A working agent for roughening and texturing of a semiconductor silicon-based component surface and a preparation method thereof

Abstract

The application provides a roughening and texturing working agent for surface treatment of semiconductor silicon-based components and a preparation method thereof, and belongs to the technical field of integrated circuit electronic chemicals. In the application, the hydroxyethyl chitosan-PBA grafting product improves the wetting / liquid film stability by means of chitosan hydration and solution adjustment, and the PBA site provides reversible interaction; in the sodium hydroxide etching, the product dynamically stays in the near zone of the silicon surface, which helps to reduce bubble retention and modulate local mass transfer, and reduces random under-etching; the hydroxamic acidized polyacrylic acid adjusts the electrical properties, conformation and boundary layer mass transfer by polyacrylic acid salt, coordinates trace metals and hydrolyzates at the hydroxamic acid site, inhibits micro-deposition nuclei / point-like micro-shading, and reduces pitting; under the action of strong alkali, the two form dynamic exchange local aggregates / weak networks, realize triggerable, reversible and flushable regulation; the two components are separated, and the concentrated liquid with pH 4-6 inhibits storage complex aggregation, uses mixed trigger, and realizes rinsing depolymerization and redissolution, thereby reducing residues, and improving texture consistency and corrosion resistance life.

Description

Technical Field

[0001] This invention belongs to the field of integrated circuit electronic chemicals technology, and relates to a roughening and texturing working agent for surface treatment of semiconductor silicon-based components and its preparation method. Background Technology

[0002] Semiconductor silicon-based components (such as single-crystal silicon spray heads and silicon rings) typically require end-stage wet surface treatment during manufacturing and regeneration to remove machining damage layers, reduce the risk of particle and metal contamination, and obtain a stable surface state suitable for subsequent dry processes. In existing technologies, alkaline etching systems can texturize and roughen silicon surfaces, forming pyramid-like microstructures. However, under conditions of complex component structures and significant differences in surface curvature and flow field, the etching process is susceptible to wetting instability and bubble retention, leading to localized under-etching, wider texture size distribution, and increased regional variations. Simultaneously, trace metal ions, microparticles, and their hydrolysis / deposition products may induce point-like micro-masking, forming defects such as pitting, protrusions, or abrupt localized roughness. These defects may be amplified in the subsequent dry etching environment as uneven reaction or localized preferential consumption, affecting lifespan and consistency.

[0003] In addition, some additive routes mainly rely on reducing surface tension or improving wettability, which often makes it difficult to simultaneously suppress micro-masking sources and maintain formulation stability. Furthermore, there is a risk of additive failure or uncontrollable residues in strongly alkaline environments. Therefore, there is an urgent need for silicon-based component surface treatment technologies that can simultaneously improve wetting and mass transfer conditions, reduce the probability of random masking and defect generation, and meet cleanliness requirements. Summary of the Invention

[0004] To address the aforementioned problems, the present invention aims to provide a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. In this application, the hydroxyethyl chitosan-PBA (phenylboronic acid) graft utilizes the hydration and solution regulation of chitosan to improve wetting and liquid film stability, while the PBA sites provide reversible interaction functions. During sodium hydroxide etching, its dynamic residence in the near-field region of the silicon surface helps reduce bubble retention and modulate local mass transfer, reducing random undercuts and promoting more consistent texture nucleation. Hydroxime-acidified polyacrylic acid, in the form of polyacrylate, regulates the solution's electrical properties, conformation, and boundary layer mass transfer, and through the coordination of trace metals and their hydrolysates at the hydroxyoxime acid sites, reduces micro-deposition nuclei and dot-like micro-masking. The probability of masking formation is reduced, thereby reducing pitting and improving texture consistency and defect controllability. Under strong alkali, the two interact reversibly to form dynamically exchanged local aggregates / weak networks, affecting the random masking distribution and achieving dynamic assembly control that is "triggerable, reversible, and washable". The two components are separated and the pH of the concentrate is controlled at 4-6 to inhibit premature complexation and aggregation during storage and preparation. When used, they are mixed with alkali to trigger synergistic effects. During rinsing, they depolymerize and redissolve with solution replacement and pH changes, thereby reducing residue, improving texture consistency and contributing to subsequent corrosion resistance life.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components, the texturing and roughening agent comprising an alkaline etching component and a concentrated solution of a texturing and roughening auxiliary agent:

[0007] The alkaline etching component is a sodium hydroxide solution;

[0008] The roughening and texturing auxiliary agent concentrate includes deionized water, hydroxyethyl chitosan, polyacrylic acid, sulfate, hydroxyethyl chitosan-PBA graft and hydroxamic acidified polyacrylic acid;

[0009] The hydroxyethyl chitosan-PBA graft was obtained by first activating 4-carboxyphenylboronic acid with EDC·HCl and NHS, and then using the activated 4-carboxyphenylboronic acid to graft and modify hydroxyethyl chitosan.

[0010] The hydroxamic acidified polyacrylic acid is prepared by first activating the carboxyl groups of polyacrylic acid with EDC·HCl and NHS, and then reacting it with hydroxylamine.

[0011] Secondly, the present invention provides a method for preparing a roughening and texturing agent for surface treatment of semiconductor silicon-based components, the method comprising:

[0012] S1: Hydroxyethyl chitosan was added to deionized water to prepare a hydroxyethyl chitosan solution. Sodium bisulfate was added to the hydroxyethyl chitosan solution to adjust the pH and obtain reaction solution A. 4-Carboxyphenylboronic acid was added to deionized water to prepare a 4-carboxyphenylboronic acid solution. EDC·HCl and NHS were added to the 4-carboxyphenylboronic acid solution, and the mixture was stirred to obtain an activation solution. The activation solution was added dropwise to reaction solution A to obtain reaction solution B, and the mixture was stirred to react. After the reaction was completed, the mixture was purified using a dialysis bag. After purification, it was filtered through a filter membrane and freeze-dried to obtain the hydroxyethyl chitosan-PBA graft.

[0013] S2: Polyacrylic acid was added to deionized water to prepare a polyacrylic acid solution. Sodium bisulfate was added to the polyacrylic acid solution to adjust the pH to obtain reaction solution C. EDC·HCl and NHS were added to reaction solution C, and the mixture was stirred to obtain a second activating solution. Hydroxylamine was added to deionized water to prepare a hydroxylamine solution. The pH of the hydroxylamine solution was adjusted with sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to the second activating solution to obtain reaction solution E, and the mixture was stirred to obtain reaction solution E. After the reaction was completed, the solution was purified using a dialysis bag, filtered through a filter membrane, and freeze-dried to obtain hydroxyoxime-acidified polyacrylic acid.

[0014] S3: Prepare a sulfate solution, add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system; add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, adjust the pH of the concentrated solution with sodium bisulfate solution and filter it through a filter membrane to obtain a roughening and texturing auxiliary agent concentrate.

[0015] S4: Take sodium hydroxide solution as the alkaline etching component, and add the concentrated roughening and texturing auxiliary agent to the alkaline etching component to obtain a roughening and texturing working agent for surface treatment of semiconductor silicon-based components.

[0016] As a preferred technical solution of the present invention, in S1, the mass ratio of hydroxyethyl chitosan to deionized water is 1:(80-150), for example, it can be 1:80, 1:87, 1:94, 1:101, 1:108, 1:115, 1:122, 1:129, 1:136, 1:143 or 1:150, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0017] In some optional embodiments, sodium bisulfate is added to the hydroxyethyl chitosan solution to adjust the pH to 4.8-6.0. For example, the pH can be adjusted to 4.80, 4.92, 5.04, 5.16, 5.28, 5.40, 5.52, 5.64, 5.76, 5.88, or 6.00, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0018] In some optional embodiments, the mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:(100-200), for example, it can be 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190 or 1:200, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0019] In some optional embodiments, the molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is (1.0-1.5):1, for example, it can be 1.00:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, 1.35:1, 1.40:1, 1.45:1 or 1.50:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0020] In some optional embodiments, the molar ratio of NHS to 4-carboxyphenylboronic acid is (1.0-1.5):1, for example, it can be 1.00:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, 1.35:1, 1.40:1, 1.45:1 or 1.50:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0021] In some optional embodiments, the temperature at which EDC·HCl and NHS are added to the 4-carboxyphenylboronic acid solution and stirred is 0-10°C, for example, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C or 10°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0022] In some optional embodiments, the reaction time after adding EDC·HCl and NHS to the 4-carboxyphenylboronic acid solution and stirring is 0.5-2 h, for example, it can be 0.50 h, 0.65 h, 0.80 h, 0.95 h, 1.10 h, 1.25 h, 1.40 h, 1.55 h, 1.70 h, 1.85 h or 2.00 h, but is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0023] In some optional embodiments, the molar ratio of the 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan is (0.005-0.03):1, for example, it can be 0.0050:1, 0.0075:1, 0.0100:1, 0.0125:1, 0.0150:1, 0.0175:1, 0.0200:1, 0.0225:1, 0.0250:1, 0.0275:1 or 0.0300:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0024] In some optional embodiments, the reaction temperature of the reaction solution B is 15-30°C, for example, it can be 15.0°C, 16.5°C, 18.0°C, 19.5°C, 21.0°C, 22.5°C, 24.0°C, 25.5°C, 27.0°C, 28.5°C or 30.0°C, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0025] In some optional embodiments, the reaction time of the reaction solution B is 2-12 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, but not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0026] In some optional embodiments, the ratio of dialysate volume to reaction liquid volume during the purification process of the dialysis bag is (100-300):1, for example, it can be 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 220:1, 240:1, 260:1, 280:1 or 300:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0027] In some optional embodiments, the number of water changes during the dialysis bag purification process is 3-10 times, for example, 3.0 times, 3.7 times, 4.4 times, 5.1 times, 5.8 times, 6.5 times, 7.2 times, 7.9 times, 8.6 times, 9.3 times, or 10.0 times, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0028] In some optional embodiments, the total dialysis time during the purification process of the dialysis bag is 24-72 hours, for example, it can be 24.0 hours, 28.8 hours, 33.6 hours, 38.4 hours, 43.2 hours, 48.0 hours, 52.8 hours, 57.6 hours, 62.4 hours, 67.2 hours or 72.0 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0029] In some optional embodiments, the pore size of the filter membrane is 0.22-0.45 μm, for example, it can be 0.220 μm, 0.243 μm, 0.266 μm, 0.289 μm, 0.312 μm, 0.335 μm, 0.358 μm, 0.381 μm, 0.404 μm, 0.427 μm or 0.450 μm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0030] As a preferred technical solution of the present invention, in S2, the mass ratio of polyacrylic acid to deionized water is 1:(30-80), for example, it can be 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75 or 1:80, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0031] In some alternative embodiments, the pH value of the reaction solution C is 4.5-6.0, for example, it can be 4.50, 4.65, 4.80, 4.95, 5.10, 5.25, 5.40, 5.55, 5.70, 5.85 or 6.00, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0032] In some optional embodiments, the target activated carboxyl groups in the polyacrylic acid are 0.5-5% of the total carboxyl groups in the polyacrylic acid, for example, 0.50%, 0.95%, 1.40%, 1.85%, 2.30%, 2.75%, 3.20%, 3.65%, 4.10%, 4.55%, or 5.00%, but are not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0033] In some optional embodiments, the molar ratio of the EDC·HCl to the target activated carboxyl group in polyacrylic acid is (1.0-1.5):1, for example, it can be 1.00:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, 1.35:1, 1.40:1, 1.45:1 or 1.50:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0034] In some optional embodiments, the molar ratio of the NHS to the target activated carboxyl group in the polyacrylic acid is (1.0-1.5):1, for example, it can be 1.00:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, 1.35:1, 1.40:1, 1.45:1 or 1.50:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0035] In some optional embodiments, after adding EDC·HCl and NHS to the reaction solution C, the stirring reaction temperature is 0-25℃, for example, it can be 0.0℃, 2.5℃, 5.0℃, 7.5℃, 10.0℃, 12.5℃, 15.0℃, 17.5℃, 20.0℃, 22.5℃ or 25.0℃, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0036] In some optional embodiments, after adding EDC·HCl and NHS to the reaction solution C, the stirring reaction time is 0.5-2h, for example, it can be 0.50h, 0.65h, 0.80h, 0.95h, 1.10h, 1.25h, 1.40h, 1.55h, 1.70h, 1.85h or 2.00h, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0037] In some alternative embodiments, the mass ratio of hydroxylamine to deionized water is 1:(20-100), for example, 1:20, 1:28, 1:36, 1:44, 1:52, 1:60, 1:68, 1:76, 1:84, 1:92 or 1:100, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0038] In some alternative embodiments, the concentration of the sodium hydroxide solution is 1-2M, for example, it can be 1M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, 1.6M, 1.7M, 1.8M, 1.9M or 2M, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0039] In some alternative embodiments, the pH value of the reaction solution D is 6.0-7.5, for example, it can be 6.00, 6.15, 6.30, 6.45, 6.60, 6.75, 6.90, 7.05, 7.20, 7.35 or 7.50, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0040] In some optional embodiments, the molar ratio of the hydroxylamine to the target activated carboxyl group in the polyacrylic acid is (1.5-2.5):1, for example, it can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1 or 2.5:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0041] In some optional embodiments, the reaction temperature of the reaction solution E is 0-25°C, for example, it can be 0.0°C, 2.5°C, 5.0°C, 7.5°C, 10.0°C, 12.5°C, 15.0°C, 17.5°C, 20.0°C, 22.5°C or 25.0°C, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0042] In some optional embodiments, the reaction time of the reaction solution E is 1-8 hours, for example, it can be 1.0 hours, 1.7 hours, 2.4 hours, 3.1 hours, 3.8 hours, 4.5 hours, 5.2 hours, 5.9 hours, 6.6 hours, 7.3 hours or 8.0 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0043] In some optional embodiments, the volume ratio of dialysate to reaction liquid during the purification process of the dialysis bag is (100-300):1, for example, it can be 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 220:1, 240:1, 260:1, 280:1 or 300:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0044] In some optional embodiments, the number of water changes during the dialysis bag purification process is 3-10 times, for example, 3.0 times, 3.7 times, 4.4 times, 5.1 times, 5.8 times, 6.5 times, 7.2 times, 7.9 times, 8.6 times, 9.3 times, or 10.0 times, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0045] In some optional embodiments, the total dialysis time during the purification process of the dialysis bag is 24-72 hours, for example, it can be 24.0 hours, 28.8 hours, 33.6 hours, 38.4 hours, 43.2 hours, 48.0 hours, 52.8 hours, 57.6 hours, 62.4 hours, 67.2 hours or 72.0 hours, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0046] In some optional embodiments, the pore size of the filter membrane is 0.22-0.45 μm, for example, it can be 0.220 μm, 0.243 μm, 0.266 μm, 0.289 μm, 0.312 μm, 0.335 μm, 0.358 μm, 0.381 μm, 0.404 μm, 0.427 μm or 0.450 μm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0047] As a preferred technical solution of the present invention, in S3, the mass ratio of sulfate to deionized water is 1:(100-200), for example, it can be 1:100, 1:110, 1:120, 1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190 or 1:200, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0048] The sulfate is one or more of sodium sulfate, sodium bisulfate, and ammonium sulfate;

[0049] In some optional embodiments, the mass ratio of the hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is (0.2-1):1, for example, it can be 0.20:1, 0.28:1, 0.36:1, 0.44:1, 0.52:1, 0.60:1, 0.68:1, 0.76:1, 0.84:1, 0.92:1 or 1.00:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0050] In some optional embodiments, the mass ratio of the hydroxamic acidified polyacrylic acid to polyacrylic acid is (0.2-1):1, for example, it can be 0.20:1, 0.28:1, 0.36:1, 0.44:1, 0.52:1, 0.60:1, 0.68:1, 0.76:1, 0.84:1, 0.92:1 or 1.00:1, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0051] In some optional embodiments, the mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:(1-3), for example, it can be 1:1.0, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.0, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3.0, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0052] In some alternative embodiments, the mass ratio of the sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan, and hydroxyethyl chitosan-PBA graft is (0.5-3):1, for example, it can be 0.50:1, 0.75:1, 1.00:1, 1.25:1, 1.50:1, 1.75:1, 2.00:1, 2.25:1, 2.50:1, 2.75:1, or 3.00:1, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0053] In some alternative embodiments, the concentration of the sodium bisulfate solution is 0.1-1M, for example, it can be 0.10M, 0.19M, 0.28M, 0.37M, 0.46M, 0.55M, 0.64M, 0.73M, 0.82M, 0.91M or 1.00M, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0054] In some alternative embodiments, the pH value of the concentrate is 4-6, for example, it may be 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8 or 6.0, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0055] In some optional embodiments, the pore size of the filter membrane is 0.22-0.45 μm, for example, it can be 0.220 μm, 0.243 μm, 0.266 μm, 0.289 μm, 0.312 μm, 0.335 μm, 0.358 μm, 0.381 μm, 0.404 μm, 0.427 μm or 0.450 μm, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0056] As a preferred technical solution of the present invention, in step S4, the concentration of the sodium hydroxide solution is 1-6M, for example, it can be 1.0M, 1.5M, 2.0M, 2.5M, 3.0M, 3.5M, 4.0M, 4.5M, 5.0M, 5.5M or 6.0M, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0057] In some optional embodiments, the volume ratio of the texturing aid concentrate to the alkaline etching component is 1:(200-2000), for example, it can be 1:200, 1:380, 1:560, 1:740, 1:920, 1:1100, 1:1280, 1:1460, 1:1640, 1:1820 or 1:2000, but is not limited to the listed values, other unlisted values ​​within this range are also applicable.

[0058] This application introduces water-soluble chitosan derivatives and polyacrylic acid as the basic framework in the roughening and texturing auxiliary agent concentrate, and further uses two self-made functional additives to regulate the formation of surface texture during alkaline etching. The introduction of hydroxyethyl chitosan-PBA grafts, with hydroxyethyl chitosan itself possessing good water solubility and hydration ability, is more likely to exhibit a wetting effect in the roughening solution, improving wetting behavior and liquid film stability, as well as a mild adjustment of near-wall viscosity / boundary layer; the introduction of phenylboronic acid sites transforms the polymer from merely a wetting agent or thickener into a functional site capable of participating in dynamic complexation. When the concentrate is added to the sodium hydroxide etching system, the adsorption-desorption balance and hydration layer formation tendency of the hydroxyethyl chitosan-PBA graft in the vicinity of the silicon surface may reduce the probability of bubbles remaining in the surface micro-regions for a long time, and have a certain modulating effect on local liquid film renewal and reactant / product diffusion. This modulation may be manifested as weakening the random under-etching caused by bubble shielding, rather than necessarily forming a continuous resist layer, thus providing more stable interface conditions for uniform nucleation of textures in different regions.

[0059] Hydroxime-modified polyacrylic acid is introduced. Polyacrylic acid can dissociate in alkaline systems to form polyacrylate segments, which helps provide a controllable electrical and solution conformational environment and affects dispersion stability and boundary layer mass transfer. The introduction of a small number of hydroxime acid sites makes the hydroxime-modified polyacrylic acid more inclined to coordinate with trace metal ions or their hydrolysates, thereby reducing the probability of metal-induced micro-deposition nuclei and dot-like micromasking to some extent. For the fine texture of silicon-based components, dot-like micromasking often causes pitting, protrusions, or localized roughness abrupt changes. These defects may become the starting point for preferential corrosion development during subsequent dry etching. Therefore, the role of hydroxime-modified polyacrylic acid in the system is not only that of a polymer in the conventional dispersion / thickening sense, but also that of a clean window regulator, improving texture consistency and defect controllability by trapping or passivating micromasking sources.

[0060] Hydroxyethyl chitosan-PBA grafts and hydroxamic acidified polyacrylic acid exhibit synergistic dynamic assembly behavior in a strongly alkaline roughening solution. Under alkaline conditions, the phenylboronic acid sites of the hydroxyethyl chitosan-PBA grafts and the oxygen-containing coordination sites carried by the hydroxamic acidified polyacrylic acid may reversibly complex or bridge, forming dynamically exchangeable local aggregates or weakly interacting networks in solution. The tendency of these transient structures to reside near the silicon surface wall may alter the spatial and temporal probability and scale distribution of uncontrollable random masking caused by bubble adhesion and micro-deposition, thus making the nucleation and growth of pyramids or rough textures more closely approximate a convergent distribution path. Compared to common practices that rely on alcohols or single surfactants to reduce surface tension, this application introduces triggerable, reversible, and washable dynamic assembly control during etching, so that morphology control does not entirely depend on permanent adsorption or strong etching inhibition mechanisms. Therefore, while ensuring etching effectiveness, it may be beneficial to achieve low residue and clean washability.

[0061] This application separates the texturing aid concentrate from the strong alkaline etching component, and controls the pH of the concentrate at 4-6 to reduce the possibility of premature complexation and aggregation between the hydroxyethyl chitosan-PBA graft and the hydroxamic acidified polyacrylic acid during storage and preparation, thereby reducing the risk of viscosity drift and particle formation, while maintaining the system's filterability and preparation stability. When the concentrate is mixed with the alkaline etching component to trigger their synergistic behavior, it is more conducive to confining dynamic assembly within the etching process. In the subsequent rinsing stage, solution displacement and pH changes promote depolymerization and resolution, thus reducing the probability of organic and particle residues. Based on this, the two-component texturing system of this application is more conducive to improving the regional consistency of texture formation, reducing random pitting defects, and improving the corrosion resistance life of subsequent dry etching on silicon-based components. Through the reversible interaction between the chitosan derivative containing PBA sites and the acrylic polymer containing hydroxamic acid sites under strong alkaline etching conditions, and the regulation of micro-masking source formation conditions, a controllable path is provided for the random masking behavior in traditional alkaline etching.

[0062] By designing the texturing temperature, texturing time, alkali amount, amount of roughening texturing auxiliary agent, and the roughness of the machining before texturing, the surface roughness of silicon-based parts after texturing can be controllably adjusted within the range of 0.9-1.8.

[0063] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0064] In this application, the hydroxyethyl chitosan-PBA graft utilizes the hydration and solution regulation of chitosan to improve wetting and liquid film stability, and the PBA sites provide reversible interaction functions; in sodium hydroxide etching, its dynamic residence in the near region of the silicon surface helps to reduce bubble retention and modulate local mass transfer, thereby reducing random undercutting and promoting more consistent texture nucleation.

[0065] In this application, hydroxamic acidified polyacrylic acid adjusts the solution's electrical properties, conformation, and boundary layer mass transfer in an alkaline system in the form of polyacrylate. By leveraging the coordination effect of hydroxamic acid sites on trace metals and their hydrolysates, it reduces the probability of metal-induced micro-deposition nuclei and dot-like micro-masking, thereby reducing defects such as pitting and improving texture consistency and defect controllability.

[0066] Hydroxyethyl chitosan-PBA grafts and hydroxamic acidified polyacrylic acid can form dynamically exchanged local aggregates / weak networks through reversible interactions between phenylboronic acid sites and oxygen-containing coordination sites under strongly alkaline conditions. This influences the random masking distribution caused by bubble adhesion and micro-deposition in the near-wall region of the silicon surface, thereby promoting more convergent texture nucleation and growth. The triggerable, reversible, and washable dynamic assembly control differs from the simple surface tension reduction approach, helping to reduce residue and improve cleaning feasibility while maintaining the etching effect.

[0067] This application separates the two components and controls the pH of the concentrate at 4-6 to reduce premature complexation and aggregation of hydroxyethyl chitosan-PBA grafts and hydroxamic acidified polyacrylic acid during storage and preparation, and to maintain stability. When used, it is mixed with alkaline solution to trigger a synergistic effect, and during rinsing, it depolymerizes and re-dissolves with solution displacement and pH changes, thereby reducing residues, improving texture consistency, reducing random defects, and contributing to subsequent corrosion resistance life.

[0068] By designing the texturing temperature, texturing time, alkali amount, amount of roughening texturing auxiliary agent, and the roughness of the machining before texturing, the surface roughness of silicon-based parts after texturing can be controllably adjusted within the range of 0.9-1.8. Attached Figure Description

[0069] Figure 1 This is a scanning electron microscope image of the surface of the silicon-based component prepared in Example 1 of this application after treatment with a roughening and texturing agent.

[0070] Figure 2 This is a high-magnification scanning electron microscope image of a localized silicon-based component surface after treatment with a roughening and texturing agent, obtained in Example 1 of this application. Detailed Implementation

[0071] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include any obvious substitutions and modifications made to the embodiments described herein.

[0072] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone further purification or processing.

[0073] Example 1

[0074] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0075] S1: Prepare a hydroxyethyl chitosan solution by adding hydroxyethyl chitosan to deionized water, wherein the mass ratio of hydroxyethyl chitosan to deionized water is 1:120; adjust the pH to 5.5 by adding sodium bisulfate to the hydroxyethyl chitosan solution to obtain reaction solution A; prepare a 4-carboxyphenylboronic acid solution by adding 4-carboxyphenylboronic acid to deionized water, wherein the mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:150; add EDC·HCl and NHS to the 4-carboxyphenylboronic acid solution, wherein the molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is 1.2:1, and the molar ratio of NHS to 4-carboxyphenylboronic acid is 1.2:1. The molar ratio of 4-carboxyphenylboronic acid was 1.3:1, and the reaction was stirred at 5℃ for 1.5 h to obtain an activated solution. The activated solution was added dropwise to reaction solution A to obtain reaction solution B, in which the molar ratio of 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan was 0.02:1, and the reaction was stirred at 25℃ for 10 h. After the reaction, the solution was purified using a dialysis bag, with a dialysis water volume to reaction solution volume ratio of 250:1, 8 water changes, and a total dialysis time of 60 h. After purification, the solution was filtered through a 0.35 μm filter membrane and freeze-dried to obtain the hydroxyethyl chitosan-PBA graft.

[0076] S2: Prepare a polyacrylic acid solution by adding polyacrylic acid to deionized water, wherein the mass ratio of polyacrylic acid to deionized water is 1:70; adjust the pH to 5.0 by adding sodium bisulfate to the polyacrylic acid solution to obtain reaction solution C; the target activated carboxyl groups in the polyacrylic acid are 4% of the total carboxyl groups in the polyacrylic acid; add EDC·HCl and NHS to reaction solution C, wherein the molar ratio of EDC·HCl to the target activated carboxyl groups in the polyacrylic acid is 1.3:1, and the molar ratio of NHS to the target activated carboxyl groups in the polyacrylic acid is 1.4:1; stir the reaction at 15°C for 1.8 h to obtain the second activated solution; add hydroxylamine to deionized water. A hydroxylamine solution was prepared with a mass ratio of hydroxylamine to deionized water of 1:80. The pH of the hydroxylamine solution was adjusted to 7.0 using a 1.5M sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to a second activating solution to obtain reaction solution E, where the molar ratio of hydroxylamine to the target activated carboxyl group in polyacrylic acid was 2.2:1. The reaction was stirred at 10°C for 6 hours. After the reaction, the solution was purified using a dialysis bag with a dialysis water volume to reaction solution volume ratio of 250:1, 8 water changes, and a total dialysis time of 60 hours. After purification, the solution was filtered through a 0.40 μm filter membrane and freeze-dried to obtain hydroxyoxime-acidified polyacrylic acid.

[0077] S3: Prepare a sulfate solution, wherein the sulfate is sodium sulfate, and the mass ratio of sulfate to deionized water is 1:170. Add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system. Add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, wherein the mass ratio of hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is 0.8:1, the mass ratio of hydroxamic acidified polyacrylic acid to polyacrylic acid is 0.9:1, the mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:2.5, and the mass ratio of sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft is 2.5:1. Adjust the pH of the concentrated solution to 5.5 using a 0.8M sodium bisulfate solution and then filter it through a 0.35μm filter membrane to obtain a roughening and texturing auxiliary agent concentrate.

[0078] S4: Take a 5M sodium hydroxide solution as the alkaline etching component, add the concentrated roughening texturing auxiliary agent to the alkaline etching component to obtain a roughening texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening texturing auxiliary agent to the alkaline etching component is 1:1500; control the surface roughness of the machined surface of the silicon-based component before texturing to 0.19, place the silicon-based component in the roughening texturing working solution and treat it at 58°C for 19 minutes, take it out, clean it with deionized water and dry it to obtain the etched semiconductor silicon-based component.

[0079] The surface of silicon-based components was treated using the roughening and texturing agent, and the surface morphology was observed after cleaning and drying. Figure 1 The image shows a low-magnification scanning electron microscope image of the surface of a silicon-based component after treatment with a texturing agent. It can be seen that the surface forms texture units composed of polyhedral protrusions, which are continuously covered in the whole. The texture units have a certain size distribution within the field of view. Figure 2 These are high-magnification scanning electron microscope images of local areas of the same processed sample, used to show the local facets and edge details of the texture units, revealing local pyramidal / pyramidal microstructural features. The low-magnification image reflects the coverage and distribution of the texture within the surface area, while the high-magnification image supplements the local structural details of the texture, together characterizing the formation of texture on the silicon surface after processing.

[0080] Example 2

[0081] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0082] S1: Prepare a hydroxyethyl chitosan solution by adding hydroxyethyl chitosan to deionized water, wherein the mass ratio of hydroxyethyl chitosan to deionized water is 1:80; adjust the pH to 4.8 by adding sodium bisulfate to the hydroxyethyl chitosan solution to obtain reaction solution A; prepare a 4-carboxyphenylboronic acid solution by adding 4-carboxyphenylboronic acid to deionized water, wherein the mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:100; add EDC·HCl and NHS to the 4-carboxyphenylboronic acid solution, wherein the molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is 1.5:1, and the molar ratio of NHS to 4-... The molar ratio of 4-carboxyphenylboronic acid was 1.0:1, and the reaction was stirred at 10℃ for 0.5 h to obtain an activation solution. The activation solution was added dropwise to reaction solution A to obtain reaction solution B, in which the molar ratio of 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan was 0.005:1, and the reaction was stirred at 15℃ for 2 h. After the reaction, the solution was purified using a dialysis bag, with the ratio of dialysis water volume to reaction solution volume being 100:1, the water being changed 3 times, and the total dialysis time being 24 h. After purification, the solution was filtered through a 0.22 μm filter membrane and freeze-dried to obtain the hydroxyethyl chitosan-PBA graft.

[0083] S2: Prepare a polyacrylic acid solution by adding polyacrylic acid to deionized water, wherein the mass ratio of polyacrylic acid to deionized water is 1:30; adjust the pH to 6.0 by adding sodium bisulfate to the polyacrylic acid solution to obtain reaction solution C; the target activated carboxyl group in the polyacrylic acid is 0.5% of the total carboxyl group in the polyacrylic acid; add EDC·HCl and NHS to reaction solution C, wherein the molar ratio of EDC·HCl to the target activated carboxyl group in the polyacrylic acid is 1.5:1, and the molar ratio of NHS to the target activated carboxyl group in the polyacrylic acid is 1.0:1; stir the reaction at 0℃ for 0.5 h to obtain the second activated solution; add hydroxylamine to deionized water. A hydroxylamine solution was prepared with a mass ratio of hydroxylamine to deionized water of 1:20. The pH of the hydroxylamine solution was adjusted to 6.0 using a 1.8M sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to a second activating solution to obtain reaction solution E, where the molar ratio of hydroxylamine to the target activated carboxyl group in polyacrylic acid was 1.5:1. The reaction was stirred at 25°C for 1 hour. After the reaction, the solution was purified using a dialysis bag with a dialysis water volume to reaction solution volume ratio of 100:1, three water changes, and a total dialysis time of 24 hours. After purification, the solution was filtered through a 0.22 μm filter membrane and freeze-dried to obtain hydroxyoxime-acidified polyacrylic acid.

[0084] S3: Prepare a sulfate solution, wherein the sulfate is ammonium sulfate, and the mass ratio of sulfate to deionized water is 1:100. Add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system. Add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, wherein the mass ratio of hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is 0.2:1, the mass ratio of hydroxamic acidified polyacrylic acid to polyacrylic acid is 1:1, the mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:1, and the mass ratio of sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft is 0.5:1. Adjust the pH of the concentrated solution to 4 using a 0.1M sodium bisulfate solution and then filter it through a 0.22μm filter membrane to obtain a roughening and texturing auxiliary agent concentrate.

[0085] S4: A 1M sodium hydroxide solution is used as the alkaline etching component. A concentrated roughening and texturing auxiliary agent is added to the alkaline etching component to obtain a roughening and texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening and texturing auxiliary agent to the alkaline etching component is 1:200. The surface roughness of the machined surface of the silicon-based component before texturing is controlled at 0.20. The silicon-based component is placed in the roughening and texturing working solution and treated at 60°C for 15 minutes. After removal, it is cleaned with deionized water and dried to obtain the etched semiconductor silicon-based component.

[0086] Example 3

[0087] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0088] S1: Prepare a hydroxyethyl chitosan solution by adding hydroxyethyl chitosan to deionized water, wherein the mass ratio of hydroxyethyl chitosan to deionized water is 1:100; adjust the pH to 5.2 by adding sodium bisulfate to the hydroxyethyl chitosan solution to obtain reaction solution A; prepare a 4-carboxyphenylboronic acid solution by adding 4-carboxyphenylboronic acid to deionized water, wherein the mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:200; add EDC·HCl and NHS to the 4-carboxyphenylboronic acid solution, wherein the molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is 1.4:1, and NHS and... The molar ratio of 4-carboxyphenylboronic acid was 1.1:1, and the reaction was stirred at 2℃ for 1.0 h to obtain an activated solution. The activated solution was added dropwise to reaction solution A to obtain reaction solution B, wherein the molar ratio of 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan was 0.01:1, and the reaction was stirred at 20℃ for 5 h. After the reaction, the solution was purified using a dialysis bag, wherein the ratio of dialysis water volume to reaction solution volume was 150:1, the water was changed 5 times, and the total dialysis time was 36 h. After purification, the solution was filtered through a 0.30 μm filter membrane and freeze-dried to obtain hydroxyethyl chitosan-PBA graft.

[0089] S2: Prepare a polyacrylic acid solution by adding polyacrylic acid to deionized water, wherein the mass ratio of polyacrylic acid to deionized water is 1:50; adjust the pH to 5.5 by adding sodium bisulfate to the polyacrylic acid solution to obtain reaction solution C; the target activated carboxyl groups in the polyacrylic acid are 2% of the total carboxyl groups in the polyacrylic acid; add EDC·HCl and NHS to reaction solution C, wherein the molar ratio of EDC·HCl to the target activated carboxyl groups in the polyacrylic acid is 1.1:1, and the molar ratio of NHS to the target activated carboxyl groups in the polyacrylic acid is 1.2:1; stir the reaction at 10°C for 1.0 h to obtain the second activated solution; add hydroxylamine to deionized water... A hydroxylamine solution was prepared in water at a mass ratio of hydroxylamine to deionized water of 1:50. The pH of the hydroxylamine solution was adjusted to 6.5 using a 2M sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to a second activating solution to obtain reaction solution E, where the molar ratio of hydroxylamine to the target activated carboxyl group in polyacrylic acid was 1.8:1. The reaction was stirred at 5°C for 4 hours. After the reaction, the solution was purified using a dialysis bag with a dialysis water volume to reaction solution volume ratio of 150:1, 5 water changes, and a total dialysis time of 48 hours. After purification, the solution was filtered through a 0.25 μm filter membrane and freeze-dried to obtain hydroxyoxime-treated polyacrylic acid.

[0090] S3: Prepare a sulfate solution, wherein the sulfate is a combination of sodium sulfate and sodium bisulfate, and the mass ratio of sulfate to deionized water is 1:200. Add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system. Add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, wherein the mass ratio of hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is 0.5:1, the mass ratio of hydroxamic acidified polyacrylic acid to polyacrylic acid is 0.5:1, the mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:1.5, and the mass ratio of sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft is 1.5:1. Adjust the pH of the concentrated solution to 4.5 using a 0.4M sodium bisulfate solution and then filter it through a 0.30μm filter membrane to obtain a roughening and texturing auxiliary agent concentrate.

[0091] S4: A 2M sodium hydroxide solution is used as the alkaline etching component. A concentrated roughening and texturing auxiliary agent is added to the alkaline etching component to obtain a roughening and texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening and texturing auxiliary agent to the alkaline etching component is 1:1000. The surface roughness of the machined surface of the silicon-based component before texturing is controlled at 0.21. The silicon-based component is placed in the roughening and texturing working solution and treated at 62°C for 20 minutes. After removal, it is cleaned with deionized water and dried to obtain the etched semiconductor silicon-based component.

[0092] Example 4

[0093] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0094] S1: Prepare a hydroxyethyl chitosan solution by adding hydroxyethyl chitosan to deionized water, wherein the mass ratio of hydroxyethyl chitosan to deionized water is 1:150; adjust the pH to 6.0 by adding sodium bisulfate to the hydroxyethyl chitosan solution to obtain reaction solution A; prepare a 4-carboxyphenylboronic acid solution by adding 4-carboxyphenylboronic acid to deionized water, wherein the mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:180; add EDC·HCl and NHS to the 4-carboxyphenylboronic acid solution, wherein the molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is 1.0:1, and NHS and... The molar ratio of 4-carboxyphenylboronic acid was 1.5:1, and the reaction was stirred at 0℃ for 2 h to obtain an activated solution. The activated solution was added dropwise to reaction solution A to obtain reaction solution B, wherein the molar ratio of 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan was 0.03:1, and the reaction was stirred at 30℃ for 12 h. After the reaction, the solution was purified using a dialysis bag, wherein the ratio of dialysis water volume to reaction solution volume was 300:1, the water was changed 10 times, and the total dialysis time was 72 h. After purification, the solution was filtered through a 0.45 μm filter membrane and freeze-dried to obtain hydroxyethyl chitosan-PBA graft.

[0095] S2: Prepare a polyacrylic acid solution by adding polyacrylic acid to deionized water, wherein the mass ratio of polyacrylic acid to deionized water is 1:80; adjust the pH to 4.5 by adding sodium bisulfate to the polyacrylic acid solution to obtain reaction solution C; the target activated carboxyl groups in the polyacrylic acid are 5% of the total carboxyl groups in the polyacrylic acid; add EDC·HCl and NHS to reaction solution C, wherein the molar ratio of EDC·HCl to the target activated carboxyl groups in the polyacrylic acid is 1.0:1, and the molar ratio of NHS to the target activated carboxyl groups in the polyacrylic acid is 1.5:1; stir the reaction at 25°C for 2 hours to obtain the second activated solution; add hydroxylamine to deionized water. A hydroxylamine solution was prepared, wherein the mass ratio of hydroxylamine to deionized water was 1:100. The pH of the hydroxylamine solution was adjusted to 7.5 with a 1M sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to a second activating solution to obtain reaction solution E, wherein the molar ratio of hydroxylamine to the target activated carboxyl group in polyacrylic acid was 2.5:1. The reaction was stirred at 0℃ for 8 h. After the reaction, the solution was purified using a dialysis bag, wherein the volume ratio of dialysis water to reaction solution was 300:1, the water was changed 10 times, and the total dialysis time was 72 h. After purification, the solution was filtered through a 0.45 μm filter membrane and freeze-dried to obtain hydroxyoxime-acidified polyacrylic acid.

[0096] S3: Prepare a sulfate solution, wherein the sulfate is a combination of sodium sulfate, sodium bisulfate, and ammonium sulfate, and the mass ratio of sulfate to deionized water is 1:150. Add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system. Add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, wherein the mass ratio of hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is 1:1, the mass ratio of hydroxamic acidified polyacrylic acid to polyacrylic acid is 0.2:1, the mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:3, and the mass ratio of sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan, and hydroxyethyl chitosan-PBA graft is 3:1. Adjust the pH of the concentrated solution to 6 using a 1M sodium bisulfate solution and then filter it through a 0.45μm filter membrane to obtain a roughening and texturing auxiliary agent concentrate.

[0097] S4: A 6M sodium hydroxide solution is used as the alkaline etching component. A concentrated roughening and texturing auxiliary agent is added to the alkaline etching component to obtain a roughening and texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening and texturing auxiliary agent to the alkaline etching component is 1:2000. The surface roughness of the machined surface of the silicon-based component before texturing is controlled at 0.23. The silicon-based component is placed in the roughening and texturing working solution and treated at 65°C for 24 minutes. After removal, it is cleaned with deionized water and dried to obtain the etched semiconductor silicon-based component.

[0098] Example 5

[0099] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0100] S1-S3 are the same as in Example 1;

[0101] S4: Take a 5M sodium hydroxide solution as the alkaline etching component, add the concentrated roughening texturing auxiliary agent to the alkaline etching component to obtain a roughening texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening texturing auxiliary agent to the alkaline etching component is 1:1500; control the surface roughness of the machined surface of the silicon-based component before texturing to 0.15; place the silicon-based component in the roughening texturing working solution and treat it at 55°C for 15 minutes, take it out, clean it with deionized water and dry it to obtain the etched semiconductor silicon-based component.

[0102] Example 6

[0103] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0104] S1-S3 are the same as in Example 1;

[0105] S4: Take a 5M sodium hydroxide solution as the alkaline etching component, add the concentrated roughening texturing auxiliary agent to the alkaline etching component to obtain the roughening texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening texturing auxiliary agent to the alkaline etching component is 1:1500; control the surface roughness of the machined surface of the silicon-based component before texturing to 0.25; place the silicon-based component in the roughening texturing working agent, treat it at 68℃ for 25min, take it out, clean it with deionized water and dry it to obtain the etched semiconductor silicon-based component.

[0106] Example 7

[0107] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0108] S1-S3 are the same as in Example 1;

[0109] S4: Take a 5M sodium hydroxide solution as the alkaline etching component, add the concentrated roughening texturing auxiliary agent to the alkaline etching component to obtain the roughening texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening texturing auxiliary agent to the alkaline etching component is 1:1500; control the surface roughness of the machined surface of the silicon-based component before texturing to 0.45; place the silicon-based component in the roughening texturing working agent, treat it at 80℃ for 40min, take it out, clean it with deionized water and dry it to obtain the etched semiconductor silicon-based component.

[0110] Example 8

[0111] This embodiment provides a texturing and roughening agent for surface treatment of semiconductor silicon-based components and its preparation method. The preparation method of the texturing and roughening agent for surface treatment of semiconductor silicon-based components specifically includes the following steps:

[0112] S1-S3 are the same as in Example 1;

[0113] S4: Take a 5M sodium hydroxide solution as the alkaline etching component, add the concentrated roughening texturing auxiliary agent to the alkaline etching component to obtain the roughening texturing working agent for surface treatment of semiconductor silicon-based components; wherein the volume ratio of the concentrated roughening texturing auxiliary agent to the alkaline etching component is 1:1500; control the surface roughness of the machined surface of the silicon-based component before texturing to 0.80; place the silicon-based component in the roughening texturing working agent, treat it at 88℃ for 55min, take it out, clean it with deionized water and dry it to obtain the etched semiconductor silicon-based component.

[0114] Comparative Example 1

[0115] This comparative example provides a roughening and texturing working agent for surface treatment of semiconductor silicon-based components and its preparation method. The difference from Example 1 is that only an alkaline etching component is used in S4, and no roughening and texturing auxiliary agent concentrate is added. Other operating steps and process parameters are exactly the same as in Example 1.

[0116] Comparative Example 2

[0117] This comparative example provides a roughening and texturing agent for surface treatment of semiconductor silicon-based components and its preparation method. The difference from Example 1 is that steps S1 and S2 are omitted, and hydroxyethyl chitosan-PBA graft and hydroxyoxime-acidified polyacrylic acid are not added in S3. Other operating steps and process parameters are exactly the same as in Example 1.

[0118] Comparative Example 3

[0119] This comparative example provides a roughening and texturing agent for surface treatment of semiconductor silicon-based components and its preparation method. The difference from Example 1 is that step S1 is omitted and hydroxyethyl chitosan-PBA graft material is not added in S3. Other operation steps and process parameters are exactly the same as in Example 1.

[0120] Comparative Example 4

[0121] This comparative example provides a roughening and texturing agent for surface treatment of semiconductor silicon-based components and its preparation method. The difference from Example 1 is that step S2 is omitted, and hydroxamic acidified polyacrylic acid is not added in S3. Other operation steps and process parameters are exactly the same as in Example 1.

[0122] The performance of the etched semiconductor silicon-based components prepared in Examples 1-8 and Comparative Examples 1-4 was tested, and the specific process is as follows:

[0123] The surface roughness of etched semiconductor silicon-based components was tested according to GB / T 1031-2009.

[0124] Visual inspection of the surface defects of etched semiconductor silicon-based components shall be carried out in accordance with GB / T 6624-2009.

[0125] The number of particles on the surface of etched semiconductor silicon-based components is tested according to GB / T 19921-2018.

[0126] According to GB / T 24578-2024, the surface metal contamination content of etched semiconductor silicon-based components is tested.

[0127] The test results are shown in Table 1.

[0128] Table 1. Test results of etched semiconductor silicon-based components prepared in Examples 1-8 and Comparative Examples 1-4

[0129] As can be seen from the test results of Example 1 and Comparative Example 1 in Table 1, when only alkaline etching components are used without the addition of a roughening and texturing auxiliary agent concentrate, the system lacks modulation of wetting, liquid film renewal and bubble adhesion, and also lacks coordination inhibition of trace metals and their hydrolysis / deposition species. The etching is more susceptible to bubble shielding and local mass transfer fluctuations, resulting in insufficient texture nucleation and growth and increased regional differences, thus reducing surface roughness. At the same time, random shielding and local deposition are more likely to form scatterers and residues, increasing the number of particles, making visual defects more likely to appear and more severe. Due to the lack of inhibition of metal-related micro-deposition nuclei, the level of surface metal contamination increases.

[0130] As shown in Table 1, the test results of Example 1 and Comparative Example 2 show that, omitting steps S1 and S2, and not adding hydroxyethyl chitosan-PBA graft and hydroxamic acid-modified polyacrylic acid in S3, although the system still has the solution conformation and ionic strength environment provided by the basic polymer and inorganic salt, it lacks the functionalized interface regulation and micro-masking source suppression pathway provided by PBA sites and hydroxamic acid sites. Random masking during the etching process is difficult to be effectively weakened, and the texture development and consistency improvement are limited, so the surface roughness improvement is limited; scatterers and point-like masking are more likely to occur, and the number of particles and defects increases; at the same time, the lack of coordination effect of hydroxamic acid sites on trace metals increases surface metal contamination.

[0131] As shown in Table 1, the test results of Example 1 and Comparative Example 3 show that, omitting steps S1 and S3 without adding hydroxyethyl chitosan-PBA grafts, the system lacks interfacial residence and reversible interactions involving PBA sites, which weakens the modulation of wetting-bubble adhesion behavior. Bubble shading and local mass transfer fluctuations are more likely to cause random under-etching and regional differences, thus reducing surface roughness. Bubble-related shading and under-etching are more likely to manifest as scatterers and local anomalies, with an increase in particle number and defects. However, since hydroxyoxime-acidified polyacrylic acid is still retained, it can still play a role in the coordination inhibition of trace metals and their hydrolysates, and surface metal contamination is relatively controllable.

[0132] As can be seen from the test results of Example 1 and Comparative Example 4 in Table 1, omitting steps S2 and S3 without adding hydroxamic acidified polyacrylic acid, the system lacks the coordination inhibition of trace metals and their hydrolysis / deposition species by hydroxamic acid sites, making it easier for metal-induced micro-deposition nuclei and dot-like micro-masks to form. Although it still contains hydroxyethyl chitosan-PBA grafts, the modulation of wetting and bubble adhesion may still exist, but dot-like micro-depositions and local protrusions will increase surface heterogeneity, resulting in higher surface roughness. At the same time, micro-depositions and dot-like masks will increase scatterers and residues, increase the number of particles, aggravate defects, and increase the level of surface metal contamination.

[0133] As can be seen from the test results of Examples 5-8 in Table 1, under the premise that the roughening texturing auxiliary agent formula remains unchanged, by simultaneously adjusting the surface roughness of the machining before texturing, the texturing temperature and the processing time, the surface roughness of the silicon-based parts after texturing can be graded and controlled within the range of about 0.9-1.8. At the same time, the number of particles, the total number of defects and the surface metal contamination in each example are kept at a relatively low level, indicating that the change in roughness mainly comes from controllable morphology adjustment, rather than uncontrolled corrosion or increased contamination.

[0134] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A roughening and texturing working agent for surface treatment of semiconductor silicon-based components, characterized in that, The texturing and roughening working agent includes an alkaline etching component and a concentrated solution of texturing and roughening auxiliary agent: The alkaline etching component is a sodium hydroxide solution; The roughening and texturing auxiliary agent concentrate includes deionized water, hydroxyethyl chitosan, polyacrylic acid, sulfate, hydroxyethyl chitosan-PBA graft, and hydroxamic acidified polyacrylic acid. The hydroxyethyl chitosan-PBA graft was obtained by first activating 4-carboxyphenylboronic acid with EDC·HCl and NHS, and then using the activated 4-carboxyphenylboronic acid to graft and modify hydroxyethyl chitosan. The hydroxamic acidified polyacrylic acid is prepared by first activating the carboxyl groups of polyacrylic acid with EDC·HCl and NHS, and then reacting it with hydroxylamine.

2. A method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components as described in claim 1, characterized in that, The preparation method includes: S1: Hydroxyethyl chitosan was added to deionized water to prepare a hydroxyethyl chitosan solution. Sodium bisulfate was added to the hydroxyethyl chitosan solution to adjust the pH and obtain reaction solution A. 4-Carboxyphenylboronic acid was added to deionized water to prepare a 4-carboxyphenylboronic acid solution. EDC·HCl and NHS were added to the 4-carboxyphenylboronic acid solution, and the mixture was stirred to obtain an activation solution. The activation solution was added dropwise to reaction solution A to obtain reaction solution B, and the mixture was stirred to react. After the reaction was completed, the mixture was purified using a dialysis bag. After purification, it was filtered through a filter membrane and freeze-dried to obtain the hydroxyethyl chitosan-PBA graft. S2: Polyacrylic acid was added to deionized water to prepare a polyacrylic acid solution. Sodium bisulfate was added to the polyacrylic acid solution to adjust the pH to obtain reaction solution C. EDC·HCl and NHS were added to reaction solution C, and the mixture was stirred to obtain a second activating solution. Hydroxylamine was added to deionized water to prepare a hydroxylamine solution. The pH of the hydroxylamine solution was adjusted with sodium hydroxide solution to obtain reaction solution D. Reaction solution D was added to the second activating solution to obtain reaction solution E, and the mixture was stirred to obtain reaction solution E. After the reaction was completed, the solution was purified using a dialysis bag, filtered through a filter membrane, and freeze-dried to obtain hydroxyoxime-acidified polyacrylic acid. S3: Prepare a sulfate solution, add polyacrylic acid and hydroxamic acidified polyacrylic acid to obtain an acrylic acid system; add hydroxyethyl chitosan and hydroxyethyl chitosan-PBA graft to obtain a concentrated solution, adjust the pH of the concentrated solution with sodium bisulfate solution and filter it through a filter membrane to obtain a roughening and texturing auxiliary agent concentrate. S4: Take sodium hydroxide solution as the alkaline etching component, and add the concentrated roughening and texturing auxiliary agent to the alkaline etching component to obtain a roughening and texturing working agent for surface treatment of semiconductor silicon-based components.

3. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S1: The mass ratio of the hydroxyethyl chitosan to deionized water is 1:(80-150); Sodium bisulfate was added to the hydroxyethyl chitosan solution to adjust the pH to 4.8-6.0; The mass ratio of 4-carboxyphenylboronic acid to deionized water is 1:(100-200).

4. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S1: The molar ratio of EDC·HCl to 4-carboxyphenylboronic acid is (1.0-1.5):1; The molar ratio of NHS to 4-carboxyphenylboronic acid is (1.0-1.5):1; The temperature at which EDC·HCl and NHS are added to the 4-carboxyphenylboronic acid solution and stirred is 0-10℃. The molar ratio of the 4-carboxyphenylboronic acid to the free primary amine group in hydroxyethyl chitosan is (0.005-0.03):

1.

5. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S2: The mass ratio of the polyacrylic acid to deionized water is 1:(30-80); The pH value of the reaction solution C is 4.5-6.0; The target activated carboxyl groups in the polyacrylic acid are 0.5-5% of the total carboxyl groups in the polyacrylic acid.

6. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 5, characterized in that, In S2: The molar ratio of EDC·HCl to the target activated carboxyl group in polyacrylic acid is (1.0-1.5):1; The molar ratio of NHS to the target activated carboxyl group in polyacrylic acid is (1.0-1.5):1; The reaction solution C is stirred after adding EDC·HCl and NHS at a temperature of 0-25℃.

7. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S2: The mass ratio of hydroxylamine to deionized water is 1:(20-100); The pH value of the reaction solution D is 6.0-7.5; The molar ratio of hydroxylamine to the target activated carboxyl group in polyacrylic acid is (1.5-2.5):1; The reaction temperature of the reaction solution E is 0-25℃.

8. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S3: The mass ratio of the sulfate to the deionized water is 1:(100-200); The sulfate is one or more of sodium sulfate, sodium bisulfate, and ammonium sulfate; The mass ratio of the hydroxyethyl chitosan-PBA graft to hydroxyethyl chitosan is (0.2-1):1; The mass ratio of the hydroxamic acidified polyacrylic acid to polyacrylic acid is (0.2-1):

1.

9. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S3: The mass ratio of hydroxyethyl chitosan to polyacrylic acid is 1:(1-3); The mass ratio of the sulfate to the total mass of polyacrylic acid, hydroxamic acidified polyacrylic acid, hydroxyethyl chitosan, and hydroxyethyl chitosan-PBA graft is (0.5-3):

1. The pH value of the concentrate is 4-6.

10. The method for preparing a roughening and texturing working agent for surface treatment of semiconductor silicon-based components according to claim 2, characterized in that, In S4: The concentration of the sodium hydroxide solution is 1-6M; The volume ratio of the texturing auxiliary agent concentrate to the alkaline etching component is 1:(200-2000).

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