Environment-friendly cleaning process for semiconductor ceramic structure

Abstract

This invention discloses an environmentally friendly cleaning process for semiconductor ceramic structural components in the field of semiconductor precision component surface cleaning technology. The process uses deionized water, citric acid monohydrate, oxalic acid dihydrate, aminosulfonic acid, and sodium gluconate to prepare a weak acid base solution, and adds polyaspartic acid silane complex micelles, betaine tartaric acid corrosion inhibitor complex salts, alkyl glycoside aqueous solution, hydrogen peroxide aqueous solution, and ammonia to prepare a weak acid composite cleaning solution. After pretreatment, reverse purging, replenishment washing, immersion cleaning, rinsing, megasonic bleaching, isopropanol aqueous solution cleaning, spray rinsing, immersion rinsing, overflow rinsing, drying, and post-treatment, this process can remove polishing powder, alkaline deposits, particles, and organic residues from micropores, blind holes, grooves, and sealing surfaces of ceramic structural components under fluorine-free conditions, reducing cleaning corrosion and ion residues, and improving cleanliness and environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of surface cleaning technology for semiconductor precision components, and specifically relates to an environmentally friendly cleaning process for semiconductor ceramic structural components. Background Technology

[0002] Semiconductor ceramic structural components are widely used in wafer fabrication, vacuum adsorption, etching support, heat treatment support, insulation positioning, gas flow, and precision clamping processes. Common materials include alumina ceramics, aluminum nitride ceramics, silicon carbide ceramics, silicon nitride ceramics, and porous ceramics. These structural components typically possess high hardness, high heat resistance, high insulation, low thermal expansion, and good corrosion resistance. However, their surface and internal structures often exhibit complex morphologies such as micropores, blind holes, grooves, deep trenches, narrow slits, flow channels, mating surfaces, and sealing surfaces. During processing, grinding, polishing, sintering, assembly, and recycling, polishing powder, alkaline deposits, metal ions, organic additives, oil, particulate matter, and fine dust can easily remain on the ceramic surface. These contaminants can penetrate deep into pores and trenches and form an adhesive layer. If cleaning is not thorough, this can easily lead to particle shedding, ion contamination, adsorption failure, decreased insulation performance, and reduced process stability in subsequent semiconductor processes.

[0003] Existing cleaning methods for semiconductor ceramic structural components often employ a combination of processes, including alkaline degreasing, strong acid pickling, fluorinated acid pickling, ultrasonic rinsing, and hot air drying. While alkaline cleaning is effective at removing oil and some organic residues, its ability to remove alkaline inorganic deposits, oxide polishing powder, and particles within deep pores is limited. Strong acid systems, although improving the dissolution of inorganic scale, can easily corrode ceramic grain boundaries, surface roughness, and areas with metal inserts. Fluorinated acid pickling relies on etching to remove inorganic residues and has strong cleaning capabilities, but it suffers from problems such as fluoride ion residue, high wastewater treatment pressure, high environmental risk, and difficulty in completely removing residues within ceramic micropores. For porous ceramic vacuum chucks, ceramic clamps, and irregularly shaped ceramic flow channels, traditional single immersion or single ultrasonic methods are insufficient to simultaneously remove surface contaminants and clean internal pores, easily creating cleaning dead zones and particle redeposition.

[0004] As semiconductor manufacturing demands increasingly green, low-residue, and high-cleanliness standards, the cleaning process for ceramic structural components needs to achieve the synergistic removal of inorganic deposits, organic residues, and fine particles without relying on fluorine-containing highly corrosive systems. Weak acid complexation systems, due to their mild scaling, low corrosion, and easy rinsing properties, are gradually becoming an important alternative to fluorine-containing cleaning methods. However, single weak acid or ordinary surfactant systems still suffer from drawbacks such as insufficient complexing ability, weak microporous permeability, poor particle dispersion stability, inadequate corrosion inhibition protection for metal inserts, and inconsistent mass production performance. Therefore, it is necessary to develop an environmentally friendly cleaning process suitable for complex semiconductor ceramic structural components. This process should utilize the synergistic effects of weak acid compounding, complexation dispersion, corrosion inhibition protection, immersion cleaning, ultrasonic rinsing, megasonic fine rinsing, and multi-stage rinsing to improve the removal efficiency of contaminants in micropores, blind holes, deep grooves, and sealing surfaces while reducing corrosion and environmental burden. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of this invention is to provide an environmentally friendly cleaning process for semiconductor ceramic structural components.

[0006] This invention provides an environmentally friendly cleaning process for semiconductor ceramic structural components, comprising the following steps:

[0007] S1. By weight, mix 760.0-930.0 parts deionized water, 18.0-40.0 parts citric acid monohydrate, 5.0-15.0 parts oxalic acid dihydrate, 8.0-25.0 parts aminosulfonic acid and 5.0-20.0 parts sodium gluconate to obtain a weak acid base solution; add 1.5-7.0 parts polyaspartic acid silane complexing micelles, 1.0-6.0 parts betaine tartaric acid corrosion inhibitor complexing salt, and 0.8-5.0 parts alkyl glycoside aqueous solution to the weak acid base solution, continue mixing, add 1.5-9.0 parts hydrogen peroxide aqueous solution, adjust the pH with ammonia, filter, and obtain a weak acid composite cleaning solution;

[0008] S2. Pre-treat the surface of the semiconductor ceramic structural component to obtain a pre-cleaned structural component; use dry compressed air to blow along the machining texture of the pre-cleaned structural component in the reverse direction to obtain a blown structural component; use high-pressure deionized water to clean the micropores, blind holes, grooves, deep grooves, narrow slots, flow channels, mating surfaces and sealing surfaces of the blown structural component to obtain a pre-de-powdered structural component.

[0009] S3. The pre-de-powdered structural parts are soaked and cleaned with 80.0-160.0 parts of weak acid composite cleaning solution to obtain the rough-cleaned structural parts; the rough-cleaned structural parts are ultrasonically rinsed and mega-sound fine rinsing with deionized water to obtain the rinsed structural parts; the rinsed structural parts are scanned and cleaned line by line with high-pressure deionized water to obtain the repaired structural parts; the repaired structural parts are cleaned with isopropanol aqueous solution using mega-sound cleaning, and then sprayed, immersed, and overflow rinsed with deionized water in sequence, followed by drying and post-treatment.

[0010] In this invention, in the environmentally friendly cleaning process for semiconductor ceramic structural components, deionized water, citric acid monohydrate, oxalic acid dihydrate, aminosulfonic acid, and sodium gluconate are mixed to form a weakly acidic base solution. Citric acid monohydrate and oxalic acid dihydrate dissolve alkaline deposits, metal ions on the surface of polishing powder, and inorganic scale through carboxyl complexation. Aminosulfonic acid provides mild acidity and promotes the conversion of carbonate, oxide, and hydroxide residues into soluble or easily dispersible states. Sodium gluconate further complexes calcium, magnesium, iron, aluminum, and other ions and inhibits secondary deposition. When polyaspartic acid silane complex micelles are added to a weak acid base solution, their carboxylate structure adsorbs and encapsulates metal sites on the particle surface. The silane structure improves the wetting access to hydroxylated ceramic surfaces, and the hydrophobic segments help loosen oil stains and organic additive residues. Betaine tartaric acid corrosion-inhibiting complex salts reduce the corrosion risk of metal inserts and locally active surfaces under weak acid conditions through hydrogen bonding, polycarboxyl group complexation, and weak adsorption protection. Alkyl glycoside aqueous solutions reduce the interfacial tension of the weak acid composite cleaning solution, making it easier to penetrate micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces. Hydrogen peroxide aqueous solutions maintain high stability in a weak acid environment and are effective against organic residues and some reducing contaminants. A mild oxidation process is generated; ammonia is used to adjust the pH of the weak acid composite cleaning solution, so that the acid dissolution, complexation dispersion and corrosion inhibition protection are in a balanced state; dry compressed air reverse blowing removes loose particles first, and high-pressure deionized water replenishment wash removes free powder from the channels and grooves; immersion cleaning allows the weak acid composite cleaning solution to fully penetrate the complex structure and loosen the adhering contaminants; ultrasonic rinsing and mega-sound fine rinsing promote the desorption of particles from the ceramic surface and pores; line-by-line scanning replenishment wash removes local dead corner residues; isopropanol aqueous solution mega-sound cleaning reduces water film adhesion and organic residues; and then through spray rinsing, immersion rinsing, overflow rinsing, drying and post-treatment, a cleaning effect of low corrosion, low ion residue and fluorine-free environmental protection is obtained.

[0011] According to a preferred embodiment of the present invention, in step S1, the alkyl glycoside aqueous solution is a C8-C10 alkyl polysaccharide aqueous solution; the pH is adjusted to 3.2-4.6.

[0012] According to a preferred embodiment of the present invention, in step S2, the pressure of the drying compressed air is 0.15-0.35 MPa, the reverse purging time is 3-8 min, and the rewashing time is 10-40 s.

[0013] According to a preferred embodiment of the present invention, in step S3, the temperature of the soaking and cleaning is 35-45°C, the soaking and cleaning time is 10-18 min, the ultrasonic rinsing time is 3-8 min, the megason rinsing time is 3-6 min, and the line-by-line scanning replenishment time is 10-40 s.

[0014] According to a preferred embodiment of the present invention, the method for preparing the polyaspartic acid silane complex micelles includes:

[0015] A1. By weight, mix 28.0-34.0 parts of maleic anhydride and 34.0-40.0 parts of ammonium carbonate, pre-react at 60-90℃, then heat to 175-215℃ for polycondensation, cool, and pulverize to obtain crude polysuccinimide product; mix 90.0-150.0 parts of deionized water, 6.8-21.0 parts of sodium hydroxide, and 15.0-38.0 parts of crude polysuccinimide product, hydrolyze at 50-65℃, add glacial acetic acid, adjust the pH to 7.2-8.2, and obtain sodium polyaspartate base solution; 8.0-1 8.0 parts anhydrous ethanol, 1.5-4.5 parts γ-glycidyl etheroxypropyltrimethoxysilane, 2.0-7.0 parts deionized water and 0.05-0.30 parts glacial acetic acid are mixed and hydrolyzed at 20-30℃. Then, 0.8-3.5 parts C12-C14 alkyl glycidyl ether are added and mixed to obtain a silane hydrophobic pre-modified solution. 12.0-33.0 parts of the silane hydrophobic pre-modified solution are added to a sodium polyaspartate base solution, and the pH is adjusted to 7.8-8.8 with ammonia water. The mixture is stirred at 50-65℃ to obtain a crude solution of polyaspartate silane complex micelles.

[0016] A2. Mature 100.0-210.0 parts of the crude solution of polyaspartic acid silane complex micelles at 45-60℃, cool down to 25-35℃, add 0.05-0.20 parts of citric acid and 0.05-0.30 parts of activated carbon, stir, let stand to defoam, filter, concentrate and dry.

[0017] In this invention, during the preparation of polyaspartic acid silane complex micelles, maleic anhydride and ammonium carbonate undergo ring-opening, addition, and dehydration condensation reactions under heating conditions. A pre-reaction is first carried out at a lower temperature, where ammonium carbonate decomposes upon heating, releasing nitrogen-containing components and carbon dioxide. The nitrogen-containing components undergo nucleophilic addition and ring-opening with the maleic anhydride structure, generating maleamic acid and ammonium maleate salt intermediates. This ensures sufficient binding between the nitrogen-containing components and maleic anhydride, preventing the nitrogen-containing components from being violently volatilized and lost due to rapid heating, and avoiding material overflow caused by the melting and sublimation of maleic anhydride. Subsequently, the temperature is raised to enter the high-temperature condensation stage, where ammonium carbonate decomposes upon heating, releasing nitrogen-containing components and undergoing nucleophilic addition with the maleic anhydride structure, gradually forming a crude polysuccinimide product containing an imide ring structure. The resulting crude product, after cooling and pulverization, presents a reddish-brown, water-insoluble solid. The crude polysuccinimide product was mixed with deionized water and sodium hydroxide and subjected to alkaline hydrolysis under heating. The hydroxide ions provided by sodium hydroxide act as strong nucleophiles, attacking the carbonyl carbon atom in the imide ring, causing the imide ring to open and generating a sodium polyaspartate base solution containing sodium carboxylate and amide structures. The amount of sodium hydroxide was matched with the number of polysuccinimide units to ensure complete ring-opening hydrolysis of the imide ring and avoid residual cyclic imide groups that could affect subsequent complexation and dispersion capabilities. Since the system was in a strongly alkaline state after hydrolysis, glacial acetic acid was added to adjust the pH of the sodium polyaspartate base solution, transforming it from a strongly alkaline state to a weakly alkaline state suitable for subsequent composite modification. This prevented uncontrolled gel aggregation or excessively rapid ring-opening of epoxy groups due to localized rapid condensation of the silanol structure after the addition of the hydrophobic silane pre-modified solution caused by violent acid-base neutralization. Anhydrous ethanol, γ-glycidoxypropyltrimethoxysilane, deionized water, and glacial acetic acid are mixed. Glacial acetic acid acts as a weak acid catalyst to maintain the pH of the system within a weakly acidic range. The methoxy group in γ-glycidoxypropyltrimethoxysilane undergoes hydrolysis under weak acid catalysis and releases methanol, generating a pre-hydrolyzed product containing a silanol structure. Subsequently, C12-C14 alkyl glycidyl ether is added and mixed to introduce long-chain hydrophobic segments and epoxy active structures into the system. The epoxy groups attached to the long-chain alkyl groups do not undergo significant hydrolysis in this temperature range, thus obtaining a silane hydrophobic pre-modified liquid that combines silanol activity, epoxy activity, and hydrophobic segments. After adding a weakly alkaline sodium polyaspartate base solution to the silane hydrophobic pre-modified solution, the pH of the system transitions from a weakly acidic to a near-neutral region, avoiding the instantaneous strong-base condensation of silanol structures and the instantaneous rapid ring-opening of epoxy groups. Under the weakly alkaline environment regulated by ammonia and the action of heating and stirring, the epoxy groups in the silane hydrophobic pre-modified solution undergo ring-opening bonding with the carboxylates, carboxyl end groups, or hydroxyl groups generated by hydrolysis in the sodium polyaspartate base solution, causing silane segments and long-chain alkyl segments to be covalently grafted onto the sodium polyaspartate backbone. At the same time, some silanol structures undergo dehydration condensation to form a silicon-oxygen network, which further connects adjacent sodium polyaspartate segments. Long-chain alkyl structures form hydrophobic microregions through hydrophobic association, enabling the entire system to self-assemble into a micromicelle structure with both a hydrophilic shell and a hydrophobic core.The crude solution was matured to stabilize the three processes of covalent grafting, siloxane condensation, and hydrophobic association. Citric acid was then added to adjust the pH and inhibit excessive cross-linking. Activated carbon was added to adsorb trace colored impurities and unstable byproducts. After standing to defoam, filtration, concentration, and drying, polyaspartic acid silane complex micelles were obtained. These polyaspartic acid silane complex micelles possess carboxylate complexation sites, silane wetting sites, and hydrophobic dispersion sites, enabling them to redisperse in subsequent weakly acidic composite cleaning solutions and act on polishing powder, inorganic deposits, and organic residues.

[0018] According to a preferred embodiment of the present invention, in step A1, the pre-reaction time at 60-90°C is 1.0-2.0 h; the polycondensation time at 175-215°C is 1.5-3.5 h; the hydrolysis time at 50-65°C is 1.0-3.0 h; the stirring hydrolysis time at 20-30°C is 30-60 min; and the stirring time at 50-65°C is 2.0-5.0 h.

[0019] According to a preferred embodiment of the present invention, in step A2, the curing time at 45-60°C is 1.0-2.5h, the standing defoaming time is 1-3h, and the drying temperature is 60-85°C.

[0020] According to a preferred embodiment of the present invention, the preparation method of the betaine tartaric acid corrosion-inhibiting complex salt includes:

[0021] B1. By weight, mix 60.0-100.0 parts deionized water, 15.0-35.0 parts anhydrous betaine, 10.0-26.0 parts L-tartaric acid, 2.0-8.0 parts sodium gluconate and 1.0-4.0 parts glycerol, and stir at 40-55℃ to obtain a betaine-tartaric acid pre-complexing solution; add 1.0-4.0 parts sodium citrate, 0.5-2.0 parts polyethylene glycol 400 and 0.5-2.5 parts polyvinylpyrrolidone to the betaine-tartaric acid pre-complexing solution, and continue stirring to obtain a corrosion-inhibiting complexing base solution;

[0022] B2. Add 0.5-3.0 parts of anhydrous betaine to 85.0-180.0 parts of corrosion-inhibiting complexing base solution, adjust the pH to 3.6-4.6 with L-tartaric acid, mature at 60-80℃, cool to 25-35℃, add 0.05-0.20 parts of activated carbon, stir, let stand to defoam, filter, concentrate, dry, pulverize, and sieve.

[0023] In this invention, the formation of the betaine-tartaric acid corrosion-inhibiting complex salt mainly originates from the hydrogen bonding, acid-base pairing, complexation dispersion, and film-forming protection effects among anhydrous betaine, L-tartaric acid, sodium gluconate, glycerol, sodium citrate, polyethylene glycol 400, and polyvinylpyrrolidone. Anhydrous betaine possesses a quaternary ammonium inner salt structure, providing stable polar centers and carboxylate sites; L-tartaric acid, with its carboxyl and hydroxyl groups, can form hydrogen-bonded complexes and acid-base association structures with anhydrous betaine, giving the system weak acid buffering capacity and hydrophilic complexing ability; sodium gluconate contains polyhydroxyl groups and a carboxylate structure, enhancing the system's complexation ability for calcium, magnesium, iron, and aluminum ions and reducing the redeposition tendency of dissolved ions in ceramic channels; glycerol improves the system's homogeneity and aging stability through polyhydroxyl hydrogen bonding. When sodium citrate, polyethylene glycol 400, and polyvinylpyrrolidone are added to the betaine-tartaric acid pre-complexing solution, sodium citrate provides polycarboxyl complexation sites and forms a polyacid-polybase synergistic system with anhydrous betaine and L-tartaric acid. Polyethylene glycol 400 improves wetting and diffusion capabilities through ether oxygen bonds and terminal hydroxyl groups, while polyvinylpyrrolidone improves dispersion and protection through amide groups, thus maintaining good compatibility of the corrosion-inhibiting complexing base solution during subsequent concentration and drying processes. Anhydrous betaine was added to the corrosion-inhibiting complexing base solution, and the pH was adjusted to a weakly acidic state with L-tartaric acid. This partially protonated the sites of the anhydrous betaine carboxylate salt, further strengthening the hydrogen bond network and acid-base association stability between anhydrous betaine and L-tartaric acid. During the heating and aging process, sodium gluconate, sodium citrate, and L-tartaric acid jointly formed a multi-site complexing environment. Polyethylene glycol 400 and polyvinylpyrrolidone provided dispersion support, and activated carbon adsorbed trace colored impurities and unstable byproducts. After filtration, concentration, drying, pulverization, and sieving, the betaine-tartaric acid corrosion-inhibiting complexing salt was obtained.

[0024] According to a preferred embodiment of the present invention, in step B1, the stirring time at 40-55°C is 30-60 min.

[0025] According to a preferred embodiment of the present invention, in step B2, the curing time at 60-80°C is 1.0-3.0 h; the standing defoaming time is 1-3 h; and the drying temperature is 60-85°C.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) This invention uses citric acid monohydrate, oxalic acid dihydrate, aminosulfonic acid and sodium gluconate to construct a weak acid composite cleaning system, which can complex, dissolve and disperse the alkaline deposits, polishing powder, metal ion residues and inorganic scale on the surface of semiconductor ceramic structural parts without the use of fluorine-containing cleaning agents. Citric acid monohydrate, oxalic acid dihydrate and sodium gluconate form a multi-carboxyl complex environment, aminosulfonic acid provides mild acidity, hydrogen peroxide aqueous solution assists in the oxidation of organic residues, and alkyl glycoside aqueous solution improves wetting and penetration performance, so that the weak acid composite cleaning solution can enter micropores, blind holes, grooves, deep grooves, narrow gaps, flow channels, mating surfaces and sealing surfaces, reduce cleaning dead angles and improve the removal effect of pollutants in complex structures.

[0028] (2) This invention introduces polyaspartic acid silane complexing micelles and betaine tartaric acid corrosion-inhibiting complex salts to further improve the scale-complexing, dispersing, anti-redeposition, and corrosion-inhibiting capabilities of the weak acid cleaning system. The polyaspartic acid silane complexing micelles are prepared from maleic anhydride, ammonium carbonate, deionized water, sodium hydroxide, glacial acetic acid, anhydrous ethanol, γ-glycidyl etheroxypropyltrimethoxysilane, C12-C14 alkyl glycidyl ether, citric acid, and activated carbon, which can weaken the adhesion between particles and the ceramic surface. The betaine tartaric acid corrosion-inhibiting complex salt is prepared from deionized water, anhydrous betaine, L-tartaric acid, sodium gluconate, glycerol, sodium citrate, polyethylene glycol 400, polyvinylpyrrolidone, and activated carbon, which can complex dissolved ions and reduce the risk of localized acid corrosion.

[0029] (3) This invention employs a continuous process involving pretreatment, reverse blowing with dry compressed air, high-pressure deionized water rinsing, immersion cleaning with a weak acid composite cleaning solution, ultrasonic rinsing, megasonic rinsing, line-by-line scanning rinsing, megasonic cleaning with isopropanol aqueous solution, spray rinsing, immersion rinsing, overflow rinsing, drying, and post-treatment. This process gradually desorbs loose particles, pore residues, organic contaminants, and inorganic scale from the workpiece surface. This process is gentle on the ceramic substrate, reducing surface damage and dimensional deviations caused by strong corrosion cleaning. It also reduces ion and organic residues, improving the cleanliness, batch consistency, and environmental friendliness of semiconductor ceramic structural parts. It is suitable for cleaning porous ceramic parts, irregularly shaped ceramic parts, and precision ceramic components with complex pore and groove structures. Detailed Implementation

[0030] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0031] Example 1

[0032] This embodiment provides an environmentally friendly cleaning process for semiconductor ceramic structural components, including the following steps:

[0033] S1. Add 845.0g of deionized water to the cleaning tank, then add 29.0g of citric acid monohydrate, 10.0g of oxalic acid dihydrate, 16.5g of aminosulfonic acid, and 12.5g of sodium gluconate in sequence, and mix until completely dissolved to obtain a weak acid base solution. Add 4.25g of polyaspartic acid silane complexing micelles, 3.5g of betaine tartaric acid corrosion inhibitor complexing salt, and 2.9g of C8-C10 alkyl polysaccharide aqueous solution, wherein the mass fraction of C8-C10 alkyl polysaccharide aqueous solution is 50.0%, and continue mixing for 20min. Add 5.25g of hydrogen peroxide aqueous solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide aqueous solution is 30.0%, and adjust the pH to 3.9 with 1.8g of ammonia water, wherein the mass fraction of ammonia in the ammonia water is 25.0%. Filter with a 0.22μm filter membrane to obtain a weak acid composite cleaning solution.

[0034] S2. The surface of the semiconductor ceramic structural component is pretreated. The pretreatment process is as follows: First, use a dust-free wiping material to remove visible loose particles, edge attachments, and surface dust. Then, rinse the outer surface with 50.0g of deionized water to obtain a pre-cleaned structural component. Blow dry compressed air at a pressure of 0.25MPa along the machining texture of the pre-cleaned structural component in the opposite direction for 5.5 minutes. During blowing, the airflow passes through micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces in sequence to obtain a blown structural component. Use 100.0g of high-pressure deionized water to clean the micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces of the blown structural component for 25 seconds to obtain a pre-de-powdered structural component.

[0035] S3. The pre-de-powdered structural component is completely immersed in 120.0g of weak acid composite cleaning solution and soaked at 40℃ for 14min, turning it over once every 3min during soaking to obtain a rough-washed structural component; the rough-washed structural component is transferred to 150.0g of deionized water for ultrasonic rinsing for 5.5min at an ultrasonic frequency of 80kHz, and then transferred to 150.0g of deionized water for megaphonic fine rinsing for 4.5min at a megaphonic frequency of 1.0MHz to obtain a rinsed structural component; the rinsed structural component is then subjected to line-by-line scanning cleansing with 120.0g of high-pressure deionized water for 25s to obtain a cleaned structural component; 20.0g of isopropanol and 8 0.0g of deionized water was mixed to obtain an isopropanol aqueous solution, wherein the mass fraction of isopropanol in the isopropanol aqueous solution was 20.0%. The repaired structural parts were subjected to megasonic cleaning for 4.5 minutes with 100.0g of isopropanol aqueous solution at a megasonic frequency of 1.0MHz. Then, they were sprayed and rinsed with 120.0g of deionized water, immersed and rinsed with 150.0g of deionized water, and overflow rinsed with 180.0g of deionized water. Afterwards, they were dried at 80℃ for 40 minutes and cooled to 25℃ for post-treatment. The post-treatment involved checking the surface in a clean environment to ensure that there were no visible water marks, visible particles, or residual droplets before sealing and packaging.

[0036] Preparation steps of polyaspartic acid silane complex micelles:

[0037] A1. Add 31.0g of maleic anhydride and 37.0g of ammonium carbonate to a heat-resistant reaction vessel equipped with a condensation recovery device, mix until the solid material is evenly distributed, pre-react at 75℃ for 1.5h, then raise the temperature to 195℃ for condensation polymerization for 2.5h. After condensation polymerization, allow it to cool naturally to 25℃, pulverize the resulting solid using a pulverizer and pass it through a 250μm sieve to obtain crude polysuccinimide product. Dissolve 13.0g of sodium hydroxide in 120.0g of deionized water, and after the solution temperature drops to 30℃, add 26.5g of crude polysuccinimide product. Hydrolyze at 57.5℃ for 2.0h, keeping the material in uniform suspension during hydrolysis and gradually converting it into a homogeneous liquid. After hydrolysis, add 2.5g of ice. Acetic acid was used to adjust the pH to 7.7 to obtain a sodium polyaspartate base solution. 13.0 g anhydrous ethanol, 3.0 g γ-glycidyl etheroxypropyltrimethoxysilane, 4.5 g deionized water, and 0.18 g glacial acetic acid were mixed and hydrolyzed at 25 °C for 45 min. Then, 2.15 g C12-C14 alkyl glycidyl ether was added and mixed for another 10 min to obtain a silane hydrophobic pre-modified solution. 22.5 g of the silane hydrophobic pre-modified solution was added to the sodium polyaspartate base solution within 10 min, and the pH was adjusted to 8.3 with 1.6 g ammonia water (the ammonia mass fraction in the ammonia water was 25.0%). The mixture was stirred at 57.5 °C for 3.5 h to obtain a crude polyaspartate silane complex micelle solution.

[0038] A2. Take 155.0g of crude polyaspartic acid silane complex micelle solution, mature at 52.5℃ for 1.8h, cool to 30℃, add 0.13g of citric acid and 0.18g of activated carbon, stir for 30min until the activated carbon is evenly dispersed, let stand to defoam for 2h, filter with a 0.45μm pore size filter membrane to remove insoluble matter, concentrate the filtrate at 60℃ until the solids are in a viscous liquid state, dry at 72.5℃ to constant weight, cool to 25℃ to obtain polyaspartic acid silane complex micelles.

[0039] Preparation steps of betaine-tartaric acid corrosion-inhibiting complex salt:

[0040] B1. Add 80.0g deionized water, 25.0g anhydrous betaine, 18.0g L-tartaric acid, 5.0g sodium gluconate and 2.5g glycerol to a reaction vessel, and stir at 47.5℃ for 45min to completely dissolve the anhydrous betaine, L-tartaric acid and sodium gluconate to obtain a betaine-tartaric acid pre-complexing solution; add 2.5g sodium citrate, 1.25g polyethylene glycol 400 and 1.5g polyvinylpyrrolidone to the betaine-tartaric acid pre-complexing solution, and continue stirring for 60min to obtain a corrosion-inhibiting complexing base solution;

[0041] B2. Take 132.5g of corrosion-inhibiting complex base solution, add 1.75g ​​of anhydrous betaine, adjust the pH to 4.1 with 0.90g of L-tartaric acid, mature at 70℃ for 2.0h, cool to 30℃, add 0.13g of activated carbon, stir for 30min until uniformly dispersed, let stand to defoam for 2h, filter with a 0.45μm filter membrane to remove insoluble matter, concentrate the filtrate to a viscous liquid state at 60℃, dry at 72.5℃ to constant weight, pulverize, and pass through a 180μm sieve to obtain betaine-tartaric acid corrosion-inhibiting complex salt.

[0042] Example 2

[0043] This embodiment provides an environmentally friendly cleaning process for semiconductor ceramic structural components, including the following steps:

[0044] S1. Add 760.0g of deionized water to the cleaning tank, then add 18.0g of citric acid monohydrate, 5.0g of oxalic acid dihydrate, 8.0g of aminosulfonic acid and 5.0g of sodium gluconate in sequence, and mix until completely dissolved to obtain a weak acid base solution; add 1.5g of polyaspartic acid silane complexing micelles, 1.0g of betaine tartaric acid corrosion inhibitor complexing salt and 0.8g of C8-C10 alkyl polysaccharide aqueous solution, wherein the mass fraction of C8-C10 alkyl polysaccharide in the C8-C10 alkyl polysaccharide aqueous solution is 50.0%, continue mixing for 20min, add 1.5g of hydrogen peroxide aqueous solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide aqueous solution is 30.0%, adjust the pH to 3.2 with ammonia water, wherein the mass fraction of ammonia in the ammonia water is 25.0%, filter with a 0.22μm filter membrane to obtain a weak acid composite cleaning solution;

[0045] S2. The surface of the semiconductor ceramic structural component is pretreated. The pretreatment process is as follows: First, use a dust-free wiping material to remove visible loose particles, edge attachments, and surface dust. Then, rinse the outer surface with 50.0g of deionized water to obtain a pre-cleaned structural component. Use dry compressed air at a pressure of 0.15MPa to blow along the machining texture of the pre-cleaned structural component in the opposite direction for 3 minutes. During blowing, the airflow passes through micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces in sequence to obtain a blown structural component. Use 100.0g of high-pressure deionized water to rinse the micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces of the blown structural component for 10 seconds to obtain a pre-de-powdered structural component.

[0046] S3. Completely immerse the pre-de-powdered structural component in 80.0g of weak acid composite cleaning solution and soak and clean it at 35℃ for 10min, turning it over once every 3min during soaking to obtain a rough-cleaned structural component; transfer the rough-cleaned structural component to 150.0g of deionized water for ultrasonic rinsing for 3min at an ultrasonic frequency of 80kHz, then transfer it to 150.0g of deionized water for mega-sonic fine rinsing for 3min at a mega-sonic frequency of 1.0MHz to obtain a rinsed structural component; use 120.0g of high-pressure deionized water to perform line-by-line scanning cleansing on the rinsed structural component for 10s to obtain a cleaned structural component; add 20.0g of isopropanol and 80... Mix 0g of deionized water to obtain an isopropanol aqueous solution, wherein the mass fraction of isopropanol in the isopropanol aqueous solution is 20.0%. The repaired structural parts are subjected to megasonic cleaning for 3 minutes with 100.0g of isopropanol aqueous solution at a megasonic frequency of 1.0MHz. Then, they are sequentially rinsed with 120.0g of deionized water, immersed in 150.0g of deionized water, and overflow rinsed with 180.0g of deionized water. Afterward, they are dried at 80℃ for 40 minutes, cooled to 25℃, and then subjected to post-treatment. The post-treatment involves checking in a clean environment for visible watermarks, visible particles, and residual droplets before sealing and packaging.

[0047] Preparation steps of polyaspartic acid silane complex micelles:

[0048] A1. Add 28.0g of maleic anhydride and 34.0g of ammonium carbonate to a heat-resistant reaction vessel equipped with a condensation recovery device, mix until the solid material is evenly distributed, pre-react at 60℃ for 1.0h, then heat to 175℃ for condensation polymerization for 1.5h. After condensation polymerization, allow to cool naturally to 25℃, pulverize the resulting solid using a pulverizer and pass it through a 250μm sieve to obtain crude polysuccinimide product; Dissolve 6.0g of sodium hydroxide in 70.0g of deionized water, and after the solution temperature drops to 30℃, add 15.0g of crude polysuccinimide product, hydrolyze at 50℃ for 1.0h, keeping the material evenly suspended during hydrolysis and gradually converting it into a homogeneous liquid. After hydrolysis, add 0.5g of ice. Acetic acid was used to adjust the pH to 7.2 to obtain a sodium polyaspartate base solution. 8.0 g anhydrous ethanol, 1.5 g γ-glycidyl etheroxypropyltrimethoxysilane, 2.0 g deionized water, and 0.05 g glacial acetic acid were mixed and hydrolyzed at 20 °C for 30 min. Then, 0.8 g C12-C14 alkyl glycidyl ether was added and mixed for another 10 min to obtain a silane hydrophobic pre-modified solution. 12.0 g of the silane hydrophobic pre-modified solution was added to the sodium polyaspartate base solution within 10 min. The pH was adjusted to 7.8 with 0.6 g ammonia water (25.0% ammonia by mass). The mixture was stirred at 50 °C for 2.0 h to obtain a crude polyaspartate silane complex micelle solution.

[0049] A2. Take 100.0g of crude polyaspartic acid silane complex micelle solution, mature at 45℃ for 1.0h, cool to 25℃, add 0.05g citric acid and 0.05g activated carbon, stir for 30min until the activated carbon is evenly dispersed, let stand to defoam for 1h, filter with a 0.45μm filter membrane to remove insoluble matter, concentrate the filtrate at 60℃ until the solids are in a viscous liquid state, dry at 60℃ to constant weight, and cool to 25℃ to obtain polyaspartic acid silane complex micelles.

[0050] Preparation steps of betaine-tartaric acid corrosion-inhibiting complex salt:

[0051] B1. Add 60.0g deionized water, 15.0g anhydrous betaine, 10.0g L-tartaric acid, 2.0g sodium gluconate and 1.0g glycerol to a reaction vessel, and stir at 40℃ for 30min to completely dissolve the anhydrous betaine, L-tartaric acid and sodium gluconate to obtain a betaine-tartaric acid pre-complexing solution; add 1.0g sodium citrate, 0.5g polyethylene glycol 400 and 0.5g polyvinylpyrrolidone to the betaine-tartaric acid pre-complexing solution, and continue stirring for 30min to obtain a corrosion-inhibiting complexing base solution;

[0052] B2. Take 85.0g of corrosion-inhibiting complex base solution, add 0.5g of anhydrous betaine, adjust the pH to 3.6 with 0.30g of L-tartaric acid, mature at 60℃ for 1.0h, cool to 25℃, add 0.05g of activated carbon, stir for 30min until uniformly dispersed, let stand to defoam for 1h, filter with a 0.45μm filter membrane to remove insoluble matter, concentrate the filtrate at 60℃ to a viscous liquid state, dry at 60℃ to constant weight, pulverize, and pass through a 180μm sieve to obtain betaine-tartaric acid corrosion-inhibiting complex salt.

[0053] Example 3

[0054] This embodiment provides an environmentally friendly cleaning process for semiconductor ceramic structural components, including the following steps:

[0055] S1. Add 930.0g of deionized water to the cleaning tank, then add 40.0g of citric acid monohydrate, 15.0g of oxalic acid dihydrate, 25.0g of aminosulfonic acid, and 20.0g of sodium gluconate in sequence, and mix until completely dissolved to obtain a weak acid base solution; add 7.0g of polyaspartic acid silane complexing micelles, 6.0g of betaine tartaric acid corrosion inhibitor complexing salt, and 5.0g of C8-C10 alkyl polysaccharide aqueous solution, wherein the mass fraction of C8-C10 alkyl polysaccharide in the C8-C10 alkyl polysaccharide aqueous solution is 50.0%, continue mixing for 20min, add 9.0g of hydrogen peroxide aqueous solution, wherein the mass fraction of hydrogen peroxide in the hydrogen peroxide aqueous solution is 30.0%, adjust the pH to 4.6 with 3.2g of ammonia water, wherein the mass fraction of ammonia in the ammonia water is 25.0%, filter with a 0.22μm filter membrane to obtain a weak acid composite cleaning solution;

[0056] S2. The surface of the semiconductor ceramic structural component is pretreated. The pretreatment process is as follows: First, use a dust-free wiping material to remove visible loose particles, edge attachments, and surface dust. Then, rinse the outer surface with 50.0g of deionized water to obtain a pre-cleaned structural component. Use dry compressed air at a pressure of 0.35MPa to blow in the reverse direction along the processing texture of the pre-cleaned structural component for 8 minutes. During blowing, the airflow passes through micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces in sequence to obtain a blown structural component. Use 100.0g of high-pressure deionized water to clean the micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces of the blown structural component for 40 seconds to obtain a pre-de-powdered structural component.

[0057] S3. The pre-de-powdered structural component is completely immersed in 160.0g of weak acid composite cleaning solution and soaked at 45℃ for 18min, turning it over once every 3min during soaking to obtain a rough-washed structural component; the rough-washed structural component is transferred to 150.0g of deionized water for ultrasonic rinsing for 8min at an ultrasonic frequency of 80kHz, and then transferred to 150.0g of deionized water for megaphonic fine rinsing for 6min at a megaphonic frequency of 1.0MHz to obtain a rinsed structural component; the rinsed structural component is then subjected to line-by-line scanning cleansing with 120.0g of high-pressure deionized water for 40s to obtain a cleaned structural component; 20.0g of isopropanol and 80 Mix 0.0g of deionized water to obtain an isopropanol aqueous solution, wherein the mass fraction of isopropanol in the isopropanol aqueous solution is 20.0%. The repaired structural parts are subjected to megasonic cleaning for 6 minutes with 100.0g of isopropanol aqueous solution at a megasonic frequency of 1.0MHz. Then, they are sequentially rinsed with 120.0g of deionized water, immersed in 150.0g of deionized water, and overflow rinsed with 180.0g of deionized water. Afterward, they are dried at 80℃ for 40 minutes, cooled to 25℃, and then post-treated. The post-treatment involves checking in a clean environment for visible watermarks, visible particles, and residual droplets before sealing and packaging.

[0058] Preparation steps of polyaspartic acid silane complex micelles:

[0059] A1. Add 34.0g of maleic anhydride and 40.0g of ammonium carbonate to a heat-resistant reaction vessel equipped with a condensation recovery device, mix until the solid material is evenly distributed, pre-react at 90℃ for 2.0h, then raise the temperature to 215℃ for condensation polymerization for 3.5h. After the condensation polymerization is completed, allow it to cool naturally to 25℃, pulverize the resulting solid with a pulverizer and pass it through a 250μm sieve to obtain crude polysuccinimide product; Dissolve 17.0g of sodium hydroxide in 120.0g of deionized water, and after the solution temperature drops to 30℃, add 38.0g of crude polysuccinimide product, hydrolyze at 65℃ for 3.0h, keeping the material in uniform suspension during hydrolysis and gradually converting it into a homogeneous liquid. After the hydrolysis is completed, add 5.0g of... Glacial acetic acid was used to adjust the pH to 8.2 to obtain a sodium polyaspartate base solution. 18.0 g anhydrous ethanol, 4.5 g γ-glycidyl etheroxypropyltrimethoxysilane, 7.0 g deionized water, and 0.30 g glacial acetic acid were mixed and hydrolyzed at 30 °C for 60 min. Then, 3.5 g C12-C14 alkyl glycidyl ether was added and mixed for another 10 min to obtain a silane hydrophobic pre-modified solution. 33.0 g of the silane hydrophobic pre-modified solution was added to the sodium polyaspartate base solution within 10 min, and the pH was adjusted to 8.8 with 2.8 g ammonia water (ammonia mass fraction of 25.0%). The mixture was stirred at 65 °C for 5.0 h to obtain a crude polyaspartate silane complex micelle solution.

[0060] A2. Take 210.0g of crude polyaspartic acid silane complex micelle solution, mature at 60℃ for 2.5h, cool to 35℃, add 0.20g citric acid and 0.30g activated carbon, stir for 30min until the activated carbon is evenly dispersed, let stand to defoam for 3h, filter with a 0.45μm pore size filter membrane to remove insoluble matter, concentrate the filtrate at 60℃ until the solids are in a viscous liquid state, dry at 85℃ to constant weight, and cool to 25℃ to obtain polyaspartic acid silane complex micelles.

[0061] Preparation steps of betaine-tartaric acid corrosion-inhibiting complex salt:

[0062] B1. Add 100.0g deionized water, 35.0g anhydrous betaine, 26.0g L-tartaric acid, 8.0g sodium gluconate and 4.0g glycerol to a reaction vessel, and stir at 55℃ for 60min to completely dissolve the anhydrous betaine, L-tartaric acid and sodium gluconate to obtain a betaine-tartaric acid pre-complexing solution; add 4.0g sodium citrate, 2.0g polyethylene glycol 400 and 2.5g polyvinylpyrrolidone to the betaine-tartaric acid pre-complexing solution, and continue stirring for 90min to obtain a corrosion-inhibiting complexing base solution;

[0063] B2. Take 180.0g of corrosion-inhibiting complexing base solution, add 3.0g of anhydrous betaine, adjust the pH to 4.6 with 1.50g of L-tartaric acid, mature at 80℃ for 3.0h, cool to 35℃, add 0.20g of activated carbon, stir for 30min until uniformly dispersed, let stand to defoam for 3h, filter with a 0.45μm filter membrane to remove insoluble matter, concentrate the filtrate to a viscous liquid state at 60℃, dry at 85℃ to constant weight, pulverize, and pass through a 180μm sieve to obtain betaine-tartaric acid corrosion-inhibiting complexing salt.

[0064] Comparative Example 1

[0065] The difference between this comparative example and Example 1 is that 4.25g of polyaspartic acid silane complex micelles are not added in step S1, while the rest is the same as in Example 1.

[0066] Comparative Example 2

[0067] The difference between this comparative example and Example 1 is that 3.5g of betaine tartaric acid corrosion inhibitory complex salt is not added in step S1, while the rest is the same as in Example 1.

[0068] Comparative Example 3

[0069] The difference between this comparative example and Example 1 is that 4.25g of polyaspartic acid silane complex micelles and 3.5g of betaine tartaric acid corrosion inhibitory complex salt are not added in step S1; otherwise, it is the same as Example 1.

[0070] A series of standardized tests were conducted on the environmentally friendly cleaning processes of the semiconductor ceramic structural components described in Examples 1-3 and Comparative Examples 1-3, respectively.

[0071] Alumina semiconductor ceramic structural components from the same batch and in the same processing state were selected as test samples. The semiconductor ceramic structural components were alumina ceramic focusing rings with an outer diameter of 300 mm, an inner diameter of 200 mm, and a thickness of 8 mm. Five parallel samples were set in each group, with a single sample mass of 100.0 g. The sample surface was provided with micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces. Before testing, the sample surface and the hole and groove structure were rinsed with deionized water, dried at 80℃ for 40 min, cooled to 25℃, weighed, and the mass before cleaning was recorded. Alumina polishing powder, silica polishing powder, calcium carbonate, magnesium oxide, machining oil, and polyethylene glycol 400 were mixed in a mass ratio of 25:25:15:10:15:10. A small amount of deionized water was added to form a uniform paste of artificial contaminant. 0.50g of artificial contaminant was weighed for each sample and uniformly coated on the outer surface, micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces, and sealing surfaces. Fine needles were used to help the artificial contaminant penetrate into the micropores, blind holes, and narrow slits. After aging at 60°C for 2 hours, the mixture was cooled to 25°C and cleaned according to the processes of Examples 1, 2, 3, Comparative Examples 1, 2, and 3, respectively.

[0072] The particle count test was conducted as follows: After cleaning, rinsing, and drying, the sample was placed in a clean environment, and the number of particles ≥0.5μm was detected using a laser surface particle counting method. For each sample, one test area was selected from each of the micropore area, blind hole area, groove area, mating surface area, and sealing surface area, with each test area having an area of ​​1.0 cm². 2 Record the number of particles in 5 regions and calculate the average value of each individual sample. Then calculate the average value of each group of 5 samples. The result is expressed as particles / cm². 2 .

[0073] The alkaline sediment removal rate test was conducted as follows: Before cleaning, the contaminated and aged sample was placed in 200.0 mL of deionized water and shaken for 30 min for extraction. The titratable alkalinity of the extract was measured. After cleaning, the sample was placed in 200.0 mL of deionized water again and shaken for 30 min for extraction. The titratable alkalinity after cleaning was measured. The alkaline sediment removal rate was calculated based on the percentage decrease in titratable alkalinity before and after cleaning. The result is in units of .

[0074] The organic residue test was performed as follows: the washed and dried sample was placed in 200.0 mL of deionized water and extracted by shaking for 30 min. The total organic carbon content of the extract was measured, and the organic residue per unit area was calculated based on the effective contact area of ​​the sample. The result is expressed in ng / cm². 2 .

[0075] The total metal residue of Al, Ca, Mg, and Fe was tested as follows: The cleaned and dried sample was placed in 200.0 mL of 2% nitric acid aqueous solution and extracted by shaking at 40°C for 60 min. This ensured that all solid particles and ionic metals, including alumina polishing powder, silica polishing powder, calcium carbonate, and magnesium oxide, remaining on the sample surface and in the pores were dissolved into the extraction solution. After filtration through a 0.22 μm microporous membrane, the contents of Al, Ca, Mg, and Fe were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES) or ICP-AES mass spectrometry (ICP-MS). The contents of the four elements were summed, and the total metal residue per unit area was calculated based on the effective contact area of ​​the sample. The result was expressed in ng / cm². 2 .

[0076] The surface roughness change test was conducted as follows: Before cleaning, the contaminated and aged samples were sequentially degreased by immersion in 99.5% isopropanol for 30 seconds, rinsed with deionized water for 30 seconds, and purged with 99.999% high-purity nitrogen until the surface was completely dry. During the test, a white light interferometer was used to measure the three-dimensional surface morphology of the mating and sealing surfaces of the samples. Five fixed positions were selected on the mating surface and five fixed positions were selected on the sealing surface for each sample. The test area at each position was 0.5 mm × 0.5 mm, and the surface roughness Ra value before cleaning was recorded. After cleaning, rinsing, and drying, the pretreatment process of isopropanol degreasing, deionized water rinsing, and high-purity nitrogen purging was repeated for the samples. The surface roughness Ra value was measured again at the same fixed positions as before cleaning using a white light interferometer, and the Ra difference at the same position before and after cleaning was calculated. The average Ra difference of 10 positions on the mating and sealing surfaces for each group of 5 samples was calculated, and the result was expressed in μm.

[0077] The mass loss rate test was conducted as follows: Alumina ceramic focusing ring samples from the same batch, under the same processing condition, and without artificial contaminant coating were selected as corrosion test samples. Five parallel samples were set up for each group, with each sample weighing 100.0 g. The corrosion test samples were first dried at 120°C for 4 hours, then cooled to 25°C in a desiccator containing color-changing silica gel and weighed. They were then dried again at 120°C for 1 hour and cooled to 25°C before weighing. When the difference between two consecutive weighings was less than 0.1 mg, it was considered a constant weight, and this constant weight value was recorded as the mass before cleaning. The corrosion test samples were then cleaned, rinsed, and dried according to the same process flow as the contaminated samples (either the embodiment or comparative example). After treatment, the mass after cleaning was obtained by repeating the process of drying at 120°C for 4 hours, cooling and weighing, drying at 120°C for 1 hour, cooling and weighing, and determining constant weight. The mass loss rate was calculated based on the ratio of the difference in constant weight before and after cleaning to the constant weight before cleaning. The result is expressed in units of %.

[0078] All the above tests were conducted at 25℃ and 50%RH, and the resistivity of the deionized water used was not less than 18.0 MΩ·cm.

[0079] The performance test data above are shown in Table 1.

[0080] Table 1 Performance Test Results

[0081] Test Project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 <![CDATA[Number of particles ≥ 0.5μm (particles / cm 2 )]]> 18 32 25 86 43 138 Alkaline sediment removal rate (%) 99.3 98.6 98.8 93.6 98.1 90.8 <![CDATA[Organic residue amount (ng / cm 2 )]]> 4.6 7.9 6.1 18.7 8.5 27.4 <![CDATA[Total metal ion residue of Al, Ca, Mg, Fe (ng / cm 2 )]]> 2.8 5.4 4.1 8.9 16.8 24.6 Surface roughness change (μm) 0.004 0.006 0.007 0.009 0.018 0.026 Quality loss rate (%) 0.006 0.009 0.011 0.014 0.032 0.041

[0082] As can be seen from the above, Examples 1-3, compared with Comparative Examples 1-3, can simultaneously reduce particle residue, organic residue, metal ion residue, surface roughness change and mass loss rate, while maintaining a high alkaline deposit removal rate. This indicates that the present invention solves the technical problems of insufficient removal of contaminants in micropores, blind holes, grooves, deep grooves, narrow slits, flow channels, mating surfaces and sealing surfaces, particle redeposition after cleaning, insufficient complexing and dispersion ability of weak acid systems, and high risk of cleaning corrosion in the cleaning of existing semiconductor ceramic structural parts.

[0083] The number of particles ≥0.5μm in Example 1 was 18 / cm. 2 It is significantly lower than the 86 cells / cm of Comparative Example 1. 2 Compared to 138 per cm in Comparative Example 3 2 This indicates that polyaspartic acid silane complex micelles can enhance the wetting, stripping, complexing and dispersing effects of weak acid composite cleaning solution on polishing powder and fine particles, and reduce particle residue in ceramic pore structures.

[0084] The organic residue in Example 1 was 4.6 ng / cm³. 2 It was lower than the 18.7 ng / cm³ of Comparative Example 1. 2 Compared with Comparative Example 3, 27.4 ng / cm 2 This also indicates that the hydrophobic dispersion structure in polyaspartic acid silane complex micelles, when combined with aqueous solutions of alkyl glycosides and hydrogen peroxide, has a better removal effect on machining oils, organic additives, and attached contaminants.

[0085] The total residual metal ions of Al, Ca, Mg, and Fe in Example 1 were 2.8 ng / cm³. 2 It was significantly lower than the 16.8 ng / cm³ of control example 2. 2 Compared with Comparative Example 3, 24.6 ng / cm 2 This indicates that betaine-tartaric acid corrosion-inhibiting complex salts can enhance the complexation stability of metal ions and prevent redeposition.

[0086] The surface roughness change in Example 1 was 0.004 μm and the mass loss rate was 0.006%, both lower than those in Comparative Examples 2 and 3, indicating that the betaine tartrate corrosion inhibitor complex salt can reduce the risk of local acid corrosion and surface damage during weak acid cleaning.

[0087] In Comparative Example 1, the lack of polyaspartic acid silane complex micelles significantly increased the number of particles and the amount of organic residue, indicating that the simple weak acid complex system was insufficient for dispersing and removing fine particles and organic residues.

[0088] In Comparative Example 2, the lack of betaine-tartaric acid corrosion-inhibiting complex salt significantly increased the residual amount of metal ions, the change in surface roughness, and the mass loss rate, indicating that the lack of corrosion-inhibiting complex components weakens ion stability and surface protection capabilities.

[0089] Comparative Example 3, lacking both polyaspartic acid silane complex micelles and betaine tartaric acid corrosion inhibitory complex salts, showed the most significant deterioration in all indicators. This indicates that polyaspartic acid silane complex micelles and betaine tartaric acid corrosion inhibitory complex salts have a synergistic effect in a weak acid composite cleaning system, which can achieve efficient decontamination, low residue, low corrosion, and consistent cleaning of complex structures under fluorine-free and mild conditions.

Claims

1. An environmentally friendly cleaning process for semiconductor ceramic structural components, characterized by the following steps: include: S1. By weight, deionized water, citric acid monohydrate, oxalic acid dihydrate, aminosulfonic acid and sodium gluconate are mixed to obtain a weak acid base solution. Add polyaspartic acid silane descaling micelles, betaine tartaric acid corrosion inhibitor complex salt, and alkyl glycoside aqueous solution to a weak acid base solution, continue mixing, add hydrogen peroxide aqueous solution, adjust pH, filter, and obtain a weak acid composite cleaning solution. S2. The surface of the semiconductor ceramic structural component is pretreated, purged with compressed air, and washed with high-pressure deionized water in sequence to obtain a pre-de-powdered structural component. S3. Soak and clean the pre-de-powdered structural parts with a weak acid composite cleaning solution to obtain rough-cleaned structural parts; wash, dry and post-treat the rough-cleaned structural parts.

2. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 1, characterized in that, In step S1, the amounts of deionized water, citric acid monohydrate, oxalic acid dihydrate, aminosulfonic acid, sodium gluconate, polyaspartic acid silane complex micelles, betaine tartaric acid corrosion inhibitor complex salt, alkyl glycoside aqueous solution, and hydrogen peroxide aqueous solution, by weight, are 760.0-930.0 parts, 18.0-40.0 parts, 5.0-15.0 parts, 8.0-25.0 parts, 5.0-20.0 parts, 1.5-7.0 parts, 1.0-6.0 parts, 0.8-5.0 parts, and 1.5-9.0 parts, respectively; the alkyl glycoside aqueous solution is a C8-C10 alkyl polysaccharide aqueous solution; the pH is adjusted to 3.2-4.

6.

3. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 1, characterized in that, In step S2, the pressure of the compressed air is 0.15-0.35 MPa.

4. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 1, characterized in that, In step S3, the soaking and cleaning temperature is 35-45℃, and the soaking and cleaning time is 10-18 minutes.

5. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 1, characterized in that, The preparation method of the polyaspartic acid silane complex micelles includes: A1. By weight, mix 28.0-34.0 parts of maleic anhydride and 34.0-40.0 parts of ammonium carbonate, pre-react at 60-90℃, then heat to 175-215℃ for polycondensation, cool, and pulverize to obtain crude polysuccinimide product; mix 90.0-150.0 parts of deionized water, 6.8-21.0 parts of sodium hydroxide, and 15.0-38.0 parts of crude polysuccinimide product, hydrolyze at 50-65℃, add glacial acetic acid, adjust the pH to 7.2-8.2, and obtain sodium polyaspartate base solution; 8.0-1 8.0 parts anhydrous ethanol, 1.5-4.5 parts γ-glycidyl etheroxypropyltrimethoxysilane, 2.0-7.0 parts deionized water and 0.05-0.30 parts glacial acetic acid are mixed and hydrolyzed at 20-30℃. Then, 0.8-3.5 parts C12-C14 alkyl glycidyl ether are added and mixed to obtain a silane hydrophobic pre-modified solution. 12.0-33.0 parts of the silane hydrophobic pre-modified solution are added to a sodium polyaspartate base solution, and the pH is adjusted to 7.8-8.8 with ammonia water. The mixture is stirred at 50-65℃ to obtain a crude solution of polyaspartate silane complex micelles. A2. Mature 100.0-210.0 parts of the crude solution of polyaspartic acid silane complex micelles at 45-60℃, cool down to 25-35℃, add 0.05-0.20 parts of citric acid and 0.05-0.30 parts of activated carbon, stir, let stand to defoam, filter, concentrate and dry.

6. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 5, characterized in that, In step A1, the pre-reaction time at 60-90℃ is 1.0-2.0h; the polycondensation time at 175-215℃ is 1.5-3.5h; the hydrolysis time at 50-65℃ is 1.0-3.0h; the stirring hydrolysis time at 20-30℃ is 30-60min; and the stirring time at 50-65℃ is 2.0-5.0h.

7. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 5, characterized in that, In step A2, the curing time at 45-60℃ is 1.0-2.5h, the standing defoaming time is 1-3h, and the drying temperature is 60-85℃.

8. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 1, characterized in that, The preparation method of the betaine tartaric acid corrosion-inhibiting complex salt includes: B1. By weight, mix 60.0-100.0 parts deionized water, 15.0-35.0 parts anhydrous betaine, 10.0-26.0 parts L-tartaric acid, 2.0-8.0 parts sodium gluconate and 1.0-4.0 parts glycerol, and stir at 40-55℃ to obtain a betaine-tartaric acid pre-complexing solution; add 1.0-4.0 parts sodium citrate, 0.5-2.0 parts polyethylene glycol 400 and 0.5-2.5 parts polyvinylpyrrolidone to the betaine-tartaric acid pre-complexing solution, and continue stirring to obtain a corrosion-inhibiting complexing base solution; B2. Add 0.5-3.0 parts of anhydrous betaine to 85.0-180.0 parts of corrosion-inhibiting complexing base solution, adjust the pH to 3.6-4.6 with L-tartaric acid, mature at 60-80℃, cool to 25-35℃, add 0.05-0.20 parts of activated carbon, stir, let stand to defoam, filter, concentrate, dry, pulverize, and sieve.

9. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 8, characterized in that, In step B1, the stirring time is 30-60 minutes at 40-55℃.

10. The environmentally friendly cleaning process for semiconductor ceramic structural components according to claim 8, characterized in that, In step B2, the maturation time at 60-80℃ is 1.0-3.0h; the standing defoaming time is 1-3h; and the drying temperature is 60-85℃.