An asymmetric multi-armed triazole bridged gemini surfactant composition, cleaning fluid and preparation and use thereof

Abstract

The application belongs to the technical field of semiconductor package cleaning, and more particularly relates to an asymmetric multi-arm triazole bridged Gemini surfactant composition, a cleaning solution and preparation and application thereof. The asymmetric multi-arm triazole bridged Gemini surfactant composition provided by the application takes a tertiary alkyne diol as a skeleton, and covalently grafts three differentiated polyoxyethylene ether hydrophobic arms through a triazole ring. The cleaning solution provided by the application takes an alcohol ether solvent as a main solvent, cooperates with the above-mentioned Gemini surfactant composition as a core cleaning additive, and further compounding an inhibitor, a chelating agent and a pH buffer system, has excellent swelling and peeling effects on acrylate residual glue, has a fast dynamic wetting and permeation speed, low foam, a significantly reduced corrosion rate of gold and aluminum substrates, high surface cleanliness after cleaning, and is suitable for the removal process of residual glue of a support adhesive tape after semiconductor wafer cutting and thinning.

Description

Technical Field

[0001] This application belongs to the field of semiconductor packaging cleaning technology, and more specifically, relates to an asymmetric multi-arm triazole-bridged Gemini-type surfactant composition, a cleaning solution, and its preparation and application. Background Technology

[0002] In semiconductor packaging processes, wafer dicing and back-side grinding (thinning) require the use of support tapes (such as UV dicing tape and back-side grinding tape) to temporarily fix and protect the wafer. After the process is completed, the support tape needs to be peeled off, but the adhesive layer of the tape leaves nano- to micron-sized organic residues on the wafer surface. These residues are mainly composed of acrylate polymers, some of which contain cross-linked structures. If left behind, they can seriously affect the quality of subsequent wire bonding, molding, and other processes, leading to bonding failure or delamination of the molding compound. Therefore, the wafer surface must be cleaned of residual adhesive after the tape is peeled off.

[0003] Currently, the cleaning solutions for semiconductor support tape residue mainly rely on imported products. Representative examples include: Kanto Chemical's tape residue cleaning solution from Japan, Millice StripAid™ X series from CE3S in the United States, and HCH-m1 / HCH-B3 highly soluble amine solvents from Chun Hong Industrial in Taiwan. Existing products are mostly based on organic solvents, combined with surfactants and additives, to remove acrylate residues through swelling or dissolution.

[0004] Common problems with existing semiconductor support tape residue cleaning solutions: 1. Insufficient cleaning cleanliness: Ordinary solvent-based cleaning solutions do not completely remove highly cross-linked acrylate residues, which easily form monolayer adsorption residues and cannot meet the ultra-high cleanliness requirements of advanced packaging; the detached residue fragments are prone to secondary deposition.

[0005] 2. Poor metal compatibility: Some strong solvents or alkaline formulations pose a risk of corrosion to the gold and aluminum pads and passivation layers on the wafer, leading to pad discoloration, surface roughness, or even bonding failure. Existing products cannot simultaneously protect both gold and aluminum.

[0006] 3. Prominent foaming problem: Conventional surfactants added to improve cleaning effect have a large foaming capacity, which easily generates a lot of foam in the spray cleaning process, affecting the normal operation of the equipment and the uniformity of cleaning. It is necessary to add defoamer, but this may introduce new contaminants.

[0007] 4. Poor stability of physically compounded systems: Commercially available products often use a combination of multiple surfactants in a physical compound. Due to the lack of a fixed linking structure between different surfactant components, phenomena such as component migration, competitive adsorption, and interfacial behavior mismatch may occur during storage and use. At the same time, in order to reduce foaming problems, additional defoamers are often required, which further increases the complexity of the system and affects the wetting efficiency and batch stability during the cleaning process.

[0008] 5. Domestic substitution gap: High-end semiconductor-grade residual adhesive cleaning solutions are basically monopolized by foreign manufacturers, with high prices and long supply cycles. There is a lack of high-performance alternative products with independent intellectual property rights in China.

[0009] Therefore, there is an urgent need to develop a semiconductor support tape residue cleaning solution with high cleaning efficiency, low corrosion rate to gold / aluminum metals, low foaming and system stability to meet the requirements of advanced packaging processes. Summary of the Invention

[0010] To address the shortcomings of existing technologies, the purpose of this application is to provide an asymmetric multi-arm triazole-bridged Gemini-type surfactant composition, a cleaning solution containing the surfactant composition, a preparation method thereof, and its application. This aims to solve technical problems in existing semiconductor packaging processes, such as the difficulty in completely removing acrylate residues after the support tape is peeled off, the easy corrosion of metal pads such as gold / aluminum by ordinary cleaning solutions, insufficient cleanliness after cleaning, and the impact of high foaming on the spraying process.

[0011] To achieve the above objectives, in a first aspect, this application provides an asymmetric multi-arm triazole-bridged Gemini-type surfactant composition comprising the following three compounds: Compound (I): An asymmetric single-arm triazole bridging surfactant formed by linking 1,2,3-triazole-1,4-dimethyl groups with a Gerbert-type branched fatty alcohol polyoxyethylene ether as the hydrophobic arm and tertiary argyne diol as the molecular backbone. Compound (II): An asymmetric single-arm triazole bridging surfactant with branched or isomeric fatty alcohol polyoxyethylene ether as the hydrophobic arm, tertiary argyne diol as the molecular backbone, and 1,2,3-triazole-1,4-dimethyl linkage. Compound (III): An asymmetric single-arm triazole bridging surfactant with a straight-chain fatty alcohol polyoxyethylene ether as the hydrophobic arm and a tertiary argyne diol as the molecular backbone, connected by 1,2,3-triazole-1,4-dimethyl linkage. The molar ratio of compound (I), compound (II) and compound (III) is (0.5-2):(0.5-2):(0.5-2).

[0012] Preferably, the Gerbert-type branched fatty alcohol polyoxyethylene ether is selected from C8 to C96. 18The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 3 to 20; preferably C8 to C9. 16 The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 5 to 15; more preferably, it is C 10 ~C 14 The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 6–10; the most preferred is C. 10 Gerbert type fatty alcohol polyoxyethylene ether (XL-50 type); The branched or isomeric fatty alcohol polyoxyethylene ether is selected from C 10 ~C 18 The polyoxyethylene ether is a branched or isomeric fatty alcohol, with an average ethylene oxide addition number of 3 to 20; preferably, it isotridecyl polyoxyethylene ether, with an average ethylene oxide addition number of 5 to 15; more preferably, it is a highly branched isotridecyl polyoxyethylene ether, with an average ethylene oxide addition number of 8 to 12; and most preferably, it is a highly branched isotridecyl polyoxyethylene ether (TO-10 type) with an average ethylene oxide addition number of 10. The linear fatty alcohol polyoxyethylene ether is selected from C8 to C96. 18 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 3 to 20; preferably C 10 ~C 16 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 5 to 15; more preferably, they are C 12 ~C 14 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 6 to 10; the most preferred is C4 with an average ethylene oxide addition number of 7. 12 ~C 14 Linear fatty alcohol polyoxyethylene ether (AEO-7 type); The tertiary ynediol is one or more of 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 1,4-diethynyl-2,3-butanediol, and 2,5-diethynyl-2,5-hexanediol.

[0013] According to another aspect of the present invention, a method for preparing the surfactant composition is provided, comprising the following steps: (1) The terminal hydroxyl alcohol ether and the sulfonating agent are reacted with each other in an anhydrous organic solvent under the protection of an inert gas in the presence of an alkaline acid binder to obtain a sulfonate ester terminal alcohol ether intermediate; the terminal hydroxyl alcohol ether is of three types, namely Guerbert type branched fatty alcohol polyoxyethylene ether, branched or isomer fatty alcohol polyoxyethylene ether and linear fatty alcohol polyoxyethylene ether, and the three sulfonate ester terminal alcohol ether intermediates are obtained after reaction respectively; (2) The three sulfonate-terminated alcohol ether intermediates described in step (1) are subjected to nucleophilic substitution reactions with azides in a polar aprotic solvent under a sealed inert gas system to obtain three azide-terminated modified alcohol ethers, namely azide-Gelbert-type branched fatty alcohol polyoxyethylene ether, azide-branched or isomerized fatty alcohol polyoxyethylene ether and azide-linear fatty alcohol polyoxyethylene ether. (3) The three azide-terminated modified alcohol ethers obtained in step (2) are mixed in a molar ratio of (0.5-2):(0.5-2):(0.5-2) and mixed with tertiary acetylenol in the presence of a copper catalyst and a reducing agent in an alcohol-water mixed solvent under an inert atmosphere at normal pressure. The reaction is carried out by stirring and heating, so that the central acetylenol skeleton is mainly composed of monosubstituted products. After purification, a composition composed of three types of single-branched triazole bridging surfactants is obtained, namely the asymmetric multi-arm triazole bridging Gemini type surfactant composition.

[0014] According to another aspect of the present invention, a semiconductor support tape residue cleaning solution is provided, comprising, by weight: 50-70 parts of main solvent, 10-30 parts of penetrating agent, 5-15 parts of alkaline penetrating agent, 0.3-1.5 parts of corrosion inhibitor, 0.3-1 part of chelating agent, 1-10 parts of co-solvent, and 1-5 parts of the asymmetric multi-arm triazole bridging Gemini type surfactant composition as described in claim 1 or 2.

[0015] According to another aspect of the present invention, a method for preparing the semiconductor support tape residual adhesive cleaning solution is provided, comprising the following steps: The main solvent, penetrating agent, and co-solvent are mixed evenly according to the weight ratio to obtain a solvent system; the alkaline penetrating agent is mixed evenly with the solvent system, and then the corrosion inhibitor and chelating agent are added and stirred until dissolved; finally, the asymmetric multi-arm triazole bridging Gemini type surfactant composition is added and stirred until homogeneous and transparent to obtain a semiconductor support tape residue cleaning solution.

[0016] According to another aspect of the present invention, the application of the semiconductor support tape residue cleaning solution is provided in the removal of acrylate residue from the support tape after semiconductor wafer dicing and backside thinning processes.

[0017] Overall, the technical solutions conceived in this application have the following beneficial effects compared with the prior art: (1) The present invention provides a novel asymmetric multi-arm triazole-bridged Gemini surfactant composition, comprising three surfactant compounds formed by covalently grafting three differentiated hydrophobic arms with tertiary acetylenol as the core molecular skeleton through 1,2,3-triazole rings. The molecular structure is novel; the multi-hydrophobic chains synergistically solubilize and emulsify and decontaminate, and the ability is far superior to that of single surfactants and physical compound systems; it has its own acetylenol defoaming sites and asymmetric chain arrangement to destroy the liquid film, achieving self-low foaming characteristics, without the need to add additional defoamers, and is suitable for high-pressure spray cleaning processes; and it has low dynamic surface tension and fast wetting and penetration speed, and can quickly penetrate into the interface between residual adhesive and wafer.

[0018] (2) The semiconductor-grade residual adhesive cleaning solution provided by this invention uses the self-made asymmetric multi-arm triazole-bridged Gemini-type surfactant composition as the core cleaning component, which has both low foaming and high cleaning power. Moreover, the cleaning solution is a pure oil-based solvent system, which has a strong swelling and peeling effect on acrylate residues. It uses ethylene glycol monobutyl ether, propylene glycol methyl ether acetate and other alcohol ethers as the main solvents, combined with strong penetrating aids such as dimethyl sulfoxide, to form a pure oil-phase cleaning system; the cleaning solution has a significant swelling effect on cross-linked acrylate adhesives, and removes the residues through a penetration-swelling-interface peeling mechanism, rather than simple dissolution; the solvent system can penetrate deep into the cross-linked adhesive network, so that the residues are peeled off from the wafer surface as a whole, avoiding monolayer adsorption residues; no water is introduced, avoiding problems such as metal oxidation and watermarks caused by water-based cleaning solutions.

[0019] (3) In a preferred embodiment, the semiconductor-grade residual adhesive cleaning solution provided by the present invention has a gold-aluminum bimetallic corrosion inhibition and protection system. Benzotriazole (BTA) corrosion inhibitors are used to form an adsorption protective film on the gold surface; propyl gallate is used on the aluminum surface; the pH is stabilized at the aluminum safety window of 8.0-8.5 through a carbonate buffer system to avoid strong alkaline corrosion; and mild chelating agents such as sodium citrate are used instead of EDTA to avoid accelerating aluminum dissolution.

[0020] (4) The semiconductor-grade residual adhesive cleaning solution provided by this invention adopts a dual mechanism of chelation and emulsification to ensure ultra-high cleanliness. The mild chelating agent captures the metal ions washed off to prevent secondary deposition; the Gemini-type surfactant developed by this invention has strong emulsifying and dispersing capabilities to ensure that the detached residual organic matter is completely removed rather than re-attached; after cleaning, the surface organic residue and metal ions are controlled within semiconductor-grade requirements, which is suitable for high-precision cleaning of residual adhesive tape after wafer dicing, back-side grinding and other processes.

[0021] (5) Compared with traditional single surfactant or physical compound system, the cleaning solution of the preferred embodiment of the present invention can achieve an acrylate residue removal rate of more than 99%, reduce the initial foam height to 18 mm, and the gold corrosion rate is less than 0.15 Å / min and the aluminum corrosion rate is less than 0.5 Å / min, all of which are superior to the existing technology level. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the TO-10 p-toluenesulfonation reaction in the embodiments of this application; Figure 2 This is a schematic diagram of the general formula for the alcohol ether azide reaction in the embodiments of this application; Figure 3 This is a schematic diagram of the synthesis of triazole-bridged multi-arm Gemini-type surfactants in the embodiments of this application; Figure 4 These are micrographs of the wafer surface under different cleaning times with the cleaning solution in Example 1. Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Figure 5 These are micrographs of the wafer surface under different cleaning times with the cleaning solution in Example 2. Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Figure 6 These are micrographs of the wafer surface under different cleaning times with the cleaning solution in Example 3. Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Figure 7 These are micrographs of the wafer surface under different cleaning times with the cleaning solution of Comparative Example 1. Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Figure 8 These are micrographs of the wafer surface under different cleaning times with the cleaning solution in Comparative Example 2. Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0024] The technical problem to be solved by this invention: 1. The problem of incomplete removal of cross-linked acrylate adhesive residues: Existing solvent-based cleaning solutions can only dissolve the surface of highly cross-linked acrylate adhesives, failing to penetrate deep into the adhesive layer for complete peeling, easily leaving monolayer adsorption residues and resulting in insufficient cleaning effectiveness. This invention utilizes the synergistic effect of a specialized Gemini-type surfactant composition and an alcohol ether solvent to achieve a "penetration-swelling-interfacial peeling" cleaning mechanism, thoroughly removing cross-linked adhesive residues.

[0025] 2. The dilemma of balancing cleaning power and low foaming: Conventional high-cleaning-power surfactants produce a large amount of foam, making them unsuitable for spray cleaning processes; low-foaming surfactants, on the other hand, often lack sufficient cleaning power. The Gemini-type surfactant of this invention possesses an acetylenic diol defoaming site and an asymmetric chain structure, achieving a balance between self-low foaming properties and high cleaning power without the need for additional defoamers.

[0026] 3. The problem of simultaneous corrosion of gold and aluminum bimetals: Existing cleaning solutions are difficult to be compatible with both gold pads and aluminum wiring, often resulting in aluminum corrosion or gold discoloration. This invention reduces the risk of corrosion of gold and aluminum materials during cleaning by using a compound system of BTA gold corrosion inhibitor and aluminum propyl gallate corrosion inhibitor, combined with a weakly alkaline pH window.

[0027] 4. Instability of Multi-Surfactant Physically Compound Systems: When multiple common surfactants are physically mixed, problems such as competitive adsorption, differences in wetting response, and changes in compositional distribution may occur among the components during long-term storage, thus affecting the stability and batch consistency of the system. This invention covalently links different types of hydrophobic chains with a triazole ring and a tertiary acetylenic diol skeleton to form triazole-bridged surfactants with different hydrophobic structures. These triazole bridging products are then combined to form a surfactant composition, thereby reducing component competition and interfacial behavior differences arising from relying solely on the physical compounding of multiple free surfactants, and improving the compositional stability and consistency of interfacial regulation of the system.

[0028] 5. The gap in domestic alternatives for high-end semiconductor cleaning solutions: Currently, high-performance support tape residue cleaning solutions rely on imports, resulting in high costs and long delivery cycles. This invention develops a domestically produced alternative formula with independent intellectual property rights, achieving self-sufficiency and control over key materials.

[0029] To address the technical problems in existing semiconductor packaging processes, such as the difficulty in completely removing acrylate residues after support tape peeling, the tendency of ordinary cleaning solutions to corrode gold / aluminum pads, insufficient cleanliness after cleaning, and high foaming affecting spraying processes, this invention provides a novel cleaning solution formulation. This cleaning solution uses alcohol ether solvents as the main solvent, combined with a dedicated asymmetric multi-arm triazole-bridged Gemini surfactant as the core cleaning aid, and further formulated with corrosion inhibitors, chelating agents, and a pH buffer system. The Gemini surfactant uses tert-acetylenic diol as its backbone, with three differentiated polyoxyethylene ether hydrophobic arms covalently grafted onto the triazole ring. This invention's cleaning solution exhibits excellent swelling and peeling effects on acrylate residues, rapid dynamic wetting and penetration, low foaming, significantly reduced corrosion rates on gold and aluminum substrates, and high surface cleanliness after cleaning. It is suitable for removing support tape residues after semiconductor wafer dicing and thinning.

[0030] This invention provides an asymmetric multi-arm triazole-bridged Gemini-type surfactant composition comprising the following three compounds: Compound (I): An asymmetric single-arm triazole bridging surfactant formed by linking 1,2,3-triazole-1,4-dimethyl groups with a Gerbert-type branched fatty alcohol polyoxyethylene ether as the hydrophobic arm and tertiary argyne diol as the molecular backbone. Compound (II): An asymmetric single-arm triazole bridging surfactant with branched or isomeric fatty alcohol polyoxyethylene ether as the hydrophobic arm, tertiary argyne diol as the molecular backbone, and 1,2,3-triazole-1,4-dimethyl linkage. Compound (III): An asymmetric single-arm triazole bridging surfactant with a straight-chain fatty alcohol polyoxyethylene ether as the hydrophobic arm and a tertiary argyne diol as the molecular backbone, connected by 1,2,3-triazole-1,4-dimethyl linkage. The molar ratio of compound (I), compound (II) and compound (III) is (0.5-2):(0.5-2):(0.5-2).

[0031] The asymmetric multi-arm triazole-bridged Gemini-type surfactant composition provided by this invention uses tertiary argyne diol (such as 2,4,7,9-tetramethyl-5-decyn-4,7-diol) as a common core molecular skeleton. Three single-arm triazole-bridged surfactant compounds with different polyoxyethylene ether hydrophobic arms are formed through 1,2,3-triazole bridging structures. These three compounds collectively constitute the asymmetric multi-arm triazole-bridged Gemini-type surfactant composition. The three compounds share a common argyne diol core molecular skeleton and triazole bridging structure, and form an asymmetric multi-arm Gemini-type synergistic surfactant system due to the different structures of the connected polyoxyethylene ether hydrophobic arms.

[0032] Unlike traditional dimerized Gemini surfactants formed by two surfactant units linked by connecting groups, the "Gemini type" of this invention is used to characterize a synergistic surfactant structure formed by multiple surfactant units sharing a common core molecular skeleton and a common bridging structure. Specifically, this invention uses tertiary argyne diol (e.g., 2,4,7,9-tetramethyl-5-decyn-4,7-diol) as the common core molecular skeleton, and forms three structurally related single-arm triazole bridging surfactant compounds with Goerbert-type, branched or isomerized, and linear polyoxyethylene ether hydrophobic arms through 1,2,3-triazole bridging structures, respectively. These three compounds together form an asymmetric multi-arm Gemini-type surfactant composition with synergistic interfacial interactions.

[0033] The term "asymmetry" in this invention has two levels of meaning. Level 1: The tertiary acetylenic diol skeleton of this invention has two reactive acetylinic sites. Classical symmetrical surfactants bond identical hydrophobic arms at both sites, forming a symmetrical "hydrophobic arm-skeleton-hydrophobic arm" structure. In this invention, each compound bonds only one hydrophobic arm at one acetylinic site in the skeleton; therefore, the individual molecule is structurally asymmetrical—the two ends of the skeleton are not equivalent, one end has a hydrophobic arm, and the other does not. Level 2: The hydrophobic arm structures of the three compounds in the composition are different; the carbon chain structure, branching degree, and hydrophilic segment length of the three hydrophobic arms are all different, resulting in an overall asymmetric compositional characteristic of the mixture. This is the meaning of "asymmetry" in "multi-armed."

[0034] The term "multi-arm" as used in this application does not refer to a single molecule having multiple hydrophobic arms simultaneously, but rather to a multifunctional arm synergistic system composed of multiple triazole bridging surfactant units with different hydrophobic arm structures.

[0035] In the asymmetric multi-arm triazole-bridged Gemini-type surfactant composition of the present invention, the Gerbert-type branched fatty alcohol polyoxyethylene ether includes, but is not limited to, C8-C96. 18 The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 3 to 20; preferably C8 to C9. 16 The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 5 to 15; more preferably, it is C 10 ~C 14 The Gerbert structure fatty alcohol polyoxyethylene ether has an average ethylene oxide addition number of 6–10; the most preferred is C. 10 Gerbert type fatty alcohol polyoxyethylene ether (XL-50 type).

[0036] The branched or isomeric fatty alcohol polyoxyethylene ethers include, but are not limited to, those with C 10 ~C 18The polyoxyethylene ether is a branched or isomeric fatty alcohol with an average ethylene oxide addition number of 3 to 20; preferably, it isotridecyl polyoxyethylene ether with an average ethylene oxide addition number of 5 to 15; more preferably, it is a highly branched isotridecyl polyoxyethylene ether with an average ethylene oxide addition number of 8 to 12; and most preferably, it is a highly branched isotridecyl polyoxyethylene ether (TO-10 type) with an average ethylene oxide addition number of 10.

[0037] The linear fatty alcohol polyoxyethylene ether includes, but is not limited to, C8-C9. 18 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 3 to 20; preferably C 10 ~C 16 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 5 to 15; more preferably, they are C 12 ~C 14 Straight-chain fatty alcohol polyoxyethylene ethers have an average ethylene oxide addition number of 6 to 10; the most preferred is C4 with an average ethylene oxide addition number of 7. 12 ~C 14 Linear fatty alcohol polyoxyethylene ether (AEO-7 type).

[0038] This invention prepares an asymmetric multi-arm triazole-bridged Gemini-type surfactant composition using tertiary argynyl diol as the molecular backbone. The tertiary argynyl diol can be any argynyl diol compound having two argynyl sites that can participate in the azido-alkynyl cycloaddition reaction, including but not limited to one or more of 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 1,4-diethynyl-2,3-butanediol, and 2,5-diethynyl-2,5-hexanediol.

[0039] In compounds (I), (II), and (III) of this invention, the azide-terminated modified alcohol ethers corresponding to each hydrophobic arm are covalently bonded to the tertiary acetylenol skeleton via a copper-catalyzed azide-alkynyl cycloaddition reaction, and the 1,2,3-triazole-1,4-diyl group is the bridging group of the covalent bond.

[0040] This invention uses tertiary argyne diols as the covalently bonded molecular framework. Tertiary argyne diols typically possess certain interfacial adsorption regulation capabilities and low foaming tendency. Furthermore, when triazole bridging surfactant molecules with different hydrophobic structures coexist, their spatial structure differences may affect the ordered arrangement of the surface adsorption layer, thereby reducing the stability of the foam film and causing the system to exhibit a lower foaming tendency.

[0041] In some embodiments, the present invention provides a method for preparing the surfactant composition, comprising the following steps: (1) The terminal hydroxyl alcohol ether and the sulfonating agent are reacted with each other in an anhydrous organic solvent in the presence of an alkaline acid binder, under stirring at 0-5°C and under inert gas protection to obtain a sulfonate ester terminal alcohol ether intermediate; the terminal hydroxyl alcohol ether is of three types, namely Guerbert type branched fatty alcohol polyoxyethylene ether, branched or isomer fatty alcohol polyoxyethylene ether and linear fatty alcohol polyoxyethylene ether, and the three sulfonate ester terminal alcohol ether intermediates are obtained after reaction respectively; (2) The three sulfonate-terminated alcohol ether intermediates described in step (1) are respectively subjected to nucleophilic substitution reaction with azide in a polar aprotic solvent under sealed inert gas protection at 50-80℃ to obtain three azide-terminated modified alcohol ethers, namely azide-Gelbert-type branched fatty alcohol polyoxyethylene ether, azide-branched or isomerized fatty alcohol polyoxyethylene ether and azide-linear fatty alcohol polyoxyethylene ether. (3) The three azide-terminated modified alcohol ethers obtained in step (2) are mixed in a molar ratio of (0.5-2):(0.5-2):(0.5-2) and reacted with tertiary acetylenol in the presence of a copper catalyst and a reducing agent in an alcohol-water mixed solvent at 60-80°C under an inert gas atmosphere to carry out a copper-catalyzed azide-acetylenol cycloaddition reaction. Under the control of the molar ratio of azide group to acetylenol and the reaction conditions, the central acetylenol skeleton is mainly composed of monosubstituted products. After purification, a composition composed of three types of single-branched triazole bridging surfactants is obtained, namely the asymmetric multi-arm triazole bridging Gemini type surfactant composition.

[0042] The sulfonating agent mentioned in step (1) includes, but is not limited to, p-toluenesulfonyl chloride, methanesulfonyl chloride, p-nitrobenzenesulfonyl chloride, etc., preferably p-toluenesulfonyl chloride; the basic acid-binding agent includes, but is not limited to, one or more of triethylamine, pyridine, and N,N-diisopropylethylamine.

[0043] In some embodiments, the anhydrous organic solvent in step (1) is one or more of anhydrous dichloromethane, anhydrous tetrahydrofuran, anhydrous acetonitrile, anhydrous N,N-dimethylformamide, anhydrous 1,2-dichloroethane, and anhydrous toluene.

[0044] In some embodiments, the polar aprotic solvent in step (2) is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, or acetonitrile; the nucleophilic substitution reaction temperature is preferably 55-65°C; the reaction time of the copper-catalyzed azide-alkynyl cycloaddition reaction in step (3) is 3-5 hours; the alcohol in the alcohol-water mixed solvent is selected from one or more of tert-butanol, ethanol, methanol, and isopropanol; the volume ratio of alcohol to water is 1:3 to 4:1, preferably 1:2 to 3:1. The inert gas in steps (1), (2), and (3) is a gas that does not participate in the reaction, such as nitrogen or argon.

[0045] The copper catalyst mentioned in step (3) includes, but is not limited to, one or more of copper sulfate pentahydrate, copper sulfate, cuprous iodide, cuprous bromide, or cuprous chloride; the reducing agent includes, but is not limited to, one or more of ascorbic acid, sodium ascorbate, sodium sulfite, sodium bisulfite, or sodium thiosulfate; preferably, the copper catalyst is copper sulfate pentahydrate, and the reducing agent is sodium ascorbate; the molar ratio of the azide group to the alkynyl group in the mixture of the three azide-terminated modified alcohol ethers is 0.8:1 to 1.5:1, preferably 1.0:1 to 1.2:1.

[0046] The present invention also provides a cleaning solution for residual adhesive on semiconductor support tape, comprising, by weight: 50-70 parts of main solvent, 10-30 parts of penetrating agent, 5-15 parts of alkaline penetrating agent, 0.3-1.5 parts of corrosion inhibitor, 0.3-1 part of chelating agent, 1-10 parts of co-solvent, and 1-5 parts of the asymmetric multi-arm triazole bridging Gemini surfactant composition as described in claim 1 or 2.

[0047] In some embodiments, the main solvent is selected from one or more of ethers, alcohol ethers, and ester solvents; the penetrant is selected from one or more of sulfoxides, amides, and terpenes; the alkaline penetrant is selected from one or more of fatty alcohol amines; the corrosion inhibitor includes gold corrosion inhibitors and aluminum corrosion inhibitors, wherein the gold corrosion inhibitor is selected from one or more of azoles; the aluminum corrosion inhibitor is selected from one or more of polyphenols and organic acid salts; the chelating agent is selected from one or more of carboxylates or polycarboxylate chelating agents; and the co-solvent is selected from one or more of polyols and alcohol ethers.

[0048] In a preferred embodiment, the main solvent is an ethylene glycol monoether solvent and / or a propylene glycol ether ester solvent; the penetration aid is a sulfoxide solvent and / or a terpene solvent; the alkaline penetration agent is one or more alkanolamine compounds; the corrosion inhibitor includes a gold corrosion inhibitor and an aluminum corrosion inhibitor; the chelating agent is an organic carboxylate chelating agent; and the co-solvent is a polyol solvent.

[0049] In a preferred embodiment, the main solvent is ethylene glycol monobutyl ether and propylene glycol methyl ether acetate; the penetration aid is dimethyl sulfoxide and D-limonene; the alkaline penetration agent is ethanolamine and triethanolamine; the gold corrosion inhibitor is benzotriazole (BTA) and methylbenzotriazole (TTA); the aluminum slow-release agent is propyl gallate; the chelating agent is sodium citrate; and the co-solvent is ethylene glycol.

[0050] This invention provides a method for preparing the residual adhesive cleaning solution for semiconductor support tape, comprising the following steps: The main solvent, penetrating agent, and co-solvent are mixed evenly according to the weight ratio to obtain a solvent system; the alkaline penetrating agent is mixed evenly with the solvent system, and then the corrosion inhibitor and chelating agent are added and stirred until dissolved; finally, the asymmetric multi-arm triazole bridging Gemini type surfactant composition is added and stirred until uniform and transparent to obtain a semiconductor support tape residue cleaning solution.

[0051] In some embodiments, after adding the asymmetric multi-arm triazole-bridged Gemini-type surfactant composition, the mixture is stirred at 200-300 rpm for 15-30 min until the system is homogeneous and transparent.

[0052] The semiconductor support tape residue cleaning solution described in this invention can be used to remove acrylate residue from support tapes after semiconductor wafer dicing and backside thinning processes.

[0053] In some embodiments, the cleaning temperature is 55-70°C, and the cleaning is carried out by soaking and stirring or spraying. Each cleaning session lasts 10-30 minutes and is repeated 1-3 times, followed by rinsing with isopropanol and drying with hot air.

[0054] Unlike simple physical compounding, this invention uses a covalent grafting method to fix surfactant units with different hydrophobic structures and hydrophilic segments onto the same core framework via triazole bridging. This allows different functional units to participate in the interfacial adsorption process in a defined spatial proportion and relative position. In physical compounding systems, each surfactant molecule exists independently, which can easily lead to competitive adsorption, uneven interfacial arrangement, and component migration due to differences in molecular structure. The covalent bridging structure reduces the uncertainty of interfacial behavior of different components, enabling synergistic effects such as hydrophobic solubilization, wetting and penetration, and emulsification and dispersion at the single-molecule scale. Furthermore, the multi-arm structure increases the interaction sites between molecules and residual organic components, which is beneficial for improving the coating, swelling, and dispersion capabilities of complex organic residues, potentially achieving superior cleaning efficiency and stability compared to traditional physical compounding systems. The triazole bridging structure is primarily based on the high selectivity, high conversion rate, and structural controllability of the copper-catalyzed azide-alkynyl cycloaddition reaction (CuAAC). Under mild conditions, it can stably connect different types of polyoxyethylene ether surfactant units to the alkynyldiol core framework, avoiding side reactions and structural uncontrollability issues that may occur in traditional condensation reactions. Simultaneously, the 1,2,3-triazole ring possesses good chemical stability, certain polarity, and interfacial regulation capabilities, serving as a stable linking unit to maintain the spatial relationship between different surfactant structures. Tertiary alkynyldiol compounds, such as Surfynol 104, inherently exhibit rapid reduction in dynamic surface tension and low foaming characteristics; using them as the central structure is beneficial for balancing rapid wetting, low foaming control, and the synergistic effect of multiple hydrophobic chains. Therefore, this covalent bridging method not only achieves structural integration of different surfactant units but also endows the system with molecular-level synergistic interfacial regulation capabilities, distinct from purely physical mixtures.

[0055] The embodiments of the present invention are implemented under the premise of the technical solution of the present invention, and detailed implementation methods and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. The process parameters in the following embodiments that do not specify specific conditions are generally in accordance with conventional conditions.

[0056] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0057] The specifications of all raw materials used in the semiconductor support tape residual adhesive cleaning solution in this embodiment of the invention are as follows: Ethylene glycol monobutyl ether: Industrial grade, purity ≥99%; Propylene glycol methyl ether acetate (PGMEA): Electronic grade; Dimethyl sulfoxide (DMSO): electronic grade; D-Limonene: Industrial grade; Ethylene glycol: electronic grade; Ethanolamine (MEA): Electronic grade; Triethanolamine (TEOA): Electronic grade; Benzotriazole (BTA, gold corrosion inhibitor): analytical grade; Propyl gallate (PG, aluminum corrosion inhibitor): analytical grade; Sodium citrate (chelating agent): analytical grade; Homemade asymmetric multi-arm triazole-bridged Gemini-type surfactant composition: prepared in the laboratory; TO-10 Isotridecyl alcohol polyoxyethylene ether: Industrial grade; AEO-9 Fatty Alcohol Polyoxyethylene Ether: Industrial Grade; XL-50 Gerbert alcohol polyoxyethylene ether: industrial grade.

[0058] In some embodiments, the preparation steps of the self-made asymmetric multi-arm triazole-bridged Gemini-type surfactant composition of the present invention are as follows: (1) P-toluenesulfonation reaction of terminal hydroxyl alcohol ethers: The Gelbert double-branched C 10 Alkyl polyoxyethylene ether (XL-50 type, 5EO), highly branched isotracene alkyl polyoxyethylene ether (TO-10 type, 10EO), and linear C 12 -C 14 Fatty alcohol polyoxyethylene ether (AEO-7 type, 7EO) was used as a reaction substrate for terminal hydroxyl activation treatment. 1.0–1.5 mol of p-toluenesulfonyl chloride (TsCl) and 1.2–2.0 mol of triethylamine were added per mol of terminal hydroxyl alcohol ether in an anhydrous organic solvent such as anhydrous dichloromethane. The mass-to-volume ratio of terminal hydroxyl alcohol ether to anhydrous dichloromethane was controlled at 1 g: 3–8 mL. Under nitrogen or other inert gas protection, the p-toluenesulfonyl chloride solution was added dropwise at 0–5 °C, and the reaction was continued with stirring for 2–6 h to allow the terminal hydroxyl groups of the alcohol ether to undergo sulfonation with p-toluenesulfonyl chloride, generating the corresponding p-toluenesulfonate terminal alcohol ether intermediates. After the reaction, the triethylamine hydrochloride was removed by washing with water, and the organic phase was dried, filtered, and concentrated under reduced pressure to obtain the corresponding p-toluenesulfonate terminal alcohol ether intermediates of types XL-50, TO-10, and AEO-7, respectively.

[0059] (2) Azide substitution reaction: The three p-toluenesulfonate-terminated alcohol ether intermediates obtained in step (1) were subjected to azid modification. 1.0–1.5 mol of sodium azide (NaN3) was added per mol of p-toluenesulfonate-terminated alcohol ether intermediate. N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or other polar aprotic solvents were used as the reaction medium, with the mass-to-volume ratio of reaction substrate to solvent controlled at 1 g: 3–10 mL. The reaction system was protected by nitrogen or other inert gas under sealed conditions and stirred at 55–65 °C for 8–16 h to allow the p-toluenesulfonate groups in the alcohol ether end groups to undergo nucleophilic substitution, generating the corresponding azid-terminated modified alcohol ethers, including azid-Gelbert's double-branched C. 10 Alkyl polyoxyethylene ether, azido-branched isotriadecyl polyoxyethylene ether, and azido-branched linear C 12 -C 14 Fatty alkyl polyoxyethylene ethers. After the reaction, inorganic salts were removed by washing with water, and three azide-terminated alcohol ether intermediates were obtained by organic extraction, drying, and concentration purification.

[0060] (3) Copper-catalyzed azido-alkynyl cycloaddition reaction (CuAAC): The three azide-terminated modified alcohol ethers obtained in step (2) were mixed in a molar ratio of 1:1:1, so that the three polyoxyethylene ether surface active units with different structures participated in the reaction in an equimolar ratio. Then, 2,4,7,9-tetramethyl-5-decyn-4,7-diol (Surfynol 104) was added as the central alkynyl skeleton, so that the molar ratio of the azide group to the alkynyl group in the Surfynol 104 molecule was controlled at 1:1 to 1.2:1. A copper catalyst and a reducing agent were added to the reaction system. The copper catalyst was selected from copper sulfate pentahydrate, copper sulfate, or other copper salts that can provide Cu(I) active species, and its addition amount was 1 to 10 mol% of the alkynyl molar amount; the reducing agent was selected from ascorbic acid, sodium isoascorbate, or other reducing agents, and its addition amount was 1 to 3 times the molar amount of the copper catalyst. Using tert-butanol / water, ethanol / water, or isopropanol / water mixed solvents as the reaction medium, with a volume ratio controlled at 1:1 to 5:1, the reaction was carried out under nitrogen or other inert gas protection at 60–80 °C and atmospheric pressure for 3–8 h with stirring. This allowed the azide group to undergo a copper-catalyzed azido-alkynyl cycloaddition reaction with the alkynyl group, forming a stable 1,2,3-triazole bridging structure. After the reaction, copper removal, solvent removal, and purification were performed to obtain an asymmetric multi-arm triazole bridging Gemini-type surfactant composition composed of three single-branched triazole bridging products.

[0061] The p-toluenesulfonation reaction and alcohol ether azidation reaction of TO-10 are used as examples for illustration. Figure 1As shown, isomeric tridecyl alcohol polyoxyethylene ether TO-10 reacts with p-toluenesulfonyl chloride (TsCl) under triethylamine catalysis, anhydrous dichloromethane at 0-5°C, and nitrogen protection for 4 h (1.2 mol of p-toluenesulfonyl chloride (TsCl) and 1.5 mol of triethylamine are added per 1 mol of terminal hydroxyl alcohol ether, and the mass-to-volume ratio of terminal hydroxyl alcohol ether to anhydrous dichloromethane is controlled at 1 g:5 mL), generating TO-10 p-toluenesulfonate (TO-10-OTs), introducing a leaving group to the p-toluenesulfonate. Then, as... Figure 2 As shown, p-toluenesulfonate-terminated alcohol ethers (TO-10-OTs) undergo a nucleophilic substitution reaction with sodium azide (NaN3) in DMF solvent under a sealed nitrogen system at 60°C for 12 hours, generating azide-terminated modified alcohol ethers, providing azide functional groups for subsequent click chemistry reactions. The p-toluenesulfonation reaction of XL-50 and AEO-7 is the same as the alcohol ether azide reaction.

[0062] The reaction yielded three azidolated alcohol ethers: azidoTO-10 (highly branched isotriadecyl), azidoXL50 (Gelbert bibranched C), and azido-XL50 (Gelbert bibranched C). 10 Alkyl), Azide AEO-7 (linear C) 12-14 (Aliphatic alkyl groups) 1 / 3 equivalent, with the Surfynol 104 acetylenic diol skeleton in CuSO4 Catalyst: 5H₂O / ascorbic acid reducing agent; t-BuOH / H₂O mixed solvent; constant temperature reaction at 70℃ under a nitrogen atmosphere for 4 h (molar ratio of azide group to alkynyl group in Surfynol 104 molecule controlled at 1.15:1; copper catalyst added at 5 mol% of alkynyl group molarity; reducing agent added at twice the molar amount of copper catalyst); via CuAAC click cyclization reaction, a mixture of three asymmetric single-branched triazole-bridged surfactants is generated, i.e., the target multi-branched surfactant, such as... Figure 3 As shown. The product uses a stable 1,2,3-triazole five-membered heterocycle as a covalent bridging group to covalently bond three hydrophobic arms of polyoxyethylene ether with different structures and degrees of branching to the Surfynol 104 acetylenic diol molecular backbone.

[0063] The following is an example: Example 1 1. Formula Composition The composition, by weight, includes 29 parts ethylene glycol monobutyl ether, 29.5 parts PGMEA, 15.0 parts DMSO, 10.0 parts D-limonene, 4.0 parts ethylene glycol, 7.0 parts ethanolamine, 3.0 parts triethanolamine, 0.3 parts BTA, 0.5 parts propyl gallate, 0.7 parts sodium citrate, and 3.0 parts a self-made asymmetric multi-arm triazole-bridged Gemini-type surfactant composition.

[0064] 2. Preparation process Accurately weigh each component according to the corresponding formula mass percentages, and prepare the mixture at room temperature in a fixed order of addition: (1) Add ethylene glycol monobutyl ether, PGMEA, DMSO, D-limonene and ethylene glycol in sequence, stir at 200 r / min for 5 min, and mix until the solvent system is homogeneous; (2) Add ethanolamine and triethanolamine, and stir at 200 r / min for 10 min; (3) Add BTA, propyl gallate and sodium citrate, and stir continuously until the solid additives are completely dissolved and there is no visible precipitate; (4) Finally, add the corresponding type and amount of self-made asymmetric multi-arm triazole bridging Gemini type surfactant composition, stir at 200r / min for 20min until the whole solution is transparent and without layering, and obtain the finished clear and transparent semiconductor support tape residue cleaning solution.

[0065] 3. Cleaning and Testing Results A combined immersion and agitation cleaning method is used for cleaning residual adhesive on wafers and for performance testing. The complete steps are as follows: (1) Pre-cleaning: Immerse the wafer with acrylate residue after peeling off the support tape completely in the cleaning solution and let it stand for 3 minutes to allow the solvent to penetrate and swell the residue. (2) Stirring and cleaning: The system is kept at a constant temperature of 60℃, the magnetic stirring speed is 200r / min, the single cleaning time is 20min, and the cleaning is repeated 2 times; (3) Rinsing: Ultrasonic rinsing with isopropanol solvent for 3 min; (4) Rinsing: Rinse the wafer surface continuously with isopropanol for 30 seconds; (5) Drying: Dry with hot air at 80℃ for 8 minutes, and then conduct various performance tests after cooling.

[0066] Figure 4Images (a), (b), (c), and (d) are micrographs of the wafer surface before, after 20 minutes, after 40 minutes, and after 60 minutes of cleaning, respectively, for Example 1 (3% self-made asymmetric multi-arm triazole-bridged Gemini surfactant composition). It can be seen that as the cleaning time increases, the residual adhesive contamination on the wafer surface gradually decreases. After 20 minutes of cleaning, obvious swelling, shrinkage, and desorption phenomena appear in the residual adhesive area. Further extending the cleaning time to 40 minutes, the residual adhesive layer on the wafer surface is essentially effectively removed, and the surface cleanliness reaches its optimal state. This indicates that the cleaning system of the present invention can achieve efficient peeling and stable removal of residual adhesive from the support tape through the synergistic effect of solvent penetration, residual adhesive swelling, and the emulsification and dispersion of the asymmetric multi-arm triazole-bridged Gemini surfactant. Continuing to extend the cleaning time to 60 minutes, no significant improvement in the wafer surface condition is observed, indicating that 40 minutes is sufficient to achieve a relatively good cleaning effect. Therefore, this example determines 40 minutes as the preferred cleaning time, ensuring cleaning efficiency while also considering process efficiency and substrate compatibility.

[0067] The wafers with residual adhesive were treated using the above standard cleaning process, with all testing conditions standardized. Test data: Acrylic ester residue removal rate: 99.2%; gold corrosion rate: 0.12 Å / min; aluminum corrosion rate: 0.45 Å / min; initial foam height at 25℃: 18 mm, foam height at 5 min: 0 mm; dynamic surface tension at 100 ms: 27.2 mN / m; pure water contact angle: 11.8°; fluorescence residue value: 2.0 RFU.

[0068] The performance testing method is as follows: (1) Removal rate of acrylate residue: After completing the standard cleaning process, the removal rate is calculated by statistically analyzing the residual area of ​​the residue using an optical microscope; (2) Corrosion rate of gold and aluminum: The metal test piece was immersed in the cleaning solution at 60℃ for 30 min, and the corrosion rate was calculated by the change in film thickness, in Å / min; (3) Foam performance: The foam was tested at a constant temperature of 25℃ using a Roche foam tester. The initial foam height and the foam height after standing for 5 minutes were recorded. (4) Dynamic surface tension: measured by the maximum bubble pressure method with a response time of 100 ms; (5) Pure water contact angle: The contact angle of pure water on the wafer surface after cleaning is measured by a contact angle measuring instrument; (6) Residual fluorescence value (RFU): The fluorescence value of organic residues on the wafer surface is detected by SITA cleanliness tester.

[0069] 4. Effect Description In this embodiment, the self-made asymmetric multi-arm triazole-bridged Gemini-type surfactant composition, with an addition amount of 3%, exhibits optimal residual adhesive removal capability; foam can be quickly and completely defoamed, making it suitable for high-pressure spray production lines; it has the lowest dynamic surface tension and the strongest wetting and penetration capability; the gold and aluminum corrosion rates are far below the semiconductor control threshold (Au < 0.5 Å / min, Al < 1.0 Å / min); and the wafer organic residue is extremely low, meeting the clean production standards for high-end semiconductors.

[0070] Example 2 1. Formula Composition The product, by weight, includes 29.5 parts ethylene glycol monobutyl ether, 29.5 parts PGMEA, 15.0 parts DMSO, 10.0 parts D-limonene, 4.0 parts ethylene glycol, 7.0 parts ethanolamine, 3.0 parts triethanolamine, 0.3 parts BTA, 0.5 parts propyl gallate, 0.7 parts sodium citrate, and 2.0 parts self-made asymmetric multi-arm triazole-bridged Gemini surfactant.

[0071] 2. Preparation process The system was prepared using the same process as in Example 1, and the system was homogeneous and transparent, with no stratification or solid precipitation.

[0072] 3. Cleaning and Testing Results The standard cleaning process of Example 1 was used for testing, and the index data are as follows: Acrylic ester residue removal rate: 96.8%; gold corrosion rate: 0.16 Å / min; aluminum corrosion rate: 0.55 Å / min; initial foam height at 25℃: 28 mm, foam height at 5 min: 2 mm; dynamic surface tension at 100 ms: 29.5 mN / m; pure water contact angle: 16.5°; fluorescence residue value: 3.2 RFU.

[0073] Figure 5Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively, in Example 2 (2% self-developed Gemini surfactant composition). It can be seen that as the cleaning time increases, the residual adhesive contamination on the wafer surface gradually decreases, and the cleaning effect continuously improves. After 20 minutes of cleaning, the residual adhesive area on the wafer surface showed obvious shrinkage and desorption, indicating that the alcohol ether main solvent and polar penetration aid in the cleaning solution of this example can effectively promote the swelling and softening of the residual adhesive layer. When cleaning continued for 40 minutes, the residual adhesive was further peeled off and stably dispersed, and the contamination area on the wafer surface was significantly reduced, achieving a better cleaning effect. This indicates that the 2% addition of the asymmetric multi-arm triazole bridging Gemini surfactant can exert good interfacial wetting and emulsifying dispersion effects, promoting the effective removal of detached residual adhesive. Extending the cleaning time to 60 minutes did not significantly increase the degree of improvement on the wafer surface, indicating that 40 minutes was sufficient to achieve a relatively thorough residual adhesive cleaning effect. The above results show that, even with a reduced amount of Gemini-type surfactant, this embodiment still maintains high residual adhesive removal capability and good wafer surface compatibility, verifying the effective role of the surfactant composition in semiconductor residual adhesive cleaning systems.

[0074] 4. Effect Description With an addition of 2% of the Gemini-type surfactant composition, the residual adhesive removal effect decreased slightly, but it was still significantly better than conventional commercial surfactant compound systems; the amount of foam increased slightly, with only trace amounts of foam remaining after 5 minutes; the metal corrosion rate still met the requirements for semiconductor use, and the cleanliness met the requirements for conventional wafer fabrication processes.

[0075] Example 3 1. Formula Composition By weight, it includes 29.5 parts ethylene glycol monobutyl ether, 30.0 parts PGMEA, 15.0 parts DMSO, 10.0 parts D-limonene, 4.0 parts ethylene glycol, 7.0 parts ethanolamine, 3.0 parts triethanolamine, 0.3 parts BTA, 0.5 parts propyl gallate, 0.7 parts sodium citrate, and 1.0 part of a self-made asymmetric multi-arm triazole-bridged Gemini surfactant.

[0076] 2. Preparation process A stable and transparent cleaning solution was obtained by stirring and mixing using the same preparation process as in Example 1.

[0077] 3. Cleaning and Testing Results Performance obtained according to the standard process in Example 1: Acrylic ester residue removal rate: 92.5%; gold corrosion rate: 0.22 Å / min; aluminum corrosion rate: 0.85 Å / min; initial foam height at 25℃: 42 mm, foam height at 5 min: 8 mm; dynamic surface tension at 100 ms: 32.8 mN / m; pure water contact angle: 23.2°; fluorescence residue value: 5.1 RFU.

[0078] Figure 6 Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively, for Example 3 (1% self-developed Gemini surfactant composition). It can be seen that as the cleaning time increases, the residual adhesive contamination on the wafer surface gradually decreases, and the cleaning effect gradually improves. After 20 minutes of cleaning, the original residual adhesive area has changed significantly, with some adhesive layers showing swelling and desorption, indicating that the solvent component in the cleaning system of this example can effectively penetrate into the residual adhesive and promote its softening. When cleaning continues for 40 minutes, the residual contamination on the wafer surface is further reduced, the area covered by residual adhesive is significantly reduced, and the surface cleanliness reaches a superior level, indicating that even under a low addition level of 1.0%, the asymmetric multi-arm triazole-bridged Gemini surfactant can still promote the stable removal of detached residual adhesive through good interfacial wetting and emulsifying dispersion. Extending the cleaning time to 60 minutes, the wafer surface condition does not show significant further improvement, indicating that 40 minutes is sufficient to meet the cleaning requirements of this system. The above results show that the composite cleaning system constructed in this invention has a wide range of surfactant addition amounts. While reducing the amount of Gemini surfactant, it still maintains good residual adhesive removal effect and wafer surface compatibility, verifying its feasibility in cleaning residual adhesive from semiconductor support tapes.

[0079] 4. Effect Description Gemini surfactants, with a minimum addition of 1%, further reduce residual adhesive removal performance, but are still superior to ordinary single alcohol ether surfactant cleaning solutions. The foaming amount is further increased, and the metal corrosion rate is slightly improved, but the aluminum corrosion rate is still below the 1.0 Å / min control line. It can be used in wafer cleaning scenarios with moderate residual adhesive removal requirements and low corrosion priority.

[0080] Comparative Example 1 1. Formula Composition By weight, it includes 29.0 parts of ethylene glycol monobutyl ether, 29.5 parts of PGMEA, 15.0 parts of DMSO, 10.0 parts of D-limonene, 4.0 parts of ethylene glycol, 7.0 parts of ethanolamine, 3.0 parts of triethanolamine, 0.3 parts of BTA, 0.5 parts of propyl gallate, 0.7 parts of sodium citrate, and 3.0 parts of TO-10 isomeric tridecyl alcohol polyoxyethylene ether.

[0081] 2. Preparation and Testing Using the same preparation, cleaning, and testing processes as in Example 1, the performance data is as follows: Acrylic ester residue removal rate: 82.3%; gold corrosion rate: 0.35 Å / min; aluminum corrosion rate: 2.35 Å / min; initial foam: 120 mm, foam size after 5 min: 85 mm; dynamic surface tension: 38.5 mN / m; pure water contact angle: 38.6°; fluorescent residue: 18.5 RFU.

[0082] Comparative Example 1 only added a single TO-10 surfactant, otherwise it was the same as Example 1. Figure 7 Contents (a), (b), (c), and (d) are micrographs of the wafer surface of Comparative Example 1 (3% ordinary TO-10 single surfactant) before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively. Figure 7 It can be seen that its residual adhesive removal ability has decreased significantly; the amount of foam is large and the defoaming is extremely slow, making it unsuitable for spray equipment; the wetting and penetration are poor, the metal corrosion is severe, and the organic residue on the wafer surface is high, which cannot meet the requirements of semiconductor production.

[0083] Comparative Example 2 1. Formula Composition By weight, it includes 29.5 parts ethylene glycol monobutyl ether, 30.0 parts PGMEA, 15.0 parts DMSO, 10.0 parts D-limonene, 4.0 parts ethylene glycol, 7.0 parts ethanolamine, 3.0 parts triethanolamine, 0.3 parts BTA, 0.5 parts propyl gallate, 0.7 parts sodium citrate, 0.25 parts TO-10, 0.70 parts AEO-9, and 0.05 parts XL-50.

[0084] 2. Preparation and Testing The cleaning solution was prepared and tested using the same methods as in Example 1. The performance data are as follows: Acrylic ester residue removal rate: 88.6%; gold corrosion rate: 0.28 Å / min; aluminum corrosion rate: 1.86 Å / min; initial foam: 95 mm, foam thickness after 5 min: 62 mm; dynamic surface tension: 34.8 mN / m; pure water contact angle: 31.2°; fluorescent residue: 12.7 RFU.

[0085] Figure 8 Contents (a), (b), (c), and (d) are micrographs of the wafer surface before cleaning, after 20 minutes of cleaning, after 40 minutes of cleaning, and after 60 minutes of cleaning, respectively, for Comparative Example 2 (1% physical compound of three surfactants). It can be seen that its residual adhesive removal ability is significantly reduced; the amount of foam is large and defoaming is slow, making it unsuitable for spray equipment; wetting and penetration are poor, metal corrosion is severe, and there is high organic residue on the wafer surface, failing to meet the requirements of semiconductor production.

[0086] Comparative Example 3 1. Formula Composition The other example is similar to Comparative Example 2, except that the cleaning solution also contains 1 part by mass of Surfynol 104 acetylenol.

[0087] 2. Preparation and Testing The cleaning solution was prepared and tested using the same methods as in Example 1. The performance data are as follows: Acrylic ester residue removal rate: 92.3%; gold corrosion rate: 0.27 Å / min; aluminum corrosion rate: 1.58 Å / min; initial foam: 68 mm; 5 min foam: 37 mm; dynamic surface tension: 32.1 mN / m; pure water contact angle: 28.6°; fluorescent residue: 9.4 RFU.

[0088] Comparative Example 4 1. Formula Composition By weight, it includes 29.0 parts of ethylene glycol monobutyl ether, 29.5 parts of PGMEA, 15.0 parts of DMSO, 10.0 parts of D-limonene, 4.0 parts of ethylene glycol, 7.0 parts of ethanolamine, 3.0 parts of triethanolamine, 0.3 parts of BTA, 0.5 parts of propyl gallate, 0.7 parts of sodium citrate, and 3.0 parts of triazole bridging surfactant derived from AEO-9.

[0089] 2. Preparation and Testing The cleaning solution was prepared and the cleaning test was performed using the same method as in Example 1. The surfactant was prepared using the same alcohol ether end-group activation, azide formation, and CuAAC click reaction method as in this invention, except that XL-50 and TO-10 were replaced with AEO-9, so that all three hydrophobic arms were derived from linear fatty alcohol polyoxyethylene ethers. The test performance data are as follows: Acrylic ester residue removal rate: 93.5%; gold corrosion rate: 0.24 Å / min; aluminum corrosion rate: 1.32 Å / min; initial foam: 61 mm; 5 min foam: 34 mm; dynamic surface tension: 31.8 mN / m; pure water contact angle: 27.9°; fluorescent residue: 8.6 RFU.

[0090] Comparative Example 5 1. Formula Composition By weight, it includes 29.0 parts of ethylene glycol monobutyl ether, 29.5 parts of PGMEA, 15.0 parts of DMSO, 10.0 parts of D-limonene, 4.0 parts of ethylene glycol, 7.0 parts of ethanolamine, 3.0 parts of triethanolamine, 0.3 parts of BTA, 0.5 parts of propyl gallate, 0.7 parts of sodium citrate, and 3.0 parts of triazole bridging surfactant derived from TO-10.

[0091] 2. Preparation and Testing Using the same cleaning solution preparation and cleaning test methods as in Example 1, the three differentiated hydrophobic arms of this invention were uniformly replaced with the azide-terminated alcohol ether corresponding to TO-10, so that the resulting triazole bridging surfactant has three identical highly branched isotridecyl polyoxyethylene ether hydrophobic arms. The test performance data are as follows: Acrylic ester residue removal rate: 94.1%; gold corrosion rate: 0.25 Å / min; aluminum corrosion rate: 1.41 Å / min; initial foam: 57 mm; 5 min foam: 31 mm; dynamic surface tension: 32.0 mN / m; pure water contact angle: 28.4°; fluorescent residue: 8.9 RFU.

[0092] Comparative Example 6 1. Formula Composition By weight, it includes 29.0 parts of ethylene glycol monobutyl ether, 29.5 parts of PGMEA, 15.0 parts of DMSO, 10.0 parts of D-limonene, 4.0 parts of ethylene glycol, 7.0 parts of ethanolamine, 3.0 parts of triethanolamine, 0.3 parts of BTA, 0.5 parts of propyl gallate, 0.7 parts of sodium citrate, and 3.0 parts of triazole bridging surfactant derived from XL-50.

[0093] 2. Preparation and Testing Using the same cleaning solution preparation and cleaning test methods as in Example 1, the three differentiated hydrophobic arms of Example 1 were uniformly replaced with the azide-terminated alcohol ethers corresponding to XL-50, so that the resulting triazole bridging surfactant had three identical Guerbert bibranched C-chains. 10 The hydrophobic arm of alkyl polyoxyethylene ether has the following test performance data: Acrylic ester residue removal rate: 94.7%; gold corrosion rate: 0.23 Å / min; aluminum corrosion rate: 1.36 Å / min; initial foam: 63 mm; 5 min foam: 36 mm; dynamic surface tension: 31.5 mN / m; pure water contact angle: 27.5°; fluorescent residue: 8.2 RFU.

[0094] Comparative Example 7 1. Formula Composition By weight, the following components are present: 29.0 parts ethylene glycol monobutyl ether, 29.5 parts PGMEA, 15.0 parts DMSO, 10.0 parts D-limonene, 4.0 parts ethylene glycol, 7.0 parts ethanolamine, 3.0 parts triethanolamine, 0.3 parts BTA, 0.5 parts propyl gallate, 0.7 parts sodium citrate, and 3.0 parts a two-arm surfactant obtained by triazole bridging reaction of XL-50 and TO-10 azide-terminated modified alcohol ethers with Surfynol 104.

[0095] 2. Preparation and Testing Using the same cleaning solution preparation and cleaning test methods as in Example 1, the azide-terminated modified alcohol ethers corresponding to XL-50 and TO-10 were reacted with Surfynol 104 via a CuAAC reaction, wherein the molar ratio of XL-50 to TO-10 was 1:1, and both resulting hydrophobic arms were linked to the Surfynol 104 alkynol skeleton via 1,2,3-triazole rings. The azide-terminated modified alcohol ether corresponding to AEO-7 was not added. The resulting two-arm triazole bridging surfactant was used to prepare the cleaning solution, and its performance was tested using the same process as in Example 1. The test performance data are as follows: Acrylic ester residue removal rate: 95.6%; gold corrosion rate: 0.24 Å / min; aluminum corrosion rate: 1.48 Å / min; initial foam: 58 mm, 5 min foam: 32 mm; dynamic surface tension: 32.0 mN / m; pure water contact angle: 28.1°; fluorescent residue: 9.1 RFU.

[0096] The performance data of the examples and comparative examples are summarized in Table 1.

[0097] Table 1 Performance data of semiconductor residue cleaning solutions prepared in Examples 1 to 3 and Comparative Examples 1 to 7

[0098] As can be seen from Table 1, Examples 1 to 3 used the asymmetric multi-arm triazole-bridged Gemini surfactant composition synthesized in this application as the core cleaning component. The cleaning solutions prepared had a high removal rate of acrylate residue and a low gold / aluminum corrosion rate. Both the initial foam and the foam height after 5 minutes of cleaning were significantly lower than those of the comparative cleaning solution. Furthermore, the pure water contact angle and fluorescence residue value were significantly lower than those of the comparative solution.

[0099] Comparative Example 1 replaced the asymmetric multi-arm triazole-bridged Gemini-type surfactant composition of Example 1 with a single surfactant, TO-10; Comparative Example 2 did not use the covalent bonding method of Example 1 to prepare the surfactant composition, but instead simply physically compounded the three initial surfactants; Comparative Example 3 further physically compounded Surfynol 104 acetylenic diol based on Comparative Example 2; Comparative Example 4 replaced XL-50 and TO-10 in Example 1 with AEO-9, so that all three hydrophobic arms were derived from linear fatty alcohol polyoxyethylene ethers; Comparative Example 5 uniformly replaced the three differentiated hydrophobic arms of Example 1 with the azide-terminated alcohol ether corresponding to TO-10, so that the resulting triazole-bridged surfactant had three identical highly branched isotriadecyl polyoxyethylene ether hydrophobic arms; Comparative Example 6 uniformly replaced the three differentiated hydrophobic arms of Example 1 with the azide-terminated alcohol ether corresponding to XL-50, so that the resulting triazole-bridged surfactant had three identical Goerbert bibranched C-type surfactants. 10 Alkyl polyoxyethylene ether hydrophobic arms; Comparative Example 7 did not include the azide-terminated modified alcohol ether corresponding to AEO-7, and was otherwise the same as in Example 1. From the performance test results of the cleaning solutions in Comparative Examples 1 to 7, it is clear that the three structurally distinct hydrophobic arms in the Gemini-type surfactant compositions of this application are indispensable. The asymmetric multi-arm triazole-bridged Gemini-type surfactant composition proposed in this application, as the core component of the cleaning solution, can improve cleaning efficiency and effect while ensuring a low gold / aluminum corrosion rate, and simultaneously significantly reduce foam height.

[0100] This invention does not merely increase the number of hydrophobic chains to improve surface activity. Instead, it introduces polyoxyethylene ether structures with different chain lengths, degrees of branching, and spatial configurations into three types of triazole bridging surfactants, creating structural complementarity in interfacial behaviors such as wetting, penetration, solubilization, and residual dispersion. In the comparative examples, when the three types of hydrophobic arms were unified into the same structure, or when one type of hydrophobic arm was reduced, the cleaning performance decreased to varying degrees, indicating that the combination of different hydrophobic structures has a certain synergistic effect.

[0101] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. An asymmetric multi-arm triazole-bridged Gemini-type surfactant composition, characterized in that, It contains the following three compounds: Compound (I): An asymmetric single-arm triazole bridging surfactant formed by linking 1,2,3-triazole-1,4-dimethyl groups with a Gerbert-type branched fatty alcohol polyoxyethylene ether as the hydrophobic arm and tertiary argyne diol as the molecular backbone. Compound (II): An asymmetric single-arm triazole bridging surfactant with branched or isomeric fatty alcohol polyoxyethylene ether as the hydrophobic arm, tertiary argyne diol as the molecular backbone, and 1,2,3-triazole-1,4-dimethyl linkage. Compound (III): An asymmetric single-arm triazole bridging surfactant with a straight-chain fatty alcohol polyoxyethylene ether as the hydrophobic arm and a tertiary argyne diol as the molecular backbone, connected by 1,2,3-triazole-1,4-dimethyl linkage. The molar ratio of compound (I), compound (II) and compound (III) is (0.5-2):(0.5-2):(0.5-2).

2. The surfactant composition according to claim 1, characterized in that, The Gerbert-type branched fatty alcohol polyoxyethylene ether is selected from C8 to C96. 18 Guerbert structure fatty alcohol polyoxyethylene ether; The branched or isomeric fatty alcohol polyoxyethylene ether is selected from C 10 ~C 18 Polyoxyethylene ethers of branched or isomerized fatty alcohols; The linear fatty alcohol polyoxyethylene ether is selected from C8 to C96. 18 Straight-chain fatty alcohol polyoxyethylene ether; The tertiary ynediol is one or more of 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 1,4-diethynyl-2,3-butanediol, and 2,5-diethynyl-2,5-hexanediol.

3. The method for preparing the surfactant composition according to claim 1 or 2, characterized in that, Includes the following steps: (1) The terminal hydroxyl alcohol ether and the sulfonating agent are reacted with each other in an anhydrous organic solvent under the protection of an inert gas in the presence of an alkaline acid binder to obtain a sulfonate ester terminal alcohol ether intermediate; the terminal hydroxyl alcohol ether is of three types, namely Guerbert type branched fatty alcohol polyoxyethylene ether, branched or isomer fatty alcohol polyoxyethylene ether and linear fatty alcohol polyoxyethylene ether, and the three sulfonate ester terminal alcohol ether intermediates are obtained after reaction respectively; (2) The three sulfonate-terminated alcohol ether intermediates described in step (1) are subjected to nucleophilic substitution reactions with azides in a polar aprotic solvent under a sealed inert gas system to obtain three azide-terminated modified alcohol ethers, namely azide-Gelbert-type branched fatty alcohol polyoxyethylene ether, azide-branched or isomerized fatty alcohol polyoxyethylene ether and azide-linear fatty alcohol polyoxyethylene ether. (3) The three azide-terminated modified alcohol ethers obtained in step (2) are mixed in a molar ratio of (0.5-2):(0.5-2):(0.5-2) and mixed with tertiary acetylenol in the presence of a copper catalyst and a reducing agent in an alcohol-water mixed solvent under an inert atmosphere at normal pressure. The reaction is carried out by stirring and heating, so that the central acetylenol skeleton is mainly composed of monosubstituted products. After purification, a composition composed of three types of single-branched triazole bridging surfactants is obtained, namely the asymmetric multi-arm triazole bridging Gemini type surfactant composition.

4. The preparation method according to claim 3, characterized in that, The sulfonating agent in step (1) is one or more of p-toluenesulfonyl chloride, methanesulfonyl chloride, and p-nitrobenzenesulfonyl chloride; the basic acid-binding agent is one or more of triethylamine, pyridine, and N,N-diisopropylethylamine; and / or, The anhydrous organic solvent is one or more selected from anhydrous dichloromethane, anhydrous tetrahydrofuran, anhydrous acetonitrile, anhydrous N,N-dimethylformamide, anhydrous 1,2-dichloroethane, and anhydrous toluene; and / or, The polar aprotic solvent mentioned in step (2) is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, N-methylpyrrolidone, and acetonitrile; and / or, The reaction time of the copper-catalyzed azide-alkynyl cycloaddition reaction in step (3) is 3-5 hours; the alcohol in the alcohol-water mixed solvent is selected from one or more of tert-butanol, ethanol, methanol, and isopropanol; the volume ratio of alcohol to water is 1:3 to 4:

1.

5. The preparation method according to claim 3, characterized in that, The copper catalyst mentioned in step (3) is one or more of copper sulfate pentahydrate, copper sulfate, cuprous iodide, cuprous bromide, and cuprous chloride; and / or, The reducing agent is one or more selected from ascorbic acid, sodium ascorbate, sodium sulfite, sodium bisulfite, and sodium thiosulfate; and / or, The molar ratio of the azide group to the alkynyl group in the mixture of the three azide-terminated modified alcohol ethers is 0.8:1 to 1.5:

1.

6. A cleaning solution for residual adhesive on semiconductor support tape, characterized in that, The composition comprises, by weight, 50-70 parts of main solvent, 10-30 parts of penetration aid, 5-15 parts of alkaline penetration agent, 0.3-1.5 parts of corrosion inhibitor, 0.3-1 part of chelating agent, 1-10 parts of co-solvent, and 1-5 parts of the asymmetric multi-arm triazole-bridged Gemini surfactant composition as described in claim 1 or 2.

7. The cleaning solution as described in claim 6, characterized in that, The main solvent is selected from one or more of ether solvents, alcohol ether solvents, and ester solvents; The penetration enhancer is selected from one or more of sulfoxides, amides, and terpenes; The alkaline penetrant is selected from one or more fatty alcohol amine compounds; The corrosion inhibitor includes a gold corrosion inhibitor and an aluminum corrosion inhibitor, wherein the gold corrosion inhibitor is selected from one or more azole compounds; and the aluminum corrosion inhibitor is selected from one or more polyphenolic compounds and organic acid salts. The chelating agent is selected from one or more of carboxylates or polycarboxylate chelating agents; The co-solvent is selected from one or more polyols and alcohol ethers.

8. The method for preparing the semiconductor support tape residual cleaning solution as described in claim 6 or 7, characterized in that, Includes the following steps: The main solvent, penetrating agent, and co-solvent are mixed evenly according to the weight ratio to obtain a solvent system; the alkaline penetrating agent is mixed evenly with the solvent system, and then the corrosion inhibitor and chelating agent are added and stirred until dissolved; finally, the asymmetric multi-arm triazole bridging Gemini type surfactant composition is added and stirred until homogeneous and transparent to obtain a semiconductor support tape residue cleaning solution.

9. The application of the semiconductor support tape residue cleaning solution as described in claim 6 or 7 in the removal of acrylate residue from support tape after semiconductor wafer dicing and backside thinning processes.

10. The application as described in claim 9, characterized in that, When applying, the cleaning temperature is 55-70℃. Use soaking and stirring or spraying methods. Each cleaning session lasts 10-30 minutes and is repeated 1-3 times. Then rinse with isopropanol and dry with hot air.

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