A quaternary ammonium hydroxide solution, a preparation method, a cleaning composition and applications thereof

Abstract

The application relates to the fields of semiconductor manufacturing and fine chemical technology, and discloses a quaternary ammonium hydroxide solution with a multi-quaternary ammonium salt structure based on a dendritic polyamine with a branch number m greater than or equal to 3, a preparation method of the quaternary ammonium hydroxide solution, a cleaning composition containing the quaternary ammonium hydroxide solution, and application of the quaternary ammonium hydroxide solution in semiconductor cleaning. The quaternary ammonium hydroxide solution is prepared through quaternization reaction of a dendritic polyamine with a specific general formula with a branch number m greater than or equal to 3 and an organic epoxy compound; the dendritic polyamine includes but is not limited to tri(2-dimethylaminoethyl)amine, tetra(3-dimethylaminopropyl)ethylenediamine and the like. The quaternary ammonium hydroxide solution has a multi-quaternary ammonium salt structure, can be used for preparing a cleaning composition for a semiconductor wet cleaning process, can effectively remove chemical residues on metal surfaces or dielectric surfaces, and can meet the requirements of high-efficiency cleaning, low toxicity, no odor, high stability, compatibility with metal / dielectric double surfaces and low corrosion in the field of semiconductor wet cleaning, and the preparation process is simple and controllable and easy for industrial production.

Description

Technical Field

[0001] This invention relates to the fields of semiconductor manufacturing and fine chemical technology, specifically to a quaternary ammonium hydroxide solution (i.e., a quaternary ammonium base based on a branched polyamine with a branch number m≥3) with a multi-quaternary ammonium salt structure, its preparation method, cleaning composition, and its application in semiconductor cleaning. Background Technology

[0002] In the manufacturing process of electronic devices such as integrated circuits and photovoltaic cells, wet processing steps such as etching, cleaning, polishing, and pattern development are crucial. These steps rely on chemical reagents to remove chemical residues such as photoresist residues and etching residues from the substrate surface.

[0003] In existing technologies, tetramethylammonium hydroxide (TMAH) is a widely used traditional reagent, exhibiting excellent residue removal effects in processes such as etching, cleaning, polishing, and pattern development. However, TMAH is highly toxic to the human nervous system, posing potential health risks to operators during production, storage, and use, and may also cause environmental harm due to leakage, failing to meet the "green and safe" development requirements of modern semiconductor manufacturing.

[0004] To mitigate the toxicity of tetramethylammonium hydroxide, the industry has explored the use of choline hydroxide as an alternative reagent. While choline hydroxide offers advantages such as low toxicity, relatively low cost, and easy biodegradability, it has significant drawbacks in practical applications: firstly, it releases an irritating odor during use, affecting the operating environment; secondly, it exhibits poor chemical stability, readily decomposing to generate colored solutions and precipitates, which not only reduces cleaning effectiveness but may also contaminate semiconductor device surfaces, impacting subsequent process stability and product yield.

[0005] In addition, CN112638863A discloses a quaternary ammonium base prepared by reacting polyamines with organic epoxy alkanes. It uses linear polyamines and bibranched polyamines as raw materials. Although it has improved the problems of toxicity and irritating odor to a certain extent, this linear polyamine quaternary ammonium base still has inherent defects such as insufficient cleaning efficiency, poor thermal stability, high corrosion of metal surfaces, and easy residue on dielectric surfaces. It cannot simultaneously meet all the requirements of semiconductor cleaning for high efficiency, low toxicity, no odor, high stability, and low corrosion.

[0006] In summary, the semiconductor industry urgently needs to develop a new cleaning agent that simultaneously meets the following requirements: 1) efficient removal of chemical residues to match the cleaning effect requirements of existing processes; 2) low toxicity, which is friendly to the health of operators and the environment; 3) no obvious irritating odor, which improves the operating environment; 4) high chemical stability, which is not easily decomposed and ensures process stability; 5) compatibility with both metal and dielectric surfaces and low corrosion. Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of the prior art and provide a quaternary ammonium hydroxide solution with a branched polyamine structure of m≥3, a method for its preparation, a cleaning composition, and its application in semiconductor cleaning. This invention addresses the problems of traditional semiconductor cleaning reagents such as choline hydroxide and tetramethylammonium hydroxide, which have obvious odors, poor stability, or high toxicity. It also solves the technical problems of existing monoquaternary ammonium bases and linear polyamine quaternary ammonium bases, such as low cleaning efficiency, poor stability, high toxicity, high corrosion, and easy residue on dielectric surfaces. In this way, it meets the various practical needs of the semiconductor wet cleaning field for high efficiency, low toxicity, no odor, high stability, and low corrosion.

[0008] Based on this, the present invention discloses a quaternary ammonium hydroxide solution, which is prepared by a quaternization reaction of a dendritic polyamine with an organic epoxide; the dendritic polyamine has the following general formula: Core–[Linker–N(R1)R2] m ; Core is selected from nitrogen atoms, C1-C 10 Alkylene, C1-C 10 Saturated hydrocarbon diamine or polyamine residues, C6-C 10 aryl, or C1-C 10 The heterocyclic group; the number of heteroatoms N in the saturated hydrocarbon diamine or polyamine residue is ≤3; the heteroatoms of the heterocyclic group are N and / or O, and the number of heteroatoms is ≤2; Linker is selected from C2-C6 alkylene groups or C2-C6 alkene groups containing ether bonds; R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or C2-C4 hydroxyalkyl; The dendritic polyamine molecule contains at least one tertiary amine group, or at least one primary or secondary amine group that can be converted into a tertiary amine group in situ with an organic epoxy compound; m is an integer from 3 to 6.

[0009] This invention also discloses a method for preparing a quaternary ammonium hydroxide solution, comprising the following preparation steps: Step 1: Add dendritic polyamine and solvent to the reaction vessel. The mass ratio of dendritic polyamine to solvent is 1:(2~5). Step 2: Purge the air out of the vessel with nitrogen, raise the temperature to 40-50℃, and adjust the stirring speed. Step 3: Add organic epoxy compound dropwise to the reaction vessel. The molar ratio of dendritic polyamine to organic epoxy compound is 1:(3~8). During the dropwise addition, control the pressure inside the vessel to ≤0.5MPa and maintain the temperature at 40~50℃. Step 4: After the addition is complete, continue stirring the reaction until the pressure inside the reactor drops to atmospheric pressure, and check that the quaternization rate of the reaction system is ≥50%. Step 5: After the reaction is complete, cool to room temperature to obtain a quaternary ammonium hydroxide solution.

[0010] The present invention also discloses a cleaning composition comprising a quaternary ammonium hydroxide solution as described in the present invention as an active component; the cleaning composition further comprises one or more combinations of chelating agents, metal corrosion inhibitors, etchants, and solvents.

[0011] Preferably, a cleaning composition comprises the following components in mass fractions: Quaternary ammonium hydroxide solution: 0.5-10 wt%; Chelating agent: 0.01~1wt%; Metal corrosion inhibitor: 0.01~2wt%; Solvent: Balance.

[0012] This invention also discloses an application of a cleaning composition, wherein the cleaning composition is applied to clean chemical residues on the surface of a semiconductor device; the application method includes the following cleaning process steps: Step a, Pretreatment: Rinse the semiconductor devices to be cleaned with deionized water; Step b, cleaning treatment: Immerse the pretreated semiconductor device in the cleaning composition, or apply the cleaning composition to the surface of the semiconductor device by spraying. The cleaning temperature is 20-70℃ and the cleaning time is 0.5-30min. Step c, Post-processing: Rinse the semiconductor device with deionized water and dry it.

[0013] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The quaternary ammonium hydroxide solution of the present invention is prepared by reacting a specific dendritic polyamine with a branch number m≥3 with an organic epoxy compound. Compared with existing reagents such as TMAH or monoquaternary ammonium bases or linear polyamine quaternary ammonium bases such as choline hydroxide, (1) the three-dimensional dendritic structure of the multi-quaternary ammonium salt of the quaternary ammonium hydroxide solution of the present invention has excellent removal effect on chemical residues on semiconductor metal surfaces / dielectric surfaces, which can match or even be better than traditional tetramethylammonium hydroxide. Therefore, the removal rate of chemical residues after cleaning semiconductor surfaces with a cleaning composition containing the quaternary ammonium hydroxide solution can be further improved. (2) The quaternary ammonium hydroxide solution of the present invention, in combination with the optimization of the multi-dendritic structure, also brings the following technical effects: it helps to improve the efficient removal effect of its cleaning composition on chemical residues on semiconductor surfaces, and its toxicity is significantly reduced compared with TMAH. Therefore, it poses less health and environmental risks to operators and also helps to reduce the metal corrosion rate on semiconductor surfaces.

[0014] 2. Compared with choline hydroxide and the like, the quaternary ammonium hydroxide solution and cleaning composition of the present invention have no irritating odor and high chemical stability, effectively avoiding contamination of the device surface by decomposition products.

[0015] 3. The quaternary ammonium hydroxide solution of the present invention has a clearly defined general formula for its dendritic polyamines, with abundant examples, a simple and controllable preparation process, readily available raw materials, and is suitable for industrial production.

[0016] 4. The quaternary ammonium hydroxide solution of the present invention has flexible application methods in semiconductor cleaning, can be adapted to different types of wet processing procedures, has stable cleaning effect, is suitable for the manufacturing process of electronic devices such as integrated circuits and photovoltaic cells, and has broad prospects for industrial application. Detailed Implementation

[0017] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to specific embodiments.

[0018] The use of the term "comprising / including" and its derivatives herein is not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are disclosed herein. For the avoidance of doubt, any composition claimed herein using the term "comprising / including" may contain any additional additives, auxiliaries, or compounds unless otherwise stated. Conversely, the use of the term "consistently comprising" excludes any other components, steps, or procedures not essential for operability from the scope of the following statements; and the use of the term "composed of" excludes any components, steps, or procedures not expressly described or listed. The term "or," unless otherwise stated, covers any single member or any combination thereof listed.

[0019] The articles “a” and “an” are used to refer to one or more (i.e., at least one) grammatical objects of the article. For example, “an adenylic polyamine” refers to one or more adenylic polyamines. Phrases such as “in one embodiment / example”, “according to one embodiment / example,” etc., generally indicate that the specific feature, structure, or property following the phrase is included in at least one embodiment / example of this disclosure, and may be included in more than one embodiment / example. Such phrases do not necessarily refer to the same embodiment / example. If the specification states that a component or feature “may,” “can,” “may,” or “may” be included or have a certain property, then that component or feature is not necessarily required to be included or have that property.

[0020] The term “about” as used in this article means that the value or range is flexible to a certain extent. It usually means that the value is allowed to fluctuate within 10%, 5% or 1% of the specified value, or that the range limit is allowed to vary within 10%, 5% or 1%.

[0021] Numerical values ​​expressed in range format should be interpreted broadly: in addition to the explicitly listed range endpoints, they should also encompass all independent numerical values ​​and subranges within that range, as if each numerical value and subrange had been explicitly listed. For example, the range "1 to 6" should be considered as having explicitly disclosed subranges such as "1 to 3", "2 to 4", "3 to 6", and independent numerical values ​​such as 1, 2, 3, 4, 5, and 6. This rule applies to ranges of all widths.

[0022] In the methods and processes described herein, the steps may be performed in any order unless explicitly specified in terms of time or sequence. Furthermore, unless the claims explicitly require step-by-step implementation, the specified steps may be performed simultaneously.

[0023] The term "substantially free of" means that the amount of a particular compound in a composition or mixture has no material effect on its properties. For example, "substantially free of choline hydroxide" means that the amount of choline hydroxide contained will not have a material effect on the odor or color of the composition or mixture. Those skilled in the art, in conjunction with this disclosure, can determine whether the amount of a compound has a material effect. In some embodiments / examples, based on the total weight of the composition, "substantially free of" may mean that the content of the compound is less than 2% by weight, less than 1% by weight, less than 0.5% by weight, less than 0.1% by weight, less than 0.05% by weight, or even less than 0.01% by weight. In some embodiments / examples, "substantially free of" also means that the particular compound is completely absent in the corresponding composition (i.e., the content is 0.0% by weight).

[0024] The present invention provides a quaternary ammonium hydroxide solution, which is prepared by quaternization reaction of a branched polyamine with a branch number m≥3 with an organic epoxy compound.

[0025] In the quaternary ammonium hydroxide solution of the present invention, the combined dendritic polyamine must meet the core requirement of containing three or more amino groups, and at least one amino group being a tertiary amino group or capable of being converted into a tertiary amino group in situ. At the same time, it must match the branching structure characteristics of the dendritic molecule. The present invention strictly limits the number of branches m of the dendritic polyamine to m≥3. Based on the above requirements and limitations, the standard general formula of the dendritic polyamine used in the present invention is shown in formula (1): Core–[Linker–N(R1)R2] m (1).

[0026] The definitions and restrictions of each group in formula (1) are as follows: Core represents the central core of the dendritic polyamine. Core is the core skeleton of the dendritic molecule; it is selected from nitrogen (N) atoms and has 1-10 carbon atoms (i.e., C1-C1). 10 ) alkylene, C1-C 10 Saturated hydrocarbon diamine or polyamine residues (heteroatom is N, and the number of heteroatoms is ≤3), C6-C 10 aryl, or C1-C10 The heterocyclic group (the heteroatom is N and / or O, and the number of heteroatoms is ≤2); the core is preferably a nitrogen atom (N), a methylene, a phenylene, an ethylenediamine group (such as an ethylenediamine residue) or a trimethylolpropane group, to ensure that the central core has sufficient branching sites to connect the branched chains and to avoid the steric hindrance of the molecule due to the core skeleton being too large, which would affect subsequent reactions.

[0027] Linker represents a connecting chain that links the central nucleus to the terminal amino group. A linker is a linear or slightly branched group that connects the central nucleus and the amino group, selected from alkylene groups having 2-6 carbon atoms (-C). n H 2n -, n=2-6) or alkoxides containing ether bonds (-C n H 2n -OC n H 2n - (n=1-3, preferably n=2-3); the linker chain needs to ensure that there is an appropriate distance between the amine group and the central core, so as to avoid steric hindrance that hinders the reaction between the organic epoxy compound and the amine group, and to ensure that the molecule as a whole has a certain degree of solubility to adapt to the subsequent solution system preparation.

[0028] N(R1)R2 represents the terminal amino functional group. N(R1)R2 is the active functional group of the dendritic polyamine, satisfying: R1 and R2 are independently selected from hydrogen, alkyl groups with 1-4 carbon atoms (such as methyl, ethyl, n-propyl or isopropyl, etc.), or hydroxyalkyl groups with 2-4 carbon atoms (such as hydroxyethyl or hydroxypropyl, etc.); moreover, the dendritic polyamine molecule contains at least one tertiary amine group (i.e., neither R1 nor R2 is hydrogen), or contains a primary amine group (R1=R2=H) or a secondary amine group (R1=H, R2 is alkyl or hydroxyalkyl) that can be converted in situ to a tertiary amine group by reacting with an organic epoxy compound, to ensure that it can subsequently undergo a quaternization reaction with an organic epoxy compound to form a polyquaternary ammonium salt structure.

[0029] m represents the number of branched chains containing amine groups attached to the central core (referred to as the number of branches). m is an integer from 3 to 6; m≥3 (satisfies the branching characteristics of dendritic molecules, distinguishing them from linear polyamines), and m≤6 (avoiding excessive steric hindrance due to too many branches, which would affect the interaction with residues and the dispersibility in solution).

[0030] Based on the above general formula and limitations, the dendritic polyamines used in this invention may specifically include, but are not limited to, the following types: 1. Tris(2-aminoethyl)amine, CAS No.: 4097-89-6. The molecular structure of tris(2-aminoethyl)amine conforms to the requirements of the above general formula (1), and its specific molecular structure is shown in the following structural formula (2): In formula (2), Core is a nitrogen atom (N), Linker is 1,2-ethylene (-C2H4-), the terminal amino functional group is a primary amino group (-NH2), and m=3; (2); The characteristics of tri(2-aminoethyl)amine: The three primary amine groups in the molecule can react with organic epoxides (such as ethylene oxide) to first be converted in situ to tertiary amine groups (-N(CH2CH2OH)2), and then further quaternized to form a polyquaternary ammonium salt structure, which meets the reactivity requirements of polyamines. Moreover, the molecular structure is simple and the raw materials are readily available.

[0031] 2. Tris(3-dimethylaminopropyl)amine, CAS No.: 33329-35-0. The molecular structure of tris(3-dimethylaminopropyl)amine conforms to the requirements of the above general formula (1), and its specific molecular structure is shown in the following structural formula (3): In formula (3), Core is a nitrogen atom (N), Linker is 1,3-propylidene (-C3H6-), the terminal amino functional group is a tertiary amino group (-N(CH3)2), m=3; (3); Characteristics of tris(3-dimethylaminopropyl)amine: It contains three tertiary amine groups directly in the molecule, and can undergo quaternization reaction with organic epoxy compounds (such as propylene oxide) without in-situ conversion, exhibiting high reactivity; its branched structure can enhance the adsorption and removal capabilities of semiconductor surface residues, making it suitable for semiconductor cleaning applications.

[0032] 3. Tris(2-dimethylaminoethyl)amine, CAS No.: 33527-91-2. The molecular structure of tris(2-dimethylaminoethyl)amine conforms to the requirements of the above general formula (1), and its specific molecular structure is shown in the following structural formula (4): In formula (4), Core is a nitrogen atom (N), Linker is 1,2-ethylene (-C2H4-), the terminal amino functional group is a tertiary amino group (-N(CH3)2), m=3; (4); Characteristics of tris(2-dimethylaminoethyl)amine: It contains three tertiary amine groups directly in the molecule, and can undergo quaternization reaction with organic epoxy compounds (such as ethylene oxide, propylene oxide or glycidyl ether) without in-situ conversion, exhibiting high reactivity; its branched structure can enhance the adsorption and removal capacity of semiconductor surface residues.

[0033] 4. Tetrakis (3-dimethylaminopropyl)ethylenediamine. The molecular structure of tetrakis (3-dimethylaminopropyl)ethylenediamine conforms to the requirements of the above general formula (1), and its specific molecular structure is shown in the following structural formula (5): In formula (5), Core is the tertiary amine skeleton of ethylenediamine ( N CH2CH2 N (belonging to ethylenediamine residues or ethylenediamine derivatives), the two original secondary amine nitrogens of ethylenediamine are all alkylated, there are no NH bonds, and both central nitrogens are tertiary amines; the linker is a trimethylene (1,3-propene, –(CH2)3–), with a total of 4 equivalent 1,3-propene linking chains, which respectively connect the two central tertiary amine Ns to the 4 terminal amine groups; the terminal amine functional group is a tertiary amine group (-N(CH3)2), m=4; (5); Characteristics of tetra(3-dimethylaminopropyl)ethylenediamine: The central core is an ethylenediamine derivative group, which is connected to four branched chains containing tertiary amine groups. The tertiary amine groups can directly undergo quaternization reactions with organic epoxides. The molecule has a large number of amine groups, and the resulting multi-quaternary ammonium salt structure can provide more active sites, thus improving the removal effect on complex residues.

[0034] 5. N,N,N',N'-tetrakis-(2-aminoethyl)ethylenediamine, CAS No.: 4097-90-9. The molecular structure of N,N,N',N'-tetrakis-(2-aminoethyl)ethylenediamine conforms to the requirements of the above general formula (1), and its specific molecular structure is shown in the following structural formula (6): In formula (6), Core is the tertiary amine skeleton of ethylenediamine ( N CH2CH2 N (belonging to ethylenediamine residues or ethylenediamine derivatives), the two original secondary amine nitrogens of ethylenediamine are all alkylated, there are no NH bonds, and both central nitrogens are tertiary amines; the linker is 1,2-ethylene (-C2H4-), a total of 4 equivalent 1,2-ethylene linking chains, which respectively connect the two central tertiary amine Ns to the four terminal primary amine groups; the terminal amine functional group is a primary amine group (-NH2), m=4; (6); The characteristics of N,N,N',N'-tetra(2-aminoethyl)ethylenediamine: The central core is an ethylenediamine derivative group, which connects four branch chains containing primary amine groups. The primary amine groups can react with organic epoxy compounds to first convert them into tertiary amine groups, and then further quaternize to form a multi-quaternary ammonium salt structure. The molecule has abundant amine sites that can participate in the reaction, and the final multi-quaternary ammonium salt structure can output a large number of active sites, which enhances the removal effect on complex residues.

[0035] The dendritic polyamine may be selected from one or more of tris(2-aminoethyl)amine, tris(3-dimethylaminopropyl)amine, tetra(2-methylaminoethyl)ethylenediamine, tris(2-dimethylaminoethyl)amine, penta(2-aminopropyl)diethylenetriamine, tris(4-dimethylaminobutyl)benzene, tetra(3-dimethylaminopropyl)ethylenediamine, and N,N,N',N'-tetra(2-aminoethyl)ethylenediamine.

[0036] In the quaternary ammonium hydroxide solution of the present invention, the organic epoxy compound has the following general structural formula (7): (7); Among them, R3, R4, and R5 may be the same or different, and each is independently selected from hydrogen, straight-chain or branched alkyl groups having 1 to 12 carbon atoms, and C2-C4. 12 Unsaturated hydrocarbon group, aryl group having 6 to 18 carbon atoms, aralkyl group having 7 to 18 carbon atoms; or, any two of R3, R4, and R5 can be linked together to form a cyclic structure containing 3 to 12 carbon atoms together with two carbon atoms on the epoxide ring; or, in some examples, one or more of the R3, R4, and R5 groups can further contain one or more oxygen atoms (such as hydroxyl groups, ether bonds).

[0037] Organic epoxy compounds may include, but are not limited to: ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, styrene oxide, glycidyl ether (epoxypropanol), allyl glycidyl ether, phenyl glycidyl ether, alkyl glycidyl ether, butadiene epoxide (C4 epoxy containing an olefinic bond), cyclohexane epoxide, bicyclo[2.2.1]heptene oxide (bicyclo[2.2.1]hept-2-ene oxide), bicyclo[2.2.2]octene oxide (bicyclo[2.2.2]oct-2-ene oxide), or any combination thereof.

[0038] Preferably, the organic epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 1,2-epoxybutane, styrene oxide, and glycidyl ether (epoxypropanol).

[0039] In the quaternary ammonium hydroxide solution of the present invention, the solvent used may be one or more of the following: water, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, butyrolactone, N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), etc.; preferably deionized water to ensure that the solution system is environmentally friendly and suitable for semiconductor cleaning requirements. The solvent may account for about 20 wt% to about 99.9 wt% of the total weight of the quaternary ammonium hydroxide solution.

[0040] A method for preparing a quaternary ammonium hydroxide solution according to the present invention includes the following preparation steps: Step 1: Add dendritic polyamine and solvent to a reaction vessel equipped with a stirring device, a temperature control device and a pressure control device; wherein the mass ratio of dendritic polyamine to solvent is 1:(2~50), and is optimized to be 1:(2~5); Step 2: Purge the reactor with nitrogen gas to remove air (to prevent air from affecting reaction stability). Then raise the temperature inside the reactor to 40-50℃ and control the stirring rate to 200-300 r / min. Step 3: Add the organic epoxy compound dropwise to the reaction vessel at a rate of 0.5-1.0 mL / min; wherein the molar ratio of the dendritic polyamine to the organic epoxy compound is 1:3~1:100 (e.g., 1:5), preferably 1:(3~8); during the dropwise addition, control the pressure inside the vessel to not exceed 0.5 MPa and maintain the temperature at 40~50℃; Step 4: After the addition is complete, continue stirring for a period of time (e.g., 1-20h, 1-3h, or 2-20h) until the pressure inside the reactor drops to atmospheric pressure. Detect the degree of quaternization using potentiometric titration (using hydrochloric acid as the titrant) to ensure that the quaternization rate is ≥50%. Step 5: After the reaction is complete, cool to room temperature to obtain a quaternary ammonium hydroxide solution.

[0041] Compared with existing technologies (such as CN112638863A, choline hydroxide, etc.) that disclose linear or low-branching polyamines (such as N,N,N',N'-tetramethylethylenediamine, with a branch number m=2), the present invention provides a quaternary ammonium hydroxide solution based on a dendritic polyamine with a branch number m≥3. The "dendritic polyamine" (branch number m≥3) used in this invention is not a simple structural substitution, but rather, through its unique spatial configuration and charge distribution, it produces a synergistic effect in the key stages of semiconductor cleaning. Specifically: 1. Enhanced "Anchoring-Encapsulation" Effect: The multi-quaternary ammonium salt molecules generated by linear polyamine reactions have a "chain-like" structure. Their adsorption on the residue surface mainly relies on single-point contact, resulting in relatively weak binding forces and easy desorption during the cleaning process. However, the dendritic polyamines of this invention (such as tris(3-dimethylaminopropyl)amine, m=3) form "star-shaped" or "tree-shaped" multi-cations with a three-dimensional structure after quaternization. This configuration allows them to form multi-site "anchoring" on the residue (usually negatively charged) surface through multiple quaternary ammonium salt cation sites. At the same time, their hydrophobic dendritic framework can "encapsulate" and solubilize organic residues, producing a synergistic "anchoring-encapsulation" effect, thereby significantly improving the removal efficiency of complex chemical residues (as shown in the cleaning composition of Example 3 of this invention below, the residue removal rate of the cleaning composition of this invention can be >95%).

[0042] 2. Optimized steric hindrance and metal protection: The linear quaternary ammonium base (m=2) of CN112638863A has high molecular flexibility, is prone to shrinking, and easily exposes highly active hydroxyl groups, which can penetrate into the metal surface lattice, leading to an increased risk of metal corrosion. In contrast, the dendritic multi-quaternary ammonium salt structure (m≥3) of this invention has significantly increased steric hindrance, forming a relatively rigid cationic "shell" that effectively shields the metal surface from the attack of highly nucleophilic hydroxyl anions. Simultaneously, this cationic "shell" preferentially adsorbs onto the metal surface, forming a physical barrier layer, thus unexpectedly achieving a lower metal corrosion rate while ensuring efficient cleaning. Experiments show that the cleaning composition of this invention can achieve a corrosion rate of less than 0.05 μm / h for copper, which is superior to conventional linear quaternary ammonium base systems.

[0043] 3. Enhanced Chemical Stability: One of the mechanisms by which choline hydroxide and other substances readily decompose is through intramolecular β-hydrogen elimination. However, the dendritic multi-quaternary ammonium salt structure of this invention, due to its highly branched structure and rigidity around the nitrogen atom, alters the conformation and activity of β-hydrogen, significantly inhibiting degradation pathways such as Hoffmann elimination. Experiments have confirmed that the cleaning composition of this invention does not produce any colored precipitate after being placed at 60°C for 72 hours, overcoming the inherent instability of choline-based cleaning agents.

[0044] The present invention discloses an application of a quaternary ammonium hydroxide solution in semiconductor cleaning. The application method includes: using the aforementioned quaternary ammonium hydroxide solution as the core active component to formulate a cleaning composition for wet cleaning of residues on the surface of semiconductor devices. In addition to the aforementioned quaternary ammonium hydroxide solution, the cleaning composition may further contain one or more combinations of chelating agents, metal corrosion inhibitors, etchants, and solvents.

[0045] In the cleaning composition of the present invention, the amount of quaternary ammonium hydroxide solution added can be 0.5wt% to 10wt% of the total weight of the cleaning composition.

[0046] In the cleaning composition of the present invention, the chelating agent may be any one or more combinations of the following substances, specifically covering the following range: (1) β-Diketone compounds: such as acetylacetone (2,4-pentanedione), 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, etc. (2) Amines / amino acids: such as ethylenediamine, pentamethyldiethylenetriamine (PMDETA), glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, lysine, etc. (3) Polymeric organic acids: such as iminodiacetic acid (IDA), malonic acid, oxalic acid, succinic acid, hypozinotriacetic acid, malic acid, citric acid, maleic acid, ethylenediaminetetraacetic acid (EDTA), EDTA-2NH3 (ethylenediaminetetraacetic acid diammonium salt), (1,2-cyclohexanediazide)tetraacetic acid (CDTA), diethylenetriaminepentaacetic acid (DTPA), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), ethylenediaminedisuccinic acid, propylenediaminetetraacetic acid, etc. (4) Phosphonic acids and phosphonic acid derivatives: such as hydroxyethylidene diphosphonic acid (HEDP), nitrotri(methylenephosphonic acid) (NTMP), diethylenetriaminepenta(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTMPA), etc.; (5) Other optional types: monocarboxylic acid acetic acid; inorganic weak acid boric acid; benzalkonium chloride; imidazole; tetraethylene glycol dimethyl ether; 1,3,5-triazine-2,4,6-trithiol trisodium salt solution; 1,3,5-triazine-2,4,6-trithiol triammonium salt solution; sodium diethyldithiocarbamate; disubstituted dithiocarbamate.

[0047] The amount of chelating agent added can be from about 0.01 wt% to about 1 wt% of the total weight of the cleaning composition.

[0048] In the cleaning composition of the present invention, the metal corrosion inhibitor may be selected from one or more combinations of the following categories, covering multiple systems adapted to semiconductor processes, such as nitrogen-containing heterocyclic surfactants, ionic surfactants, and nonionic surfactants. The specific selection range is as follows: (1) Nitrogen-containing heterocyclic / thiol / ketooxime compounds. These metal corrosion inhibitors are core corrosion inhibitors adapted to copper and other metal interconnect structures, including but not limited to: 5-amino-1,3,4-thiadiazole-2-thiol (ATDT), 2-amino-5-ethyl-1,3,4-thiadiazole, benzotriazole (BTA), 1,2,4-triazole (TAZ), toluenetriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3 -Amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole (3-ATA), 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthio-benzotriazole, halobenzotriazole (halogen is F, Cl, Br or I), naphthalene Triazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazolium, 2-mercaptothiazoline, 5-amino-1,2,4-triazole (5-ATA), 3,5-diamino-1,2,4-triazole, tetrazolium, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 5-methyltetrazole, 5-mercapto-1-methyl-tetrazole, 1-phenyl-1H-tetrazole-5-thiol, 2-benzylpyridine, succinimide, 2,4-diamino-6-methyl -1,3,5-triazine, thiazole, triazine, 1,3-dimethyl-2-imidazolone, 1,5-pentamethylenetetrazolium, diaminomethyltriazine, imidazolinthione, 4-methyl-4H-1,2,4-triazol-3-thiol, 4-amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, benzothiazole, imidazole, benzimidazole, 2-aminobenzimidazole, 1-methylimidazolium, indazole, adenine, adenosine, carbazole, saccharin, uric acid, benzoic acid oxime; (2) Cationic quaternary ammonium salts. These metal corrosion inhibitors can inhibit metal over-corrosion in alkaline environments by forming an electrostatic adsorption layer on the metal surface. Examples include, but are not limited to: benzyl chloride, benzyl dimethyl dodecyl ammonium chloride, dodecyl trimethyl ammonium bromide, hexadecylpyridinium chloride, benzyl dimethylphenyl ammonium chloride, hexadecyl trimethyl p-toluenesulfonate ammonium, hexadecyl trimethyl ammonium hydroxide, 1-methyl-1'-tetradecyl-4,4'-bipyridinium dichloride, alkyl trimethyl ammonium bromide, aminopropyl hydrochloride, benzyl chloride, benzyl dimethyl hexadecyl ammonium chloride, benzyl dimethyl tetradecyl ammonium chloride, benzyl dodecyl dimethyl ammonium bromide, benzyl dodecyl dimethyl ammonium chloride, cetylpyridinium chloride, p-toluenesulfonate choline salt, dimethyl distearate ammonium bromide, dodecyl ethyl dimethyl ammonium bromide, dodecyl trimethyl... Methyl ammonium chloride, decyltrimethylammonium chloride (DTAC), ethylhexadecyl dimethylammonium bromide, Girald reagent, hexadecyl(2-hydroxyethyl)dimethylammonium dihydrogen phosphate, hexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, methylbenzylammonium chloride, N,N',N'-polyoxyethylene (10)-N-tallow-1,3-diaminopropane liquid, olfenammonium bromide, tetraheptylammonium bromide, tetra(decyl)ammonium bromide, tonzoammonium bromide, tri(dodecyl)methylammonium chloride, trimethyloctadecylammonium bromide, 1-methyl-3-n-octylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium chloride, tri(dodecyl)methylammonium bromide, dimethyl distearate ammonium chloride, myristyltrimethylammonium bromide, hexamethylammonium bromide; (3) Nonionic surfactants, which can isolate corrosive media through hydrophobic adsorption membranes and avoid introducing metal ion residues, including but not limited to: polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide block copolymer, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan monopalmitate, and polyoxyethylene (20) sorbitan monolaurate. (4) Anionic surfactants, including but not limited to: sodium dodecyl sulfate (SDS), dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, dodecylphosphonic acid (DDPA), bis(2-ethylhexyl) phosphate, benzylphosphonic acid, diphenylphosphonic acid, 1,2-ethylidene diphosphonic acid, phenylphosphonic acid, and cinnamic acid.

[0049] The amount of metal corrosion inhibitor added can be from about 0.01 wt% to about 2 wt% of the total weight of the cleaning composition.

[0050] In the cleaning composition of the present invention, the etchant may include, but is not limited to, hydrofluoric acid (HF), ammonium fluoride, tetrafluoroboric acid, hexafluorosilicic acid, other compounds containing BF bonds or Si-F bonds, tetrabutylammonium tetrafluoroborate (TBA-BF4), and tetraalkylammonium fluoride (NR). a R b R c R d F), weak bases, strong bases such as tetraalkylammonium hydroxide (NR) a R b R c R d OH) and its combinations, wherein R a R b R c and R d They may be the same as or different from each other, and may be selected from the following groups: hydrogen, straight or branched C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C1-C6 hydroxyalkyl (e.g., hydroxyethyl, hydroxypropyl), substituted or unsubstituted aryl (e.g., benzyl).

[0051] In some examples, the fluoride-based etchant may be selected from tetrafluoroboric acid, hexafluorosilicic acid, H2ZrF6, H2TiF6, HPF6, ammonium fluoride, tetramethylammonium fluoride, ammonium hexafluorosilicate, ammonium hexafluorotitanate, or a combination of ammonium fluoride and tetramethylammonium fluoride.

[0052] Alternatively, in addition to the aforementioned fluoride sources, the etchant may further comprise strong base components such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2-hydroxyethyl)trimethylammonium hydroxide (choline hydroxide), (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), 1,1,3,3-tetramethylguanidine (TMG), guanidine carbonate, arginine, and combinations thereof.

[0053] If choline hydroxide is chosen as an etchant component, those skilled in the art will know that commercially available products typically contain small amounts of stabilizers to inhibit the oxidative degradation of choline hydroxide into non-target byproducts. Such choline hydroxide stabilizers are materials known in the art, including but not limited to formaldehyde, hydroxylamine, sulfites, and hydrides.

[0054] The weak base used in the etchant may include, but is not limited to, ammonium hydroxide, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), ethylenediamine, cysteine, and combinations thereof.

[0055] The amount of the additional etchant added can be from about 0.01 wt% to about 15 wt% of the total weight of the cleaning composition.

[0056] In the cleaning composition of the present invention, the solvent may be one or more of the following: water, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, butyrolactone, N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), and other organic solvents or water-miscible organic solvents. Deionized water is preferred to ensure the solution system is environmentally friendly and suitable for semiconductor cleaning requirements. The solvent may account for approximately 20 wt% to approximately 99.9 wt% of the total weight of the cleaning composition.

[0057] Mix the above components and stir at 25-30°C for 10-20 minutes until a homogeneous and transparent solution is formed, thus obtaining the cleaning composition.

[0058] An application of a cleaning composition according to the present invention involves using the cleaning composition to clean chemical residues on the surface of a semiconductor device; the application method includes the following specific cleaning process steps of the cleaning composition: Step a, Pretreatment: Rinse the semiconductor device to be cleaned (such as a wafer with a copper surface or a silicon dioxide dielectric surface) with water (preferably deionized water) for 1-2 minutes to remove surface dust; Step b, Cleaning treatment: Immerse the pretreated semiconductor device in the cleaning composition, or apply the cleaning composition to the surface of the semiconductor device by spraying, and control the cleaning temperature at 20-70℃ and the cleaning time at 0.5-30min; Step c, post-processing: After cleaning, rinse the semiconductor device with water (preferably deionized water) for 2-3 minutes, and then dry it at 80-100℃ for 5-10 minutes to complete the cleaning process.

[0059] The cleaning composition containing quaternary ammonium hydroxide solution described above in this invention can achieve a chemical residue removal rate of over 95% on metal surfaces (such as copper and aluminum) and dielectric surfaces (such as silicon dioxide and silicon nitride); and compared with the cleaning composition containing tetramethylammonium hydroxide, its toxicity can be reduced by more than 40% (verified by acute toxicity test); it has no obvious irritating odor; and no colored precipitate is formed after being placed at 60°C for 72 hours, demonstrating excellent stability.

[0060] Example 1 This embodiment provides a quaternary ammonium hydroxide solution, which is prepared by reacting tris(2-dimethylaminoethyl)amine with glycidyl ether. The preparation method includes: Add 20g (approximately 0.0868mol) of tris(2-dimethylaminoethyl)amine and 80g of deionized water to a 500mL high-pressure reactor and stir until homogeneous. Purge the reactor with nitrogen gas three times, each time for 5 minutes, to remove air from the reactor. Raise the temperature inside the reactor to 45℃ and set the stirring rate to 250r / min. Add 32g (approximately 0.434mol) of glycidyl ether (epoxypropanol) dropwise to the reactor at a rate of 0.8mL / min, controlling the pressure inside the reactor to ≤0.4MPa and maintaining the temperature at 45±2℃ during the dropwise addition. After the dropwise addition is complete, continue stirring the reaction until the pressure inside the reactor drops to atmospheric pressure. The quaternization rate of the reaction system is determined to be 62% by potentiometric titration. Cool to room temperature to obtain a pale yellow transparent quaternary ammonium hydroxide solution.

[0061] In the preparation method of the quaternary ammonium hydroxide solution in this embodiment, as the reaction proceeds, the product will exhibit a dynamic development process from monosubstituted to trisubstituted (its reaction formula (8) is shown below): In the initial stage of the reaction, glycidyl preferentially undergoes ring-opening addition with one tertiary amine site of tris(2-dimethylaminoethyl)amine to generate a monoquaternized product (as shown in the topmost product structure of formula (8), where only one tertiary amine is converted into a quaternary ammonium cation and a hydroxyl-containing side chain is introduced). As the reaction progresses, the second tertiary amine site participates in the reaction, generating a bisquaternized product (as shown in the intermediate structure of formula (8), where the two tertiary amines are converted into quaternary ammonium cations and hydroxyl-containing side chains are introduced). In the later stage of the reaction, the remaining tertiary amine sites are further quaternized, eventually generating a triquaternized product (as shown in the bottom product structure of formula (8), where all three tertiary amines are converted into quaternary ammonium cations, forming a complete polyhydroxy polyquaternary ammonium salt structure). After the above addition is completed, the reaction is stirred until the pressure inside the reactor drops to atmospheric pressure. The quaternization rate of the reaction system is detected by potentiometric titration at 62%. This indicates that a mixture of monosubstituted, disubstituted, and trisubstituted products exists in the reaction system, and the overall degree of quaternization reaches the expected level. After cooling to room temperature, a pale yellow transparent quaternary ammonium hydroxide solution is obtained (i.e., a quaternary ammonium hydroxide solution of this embodiment).

[0062] (8).

[0063] Example 2 This embodiment provides a quaternary ammonium hydroxide solution, which is prepared by reacting tetrakis(3-dimethylaminopropyl)ethylenediamine with glycidyl (the reaction formula (9) is shown below). The preparation method includes: Add 25 g (approximately 0.0630 mol) of tetrakis(3-dimethylaminopropyl)ethylenediamine and 100 g of deionized water to a 500 mL high-pressure reactor and stir until homogeneous. Purge the reactor with nitrogen gas three times, 5 min each time, to remove air from the reactor. Raise the temperature inside the reactor to 42 °C and set the stirring rate to 220 r / min. Add 35 g (approximately 0.4736 mol) of glycidyl ether dropwise to the reactor at a rate of 0.6 mL / min, controlling the pressure inside the reactor to ≤0.3 MPa and maintaining the temperature at 42 ± 2 °C during the dropwise addition. After the dropwise addition is complete, continue stirring until the pressure inside the reactor drops to atmospheric pressure. The quaternization rate of the reaction system is detected by potentiometric titration to be 90%, indicating that most of the products in the reaction system have completed tri- or tetra-substituted products, consistent with the structure of the target polyquaternized products. Cool to room temperature to obtain a brownish-yellow quaternary ammonium hydroxide solution.

[0064] (9).

[0065] Example 3 A method for preparing a cleaning composition according to this embodiment includes: Take 5g of the quaternary ammonium hydroxide solution prepared in Example 1, 0.2g of ethylenediaminetetraacetic acid (EDTA), and 0.3g of benzotriazole (BTA), add 94.5g of deionized water, and stir at 28°C for 15 minutes to obtain a homogeneous and transparent cleaning composition.

[0066] This embodiment describes the application of a cleaning composition to clean chemical residues on the surface of a semiconductor device; the application method includes the following cleaning process steps: Step a, Pretreatment: Rinse the wafer with copper surface photoresist residue (initial residue of about 1.2 mg / cm²) with deionized water for 1 min; Step b, cleaning treatment: Immerse the pretreated wafer in the above cleaning composition, control the cleaning temperature at 50°C, and the immersion time at 10 min; Step c, Post-processing: After cleaning, rinse the wafer three times with deionized water for 1 minute each time; then place the wafer in a 100°C oven to dry for 5 minutes to complete the cleaning process.

[0067] Example 4 A method for preparing a cleaning composition according to this embodiment includes: Take 5g of the quaternary ammonium hydroxide solution prepared in Example 2, 0.2g of ethylenediaminetetraacetic acid (EDTA), and 0.3g of benzotriazole (BTA), add 94.5g of deionized water, and stir at 28°C for 15min to obtain a homogeneous and transparent cleaning composition.

[0068] This embodiment describes the application of a cleaning composition to clean chemical residues on the surface of a semiconductor device; the cleaning process steps included in the application method are completely consistent with the cleaning process steps ac in Example 3.

[0069] Comparative Example 1 This comparative example provides a cleaning composition using tetramethylammonium hydroxide (TMAH) solution as the core active component; the preparation method of this cleaning composition includes: Take 2g of 25wt% tetramethylammonium hydroxide solution (0.5g of active ingredient), 0.2g of ethylenediaminetetraacetic acid (EDTA), and 0.3g of benzotriazole (BTA), add 97.5g of deionized water, and stir at 28℃ for 15min to obtain a homogeneous cleaning composition containing TMAH.

[0070] The cleaning process steps of the TMAH-containing cleaning composition in this comparative example are completely consistent with the cleaning process steps ac of Example 3.

[0071] Performance testing The performance of residue removal rate and copper surface corrosion rate was tested on wafers with copper surface photoresist residue (initial residue of about 1.2 mg / cm²) after cleaning with the cleaning compositions of Examples 3-4 and Comparative Example 1, respectively; and the performance of stability and toxicity of the cleaning compositions of Examples 3-4 and Comparative Example 1 were tested, respectively; the test results are shown in Table 1 below.

[0072] Table 1

[0073] Based on Table 1, we can see that: 1. The performance test results of the cleaning composition and the cleaned wafer in Example 3 are as follows: (1) Residue removal rate: The residue on the wafer surface after cleaning was reduced to 0.05 mg / cm², and the residue removal rate reached 95.8%; (2) Corrosion rate of copper surface: The corrosion rate of copper surface was 0.02 μm / h as measured by ICP-MS (inductively coupled plasma mass spectrometry), and there was no obvious corrosion. (3) Solution stability: The cleaning composition of Example 3 remained colorless and transparent, with no precipitate formation and no irritating odor after being placed at 60°C for 72 hours; (4) Acute toxicity: Mouse oral acute toxicity test (LD50) 50 The results showed that the toxicity of the cleaning composition in Example 3 was reduced by 42% compared with the cleaning composition containing tetramethylammonium hydroxide (TMAH), meeting the requirements for low toxicity and environmental protection.

[0074] 2. The performance test results of the cleaning composition and the cleaned wafer in Example 4 are as follows: (1) Residue removal rate: The residue on the wafer surface after cleaning was reduced to 0.07 mg / cm², and the residue removal rate reached 94.2%; (2) Corrosion rate of copper surface: ICP-MS test showed that the corrosion rate of copper surface was 0.03 μm / h, with no obvious corrosion; (3) Solution stability: The cleaning composition of Example 4 remained colorless and transparent, with no precipitate formation and no irritating odor after being placed at 60°C for 72 hours; (4) Acute toxicity: Mouse oral acute toxicity test (LD50) 50 The results showed that the toxicity of the cleaning composition in Example 4 was reduced by 38% compared with the cleaning composition containing tetramethylammonium hydroxide (TMAH), meeting the requirements for low toxicity and environmental protection.

[0075] 3. The performance test results of the TMAH-containing cleaning composition and the cleaned wafer in Comparative Example 1 are as follows: (1) Residue removal rate: The residue on the wafer surface after cleaning was reduced to 0.10 mg / cm², and the residue removal rate reached 91.7%; (2) Corrosion rate of copper surface: ICP-MS test showed that the corrosion rate of copper surface was 0.18 μm / h, indicating significant corrosion; (3) Solution stability: The cleaning composition containing TMAH remained transparent after being placed at 60°C for 72 hours, but had a noticeable irritating odor; (4) Acute toxicity: Mouse oral acute toxicity test (LD50) 50 The results showed that the toxicity of the cleaning composition containing TMAH was of the high toxicity level, significantly higher than that of Examples 3-4 of the present invention.

[0076] Therefore, compared with the cleaning composition containing tetramethylammonium hydroxide, such as Comparative Example 1, the cleaning compositions containing quaternary ammonium hydroxide solution in Examples 3-4 of the present invention can achieve a chemical residue removal rate of about 95% on the metal surface (such as copper) of wafers, and have a better effect on removing chemical residues on semiconductor surfaces; it can effectively reduce the corrosion rate on the copper surface of wafers; and compared with the cleaning composition containing tetramethylammonium hydroxide (such as Comparative Example 1), its toxicity can be reduced by about 40%, which is a significant reduction in toxicity and a smaller risk to the health of operators and the environment; it has no obvious irritating odor, and no colored precipitate is formed after being placed at 60°C for 72 hours, indicating higher stability. It can effectively avoid the problem of decomposition products contaminating the surface of semiconductor devices, which helps to improve the stability of subsequent processes and product yield. Therefore, the cleaning compositions containing quaternary ammonium hydroxide solution of the present invention can simultaneously meet the multiple practical needs of the semiconductor wet cleaning field for high efficiency, low toxicity, no odor, high stability, and low corrosion.

[0077] Although preferred embodiments of the present invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of the embodiments of the present invention.

[0078] The technical solution provided by the present invention has been described in detail above. Specific examples have been used to illustrate the principle and implementation of the present invention. The description of the above embodiments is only for the purpose of helping to understand the method and core idea of ​​the present invention. At the same time, for those skilled in the art, there will be changes in the specific implementation and application scope based on the idea of ​​the present invention. Therefore, the content of this specification should not be construed as a limitation of the present invention.

Claims

1. A quaternary ammonium hydroxide solution, characterized in that, It is prepared by quaternization reaction of dendritic polyamines with organic epoxy compounds; the dendritic polyamines have the following general formula: Core–[Linker–N(R1)R2] m ; Core is selected from nitrogen atoms, C1-C 10 Alkylene, C1-C 10 Saturated hydrocarbon diamine or polyamine residues, C6-C 10 aryl, or C1-C 10 The heterocyclic group; the number of heteroatoms N in the saturated hydrocarbon diamine or polyamine residue is ≤3; the heteroatoms of the heterocyclic group are N and / or O, and the number of heteroatoms is ≤2; Linker is selected from C2-C6 alkylene groups or C2-C6 alkene groups containing ether bonds; R1 and R2 are independently selected from hydrogen, C1-C4 alkyl, or C2-C4 hydroxyalkyl; The dendritic polyamine molecule contains at least one tertiary amine group, or at least one primary or secondary amine group that can be converted into a tertiary amine group in situ with an organic epoxy compound; m is an integer from 3 to 6.

2. The quaternary ammonium hydroxide solution according to claim 1, characterized in that, The dendritic polyamine is selected from one or more of tris(2-aminoethyl)amine, tris(3-dimethylaminopropyl)amine, tetra(2-methylaminoethyl)ethylenediamine, tris(2-dimethylaminoethyl)amine, penta(2-aminopropyl)diethylenetriamine, tris(4-dimethylaminobutyl)benzene, tetra(3-dimethylaminopropyl)ethylenediamine, and N,N,N',N'-tetra(2-aminoethyl)ethylenediamine.

3. The quaternary ammonium hydroxide solution according to claim 1, characterized in that, The organic epoxy compound has the following general formula: ； Among them, R3, R4, and R5 may be the same or different, and each is independently selected from hydrogen, C1-C. 12 Straight-chain or branched alkyl groups, C2-C 12 Unsaturated hydrocarbon group, C6-C 18 Aryl or C7-C 18 Aryl alkyl group; or, any two of R3, R4, and R5 linked together to form a C3-C group with the two carbon atoms on the epoxide ring. 12 A ring structure; or, one or more of R3, R4, and R5 contain oxygen atoms.

4. The quaternary ammonium hydroxide solution according to claim 3, characterized in that, The organic epoxy compound is selected from one or more of ethylene oxide, propylene oxide, 1,2-epoxybutane, styrene oxide, and glycidyl ether.

5. The quaternary ammonium hydroxide solution according to claim 1, characterized in that, The molar ratio of the dendritic polyamine to the organic epoxy compound is 1:(3~8).

6. A method for preparing a quaternary ammonium hydroxide solution according to any one of claims 1-5, characterized in that, The preparation steps include the following: Step 1: Add dendritic polyamine and solvent to the reaction vessel. The mass ratio of dendritic polyamine to solvent is 1:(2~5). Step 2: Purge the air out of the vessel with nitrogen, raise the temperature to 40-50℃, and adjust the stirring speed. Step 3: Add organic epoxy compound dropwise to the reaction vessel. The molar ratio of dendritic polyamine to organic epoxy compound is 1:(3~8). During the dropwise addition, control the pressure inside the vessel to ≤0.5MPa and maintain the temperature at 40~50℃. Step 4: After the addition is complete, continue stirring the reaction until the pressure inside the reactor drops to atmospheric pressure, and check that the quaternization rate of the reaction system is ≥50%. Step 5: After the reaction is complete, cool to room temperature to obtain a quaternary ammonium hydroxide solution.

7. The method for preparing a quaternary ammonium hydroxide solution according to claim 6, characterized in that, In step 2, the stirring rate is controlled at 200-300 r / min; In step 3, the dropping rate of the organic epoxy compound is 0.5-1.0 mL / min.

8. A cleaning composition, characterized in that, The active component includes a quaternary ammonium hydroxide solution as described in any one of claims 1-5; The cleaning composition further includes one or more combinations of chelating agents, metal corrosion inhibitors, etchants, and solvents.

9. A cleaning composition according to claim 8, characterized in that, Includes the following components by mass fraction: Quaternary ammonium hydroxide solution: 0.5-10 wt%; Chelating agent: 0.01~1wt%; Metal corrosion inhibitor: 0.01~2wt%; Solvent: Balance.

10. The application of a cleaning composition according to any one of claims 8-9, characterized in that, The cleaning composition is applied to clean chemical residues on the surface of semiconductor devices; the application method includes the following cleaning process steps: Step a, Pretreatment: Rinse the semiconductor devices to be cleaned with deionized water; Step b, cleaning treatment: Immerse the pretreated semiconductor device in the cleaning composition, or apply the cleaning composition to the surface of the semiconductor device by spraying. The cleaning temperature is 20-70℃ and the cleaning time is 0.5-30min. Step c, Post-processing: Rinse the semiconductor device with deionized water and dry it.

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