acid are added and stirred evenly. Finally, 10 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added. The mixture is then transferred to an ultrasonic disperser for 5 min, filtered through a 0.22 μm filter membrane, and allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0035] Comparative Example 2

[0036] A semiconductor electronic chip cleaning agent is prepared as follows: 45 parts of diethylene glycol monobutyl ether solvent are added to a reaction vessel and pre-stirred at 200 r / min for 2 min under a 35°C water bath. Then, 15 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the speed is increased to 500 r / min for 3 min to form a microemulsion system. 5 parts of triethanolamine and 5 parts of citric acid are added and stirred evenly. Finally, 10 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added, and the mixture is transferred to an ultrasonic disperser for 5 min. After filtration through a 0.22 μm filter membrane, the mixture is allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0037] Comparative Example 3

[0038] A semiconductor electronic chip cleaning agent is prepared as follows: 45 parts of propylene glycol ethyl ether solvent are added to a reaction vessel and pre-stirred at 200 r / min for 2 min under a 35°C water bath. Then, 15 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the speed is increased to 500 r / min for high-speed centrifugation for 3 min to form a microemulsion system. 5 parts of triethanolamine and 5 parts of citric acid are added and stirred evenly. Finally, 10 parts of polyoxyethylene fatty acid ester and the remaining deionized water are added, and the mixture is transferred to an ultrasonic disperser for 5 min. After filtration through a 0.22 μm filter membrane, the mixture is allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0039] Example 4

[0040] Unlike Example 1, the amount of alcohol ether solvent was adjusted to 40 parts, while the weight parts of the remaining components remained the same, and the preparation method was the same.

[0041] Example 5

[0042] Unlike Example 1, 35 parts of alcohol ether solvent were prepared by mixing diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of 5:10, while the remaining components were prepared in the same weight proportions and by the same method.

[0043] Example 6

[0044] A semiconductor electronic chip cleaning agent is prepared as follows: 35 parts of an alcohol ether solvent composed of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of (5:5) are added to a reaction vessel. The mixture is pre-stirred at 200 r / min for 2 min under a water bath at 35°C. Then, 10 parts of sodium N-oleoyl N-methyl taurate and 40 parts of deionized water are added, and the mixture is centrifuged at 500 r / min for 3 min to form a microemulsion system. 8 parts of triethanolamine and 3 parts of citric acid are added and stirred evenly. Finally, 5 parts of polyoxyethylene fatty acid ester and the remaining 10 parts of deionized water are added. The mixture is then transferred to an ultrasonic disperser for 5 min, filtered through a 0.22 μm filter membrane, and allowed to stand to obtain the desired semiconductor electronic chip cleaning agent.

[0045] Example 7

[0046] Unlike Example 1, 35 parts of alcohol ether solvent were prepared by mixing diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of 10:5, while the remaining components were prepared in the same weight proportions and by the same method.

[0047] The sources of each raw material component in the embodiments and comparative examples of this invention are as follows:

[0048] Alcohol and ether solvents: Diethylene glycol monobutyl ether was provided by Shanghai Yuanye Biotechnology Co., Ltd., purity: GC≥99%, catalog number: B65648-250mg; Propylene glycol ethyl ether was provided by Wuhan Beiguofeng Chemical Co., Ltd., CAS number: 1569-02-4 EINECS number: 216-374-5, purity 99%.

[0049] Sodium N-oleoyl N-methyl taurate: Manufacturer: Wuhan Smike Biotechnology Co., Ltd., CAS No.: 137-20-2, content: 99%, product number: 1869.

[0050] Triethanolamine: The manufacturer is Nanjing Kerunjiang Chemical Co., Ltd., CAS No.: 102-71-6, purity: 99.5%, EINECS No.: 203-049-8.

[0051] Citric acid: provided by Hunan Guangyi Biotechnology Co., Ltd., CAS No.: 77-92-9, product number: citric acid, EINECS No.: 201-069-1, purity 99%.

[0052] Polyoxyethylene fatty acid ester: Manufacturer is Linyi Guoli Chemical Co., Ltd., CAS No.: 90004-81-3, Model: Emulsifier LAE-4.

[0053] Cleaning effect test method: Prepare 10 sets of semiconductor electronic chips of the same size to be treated, and wipe off the surface oil with ethanol solvent. After evenly coating the chip surface with artificial oil, measure its weight and record it as W1. Weigh 500mL of semiconductor electronic chip cleaning agent from the examples and comparative examples and pour it into an ultrasonic cleaner. Clean 7 sets of chips respectively, ultrasonically clean for 5 minutes at room temperature, then rinse with deionized water for 1 minute, blow dry with nitrogen, and measure the weight of each, record it as W2. Observe the chip surface under a 1000X metallographic microscope. Calculate the cleaning effect: Cleaning effect = (W1-W2) / W1x100%. The larger the value, the better the cleaning effect of the cleaning agent on the chip.

[0054] Rust prevention performance test method: Ten sets of semiconductor electronic chip samples, after being cleaned and dried, were placed in a constant temperature and humidity chamber (temperature 40±1℃, relative humidity 95±3%) for periodic damp heat exposure testing. The test adopted a periodic exposure method, with each cycle lasting 48 hours (i.e., 2 days). After each exposure cycle, the samples were removed, and the surface morphology of the chip surface and key areas such as slits was observed using a scanning electron microscope (SEM) at 2000X magnification. The number of exposure cycles during which the first corrosion point was observed was recorded. Rust prevention performance is expressed as the cumulative time (days) during which the sample first showed corrosion points in a damp heat environment, calculated as: Cumulative days = Number of exposure cycles × 2 (days / cycle). The longer the number of days, the better the rust prevention performance.

[0055] Common and difficult-to-clean organic contaminants in semiconductor electronic chip manufacturing include photoresist residues (such as resin in the photoresist, simulating residues after photolithography), flux residues, and grease contaminants. This invention tests the cleaning effect of semiconductor electronic chip cleaning agents by removing photoresist residues.

[0056] Test method for cleaning effect of organic pollutants: Seven sets of photoresist residue samples were prepared: Semiconductor electronic chips were ultrasonically cleaned (acetone → isopropanol → deionized water), dried, coated with commercial photoresist (AZ 1500), and pre-baked (80℃, 30s) to form a 500nm thick film to simulate post-photolithography residue. The samples were cleaned in the semiconductor electronic chip cleaning agent obtained in the examples and comparative examples, rinsed with deionized water for 1 min, and then dried with nitrogen. The thickness of photoresist residue on the chip surface was measured using an ellipsometry, and the data were recorded.

[0057] Test method for cleaning effect of fine particulate impurities: Seven sets of cleaned semiconductor electronic chips were immersed in a particulate suspension (1% particulate aqueous solution, ultrasonically dispersed for 30 min) to form a uniform particulate contamination layer on the surface. After drying, the initial particle count N0 was recorded. The chips were then cleaned in the semiconductor electronic chip cleaning agents obtained in the examples and comparative examples, rinsed with deionized water for 1 min, and dried with nitrogen. The particle count N1 was detected using a surface particle analyzer, and the particle removal rate was calculated as (N0-N1) / N0×100%. The data was recorded.

[0058] The cleaning and rust prevention performance test results of this semiconductor electronic chip cleaning agent are shown in Table 1.

[0059] Table 1. Test results of cleaning and rust prevention effects in various embodiments and comparative examples.

[0060] project Cleaning effect Cleaning effectiveness Rust prevention performance (days) Example 1 There are virtually no contaminants on the chip surface and in the slits. 99.3% 316 Example 2 There are virtually no contaminants on the chip surface and in the slits. 99.5% 322 Example 3 The chip surface and slits are free of contaminants and have a bright luster. 99.7% 328 Example 4 The chip surface and slits are free of contaminants and have a bright luster. 99.4% 324 Example 5 The chip surface and slits are free of contaminants and have a bright luster. 99.8% 310 Comparative Example 1 The chip surface was free of contaminants, but there were stains in the slits. 98.0% 286 Example 6 The chip surface and slits are free of contaminants and have a bright luster. 99.8% 328 Example 7 The chip surface and slits are free of contaminants and have a bright luster. 98.1% 282 Comparative Example 2 The chip surface is contaminated, and there are obvious stains in the slits. 97.8% 280 Comparative Example 3 The chip surface has contaminants and is slightly whitish. 97.5% 274

[0061] The test results of this semiconductor electronic chip cleaning agent for cleaning specific organic pollutants and fine particulate impurities are shown in Table 2.

[0062] Table 2. Results of the material's cleaning effect on organic pollutants and fine particulate impurities.

[0063] project Cleaning effect of specific organic pollutants Cleaning effect of tiny particulate impurities Example 1 The residual thickness of photoresist on the chip surface is less than 55nm. Particle removal rate: 98.5% Example 2 The residual thickness of photoresist on the chip surface is less than 52nm. Particle removal rate: 98.7% Example 3 The residual thickness of photoresist on the chip surface is less than 47nm. Particle removal rate: 99.0% Example 4 The residual thickness of photoresist on the chip surface is less than 53nm. Particle removal rate: 98.6% Example 5 The residual thickness of photoresist on the chip surface is less than 50nm. Particle removal rate: 98.8% Comparative Example 1 The residual thickness of the photoresist on the chip surface is 80nm. Particle removal rate: 97.8% Example 6 The residual thickness of photoresist on the chip surface is less than 48nm. Particle removal rate: 98.8% Example 7 The residual thickness of the photoresist on the chip surface is 60nm. Particle removal rate: 98.5% Comparative Example 2 The residual thickness of the photoresist on the chip surface is 85nm. Particle removal rate: 97.5% Comparative Example 3 The residual thickness of the photoresist on the chip surface is 90nm. Particle removal rate: 97.2%

[0064] As shown in Table 1, Examples 3 and 6 both achieved a cleaning efficiency of over 99.7% and a rust prevention performance exceeding 328 days, significantly outperforming other examples and comparative examples. This indicates that the high-speed centrifugation process, by optimizing the microemulsion particle size distribution, makes the action of the alcohol ether solvent and rust inhibitor more efficient, thereby achieving a clean chip surface and slit areas free of contaminants and with a bright finish. In contrast, Comparative Examples 1 and 2, due to the lack of mixed alcohol ether solvents or the use of a single solvent, resulted in a cleaning efficiency below 98.0% and a rust prevention performance of less than 286 days, increasing the risk of stains or localized corrosion on the chip surface. In Example 7, although the adjustment of the alcohol ether solvent ratio (10:5) maintained the cleaning effect (cleaning efficiency 98.1%), the rust prevention performance decreased to 282 days, possibly due to uneven dispersion of the rust inhibitor.

[0065] As can be seen from the data in Table 1 for Examples 1, 2, 3, and 6, the cleaning efficiency increases with the increase of the alcohol ether solvent and the content of the anionic surfactant sodium N-oleoyl N-methyltaurate, and the rust prevention performance of the chip is also enhanced. This indicates that anionic surfactants play an important role in improving cleaning effect and rust prevention performance.

[0066] As shown in Table 2, Examples 1 to 3 showed excellent cleaning effects on specific organic pollutants, with the residual thickness of photoresist on the chip surface all being less than 55nm, among which Example 3 was the most outstanding, with a residual thickness of less than 47nm; in terms of cleaning of micro-particle impurities, the particle removal rate all exceeded 98.5%, with the highest reaching 99.0%.

[0067] Based on the test results of the above embodiments and comparative examples, the semiconductor electronic chip cleaning agent of the present invention exhibits significant advantages in both cleaning efficacy and rust prevention performance. The material in the embodiments can effectively remove contaminants from the chip surface and crevices, while forming a uniform and dense rust-preventive film layer, greatly extending the chip's service life.

[0068] Furthermore, the preparation method of this invention is simple and easy to implement, uses inexpensive raw materials, and is environmentally friendly, showing promising prospects for industrial application. In the future, the effects of different solvent systems and additive combinations on cleaning and rust prevention performance can be further explored to optimize material formulations and meet the cleaning and rust prevention needs of semiconductor electronic chips in different scenarios.

[0069] The above examples are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and should not be used to limit the scope of protection of the present invention.

Claims

1. A semiconductor electronic chip cleaning agent, characterized in that, It is made from the following components by weight: 30-45 parts alcohol ether solvent, 10-20 parts anionic surfactant, 3-8 parts triethanolamine, 1-6 parts corrosion inhibitor, 5-15 parts polyoxyethylene fatty acid ester, and 40-60 parts deionized water.

2. The semiconductor electronic chip cleaning agent according to claim 1, characterized in that, The alcohol ether solvent is a mixture of diethylene glycol monobutyl ether and propylene glycol ethyl ether in a mass ratio of (1-4):(2-5).

3. The semiconductor electronic chip cleaning agent according to claim 2, characterized in that, The diethylene glycol monobutyl ether and propylene glycol ethyl ether are in a mass ratio of 1:(1-2).

4. The semiconductor electronic chip cleaning agent according to claim 1, characterized in that, The anionic surfactant is sodium N-oleoyl N-methyltaurate.

5. The semiconductor electronic chip cleaning agent according to claim 1, characterized in that, The corrosion inhibitor is citric acid.

6. The method for preparing the semiconductor electronic chip cleaning agent according to claim 1, characterized in that, The steps are as follows: Add alcohol ether solvent to the reaction vessel and pre-stir at 200-400 r / min for 2-5 min at 30-40℃. Then add anionic surfactant and 50-90% water, and centrifuge at 500-700 r / min for 3-5 min to form a microemulsion system. Continue to add triethanolamine and corrosion inhibitor, stir evenly, and finally add polyoxyethylene fatty acid ester and remaining water. Transfer to an ultrasonic disperser for 5-10 min, filter through a filter membrane, and let stand to obtain the desired semiconductor electronic chip cleaning agent.

7. The application of the semiconductor electronic chip cleaning agent according to any one of claims 1-5 in the cleaning of semiconductor electronic chips.