A cleaning agent for TFT substrate after thinning and polishing and a preparation method thereof

Abstract

The present application relates to the technical field of detergent, disclose a kind of TFT substrate thinning polishing after cleaning agent and its preparation method, comprising: 0.5% to 5.0% N-acyl amino acid salt, 0.1% to 2.0% phytic acid or its salt, 1.0% to 8.0% organic amine, 3.0% to 8.0% alcohol ether solvent and the balance deionized water;Wherein the weight ratio of N-acyl amino acid salt and phytic acid or salt is limited in the range of 2.0 to 1 to 4.0 to 1, the saturated load system of surfactant micelle to phytic acid molecule is constructed by specific ratio, the directed migration characteristics of micelle at interface are used, phytic acid molecules are simultaneously adsorbed on metal surface, the instantaneous flash corrosion caused by corrosion inhibitor diffusion lag in strong alkali environment is eliminated, and the kinetic balance of decontamination and corrosion prevention in substrate cleaning process is realized.

Description

Technical Field

[0001] This invention relates to a cleaning agent for TFT substrate thinning and polishing and its preparation method, belonging to the field of detergent technology. Background Technology

[0002] In current thin-film transistor liquid crystal display (TFT-LCD) and organic light-emitting diode (OLED) panel manufacturing, the substrate thinning and polishing processes inevitably introduce submicron-sized glass debris, polishing fluid residue particles, and metal ion contamination onto the glass substrate surface. To remove these contaminants and maintain the surface integrity of aluminum, copper, or molybdenum metal circuits, the industry typically employs a water-based cleaning system containing alkaline components and chelating agents. This system utilizes the alkaline environment to adjust the zeta potential of the particle surface, generating electrostatic repulsion, and uses chelating agents to capture metal ions or form an adsorption film on the metal surface to inhibit alkaline corrosion. As display panel production lines evolve towards G8.5 and higher generation lines, single-sheet rotary spray cleaning becomes increasingly important due to its high efficiency. This has become the mainstream process. Under such dynamic conditions of high shear and short residence time, the residence time of the cleaning solution on the substrate surface is compressed to the second or even sub-second level. Under these kinetic conditions, the existing cleaning agent formulation system exposes the problem of mismatch between adsorption and corrosion rates. In alkaline media with a pH value greater than 10, hydroxide ions have extremely high liquid phase diffusion coefficients due to their extremely small ionic radius. They can penetrate the boundary layer and attack the metal interface within microseconds of the contact between the cleaning solution and the substrate. Traditional organophosphonic acid or heterocyclic corrosion inhibitors have large molecular volumes. In high alkaline environments, they are highly dissociated and bound by a thick solvation layer. They diffuse to the solid-liquid interface and complete the orientation adsorption, which lags behind the rate of corrosion reaction.

[0003] The asynchrony at the microscopic dynamic level means that even if the equilibrium concentration of the corrosion inhibitor in the cleaning solution is high enough, the surface of the metal circuit still suffers irreversible transient flash corrosion in the initial stage of solid-liquid contact due to the lack of immediate protection. This manifests as an increase in the root mean square roughness of the metal surface or the formation of nanoscale pitting, leading to film peeling or mottled defects in subsequent film formation processes. Simply increasing the concentration of the corrosion inhibitor to compensate for the diffusion rate is insufficient. Due to strong intermolecular interactions, a difficult-to-remove organic adsorbed layer remains on the substrate surface, causing secondary pollution. For example, Chinese invention patent application CN118165789A discloses a water-based cleaning agent for TFT-LCD glass substrates and its preparation method, which introduces components such as inorganic alkalis, organic amines, and cyclic ketones to construct a needle-like cleaning agent. The dissolution system for organic residues and UV adhesive traces relies on strong inorganic alkalis to provide the driving force for decontamination. However, when faced with high-speed rotating spraying conditions, it exposes microscopic kinetic defects: hydroxide ions have extremely small ionic radii and extremely high liquid phase diffusion coefficients, and their migration rate to the metal interface is far greater than that of large molecular organic corrosion inhibitors. Lacking a special carrier delivery mechanism, conventional corrosion inhibitors are bound by the solvation layer and cannot complete orientation adsorption in time within the microsecond window when the solution contacts the substrate. The adsorption rate and corrosion rate are severely mismatched, resulting in irreversible transient flash corrosion on the metal circuit surface in the early stage of contact due to the lack of immediate protection, which manifests as a surge in surface roughness or the appearance of nanoscale pitting corrosion.

[0004] Therefore, how to avoid the diffusion barrier of alkaline water-based systems of macromolecular corrosion inhibitors, eliminate the time lag of adsorption and corrosion kinetics, and achieve transient synchronous protection and low residue in the cleaning process has become the technical problem to be solved by this invention. Summary of the Invention

[0005] To address the problems mentioned in the background art, the technical solution of the present invention is as follows: a cleaning agent for TFT substrate thinning and polishing, the cleaning agent being a homogeneous liquid system composed of the following components in weight percentage:

[0006] 0.5% to 5.0% of an N-acyl amino acid salt, wherein the N-acyl amino acid salt is selected from at least one of sodium lauroyl sarcosinate, sodium cocoyl glutamate, or sodium lauroyl glutamate;

[0007] 0.1% to 2.0% phytic acid or its salt;

[0008] 1.0% to 8.0% of organic amines, wherein the organic amines are selected from at least one of monoethanolamine, diethylene glycolamine, triethanolamine or isopropanolamine;

[0009] The cleaning agent contains 3.0% to 8.0% alcohol ether solvents, selected from ethylene glycol monobutyl ether or diethylene glycol monobutyl ether; and is supplemented to 100% deionized water. The content of organic amines maintains the pH value of the cleaning agent in the range of 10.5 to 12.5. The weight ratio of N-acyl amino acid salt to phytic acid or its salt is strictly limited to the range of 2.0:1 to 4.0:1. This weight ratio range limits the average hydrodynamic radius of the micelles in the cleaning agent to be in the range of 8 nm to 12 nm under pH conditions, while limiting the time for the dynamic surface tension of the cleaning agent to drop from the initial value to the equilibrium value to be less than 50 milliseconds, and the resistivity of the cleaning agent at 25 degrees Celsius to be less than 100 ohm·cm. The micelle structure formed by the N-acyl amino acid salt has a saturated loading capacity for phytic acid or its salt within the weight ratio range, thereby establishing a synchronous adsorption layer of surfactant and corrosion inhibitor at the moment the cleaning agent contacts the metal surface.

[0010] Preferably, the N-acyl amino acid salt is sodium lauroyl sarcosinate, the organic amine is diethylene glycolamine, and the alcohol ether solvent is ethylene glycol monobutyl ether; the pH value of the cleaning agent is controlled between 11.0 and 12.0. At this pH value and component concentration, the absolute value of the zeta potential of the cleaning agent to cerium oxide particles is maintained above 40 mV, and the kinematic viscosity of the cleaning agent at 25 degrees Celsius is 1.0 mm² / s to 1.5 mm² / s.

[0011] Preferably, phytic acid or its salt is in a completely dissociated state in a system with a pH of 10.5 to 12.5 and is loaded in the hydrophilic barrier layer of N-acyl amino acid salt micelles; the cleaning agent has critical micelle concentration-dependent dissociation characteristics, and when the cleaning agent is diluted with pure water to below the critical micelle concentration of the N-acyl amino acid salt, the contact angle of the residue of the cleaning agent on the glass substrate surface is less than 10 degrees.

[0012] Preferably, the cleaning agent is free of silicate and phosphate inorganic corrosion inhibitors and benzotriazole organic corrosion inhibitors; the surface tension of the cleaning agent is 25 mN / m to 30 mN / m in the temperature range of 20°C to 60°C; the long-chain alkyl structure of N-acyl amino acid salt and alcohol ether solvent together constitute a penetrating dispersion system for submicron glass debris and polishing residues.

[0013] Preferably, the weight percentage concentration of N-acyl amino acid salts weight percentage concentration of phytic acid or its salt Satisfy the following regarding dynamic loading factor Relationship: Among them, dynamic loading factor Define the microscopic loading capacity boundary of a unit mass of surfactant micelles for corrosion inhibitor molecules, when When within the specified range, the corrosion current density of the cleaning agent on the aluminum or copper metal surface is less than 0.1 microamps per square centimeter, and the thickness of the adsorbed film formed by the cleaning agent on the metal surface is 1 nanometer to 3 nanometers.

[0014] Preferably, the resistivity of the deionized water at 25 degrees Celsius is greater than 18 megohm-cm, and the individual content of iron, copper, nickel, and chromium metal ion impurities in the cleaning agent is less than 10 ppb; the cleaning agent is filtered through a 0.1-micron pore size filter, and the particle size of the insoluble particles in the cleaning agent is less than 0.1 microns.

[0015] Preferably, the organic amine is a mixture of monoethanolamine and triethanolamine, wherein the mass ratio of monoethanolamine to triethanolamine is 1:1 to 2:1; the mixture forms a solubilizing system against phytic acid or its salt in the cleaning agent, and the cleaning agent does not precipitate crystals in a storage temperature range of 0 degrees Celsius to 40 degrees Celsius.

[0016] Preferably, the density of the cleaning agent is 1.01 g / cm³ to 1.05 g / cm³ at 25 degrees Celsius; the cleaning agent spreads on the glass substrate surface at a speed greater than 500 mm / s under spray conditions with a pressure of 0.1 MPa to 0.3 MPa; the cleaning agent is suitable for cleaning TFT glass substrates containing aluminum, copper, or molybdenum metal electrodes; during a single-piece rotation cleaning process with a cleaning time of 10 to 30 seconds, the root mean square roughness change of the metal electrode surface is controlled within 0.5 nanometers, and the total organic carbon residue on the substrate surface after cleaning is less than 10 micrograms per square meter.

[0017] Preferably, the N-acyl amino acid salt is sodium cocoyl glutamate, and the phytic acid or its salt is sodium phytate; the weight ratio of the N-acyl amino acid salt to sodium phytate remains constant within a dilution ratio not exceeding 100 times, and the pH value of the cleaning agent varies by no more than 0.5 units.

[0018] A method for preparing a cleaning agent for TFT substrate thinning and polishing, wherein the cleaning agent for TFT substrate thinning and polishing is prepared by the aforementioned cleaning agent for TFT substrate thinning and polishing.

[0019] Compared with the prior art, the beneficial effects of the present invention are:

[0020] 1. In the thinning and polishing of TFT substrates, the weight ratio of N-acyl amino acid salt to phytic acid or its salt is strictly controlled within the range of 2.0:1 to 4.0:1. In alkaline media, phytic acid molecules are anchored to the surfactant micelle barrier layer interface through the hydrogen bond network between phosphate groups and amino acid surfactant molecules to form a stable associative micelle carrier. Under the conditions of high shear and short residence time in single-wafer rotation cleaning, the associative system utilizes the high migration rate of the gas-liquid interface of N-acyl amino acid salt to drive the anchored phytic acid molecules to overcome the Brownian motion rate limitation and be directionally accelerated to the substrate interface. The carrier transport mechanism ensures that phytic acid molecules preferentially occupy the active sites on the aluminum or copper metal circuit surface and adsorb to form a film within a millisecond time window before the chemical corrosion of hydroxide ions. This eliminates the transient flash corrosion phenomenon caused by the lag of the corrosion rate in the diffusion rate of the corrosion inhibitor in traditional formulations and maintains the atomic-level flatness of the metal circuit surface.

[0021] 2. By utilizing a specific ratio to form a phytic acid surfactant association structure, a reversible thermodynamic equilibrium system dependent on the critical micelle concentration is established. During the pure water rinsing stage after cleaning, the concentration of the liquid film component on the substrate surface is diluted to below the critical micelle concentration. This maintains the stable adsorption of phytic acid molecules, creating a hydrophobic environment for the micelles and breaking down the hydrogen bond network. The monomolecular phytic acid film adsorbed on the metal surface loses its structural support, and the unstable phytic acid molecules desorb from the substrate surface and dissolve into the rinsing water flow. This results in high hydrophilicity and cleanliness on the glass substrate and metal electrode surfaces after cleaning, avoiding the difficulty in completely removing traditional hydrophobic film-forming corrosion inhibitors that lead to cloud-like defects in subsequent film-forming processes. This meets the requirement of low organic residue at the interface in thin-film transistor manufacturing processes.

[0022] 3. The N-acyl amino acid salt component in the composition utilizes a long-chain alkyl structure to embed into the microscopic gaps between the polishing residual cerium oxide particles, glass debris, and the substrate, reducing the solid-liquid interfacial tension. Under a specific synergistic environment, the polar head groups of amino acids adsorbed on the particle surface increase the absolute value of the negative Zeta potential on the particle surface, constructing a high-intensity electrostatic repulsion field between the particles and the substrate. The surfactant micelle structure forms a solvation layer around the particles, providing additional steric hindrance effect. The synergistic effect of electrostatics and steric hindrance blocks the secondary redeposition path of the submicron-level particle cleaning solution circulation process, reducing the defect density on the substrate surface. Attached Figure Description

[0023] Figure 1 This is a flowchart illustrating the mechanism of phytic acid surfactant association micelles and the cleaning process of this invention.

[0024] Figure 2 This is a stability curve of the micelle hydrodynamic radius as a function of temperature under different formulation systems of the present invention;

[0025] Figure 3 This is a diagram of the intelligent cleaning agent preparation and online quality monitoring closed-loop control system of the present invention. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0027] This invention proposes a cleaning agent and its preparation method for TFT substrate thinning and polishing. The cleaning agent system is composed of N-acyl amino acid salt as a surface active component, phytic acid or its salt as a corrosion inhibitor, organic amine as a pH adjustment and solubilizing component, alcohol ether solvent as a penetration component, and high-purity deionized water as a carrier. The components are combined through specific ratios, especially the strict mass ratio constraint between N-acyl amino acid salt and phytic acid or its salt, to construct an associated micelle structure with a specific hydrodynamic radius in an alkaline medium. This structure is used to achieve directional delivery of corrosion inhibitor molecules, thereby establishing a kinetic balance between adsorption and corrosion within milliseconds of the cleaning solution contacting the substrate. This invention avoids the technical obstacle of large molecular weight organophosphonic acid corrosion inhibitors in alkaline environments having a diffusion rate to the metal interface that lags behind the hydroxide ion corrosion rate due to solvation effects.

[0028] This invention strictly limits the weight ratio of N-acyl amino acid salt to phytic acid or salt to [specific value]. to Within this range, and within this specific ratio range and pH value to In an alkaline environment, the N-acyl amino acid salt, acting as the host molecule, and phytic acid, acting as the guest molecule, no longer exist in an independent free state. Instead, they self-assemble based on intermolecular hydrogen bond networks and electrostatic interactions to form phytic acid-surfactant associated micelles. The physical characteristics of this associated structure are manifested in the average hydrodynamic radius of the micelles. It exhibits nonlinear swelling, and the numerical value stabilizes at... nanometer to Within the nanometer range, and maintaining single-phase transparency, during the dynamic cleaning process, the associative micelles utilize the high surface activity and rapid migration capability of N-acyl amino acid salt molecules at the gas-liquid-solid three-phase interface. This drives phytic acid molecules anchored in the micelle fence layer to avoid the rate limitation of conventional Brownian motion and migrate directionally to the substrate interface. When the micelles contact the positively charged aluminum or copper metal oxide film surface, induced by the strong electrostatic field of the interfacial electric double layer, the phytic acid molecules dissociate from the micelle surface and preferentially occupy the active sites on the metal surface, achieving a kinetic synchronization effect of wetting and film formation, eliminating transient flash corrosion. The N-acyl amino acid salt in this system plays multiple roles, including reducing surface tension, regulating particle zeta potential, and acting as a phytic acid carrier. This invention preferably uses at least one of sodium lauroyl sarcosinate, sodium cocoyl glutamate, or sodium lauroyl glutamate. To ensure its solubility stability and controllable foaming performance in alkaline systems, the amount added is limited to... to Within the weight percentage range, when the concentration is below When the concentration is too high, the system cannot form a sufficient number of micelles to fully load phytic acid molecules, resulting in some phytic acid becoming free and thus reducing the overall diffusion rate; when the concentration is higher than... Excessive surfactant molecules can form a dense bilayer adsorption on the metal surface, hindering effective contact between phytic acid molecules and the metal substrate, and causing difficulties in subsequent rinsing. In specific implementation formulations, surfactants with a purity greater than [missing information] are used. Sodium lauroyl sarcosinate has a hydrophobic carbon chain length distribution concentrated in This is to ensure the uniformity of the micelle structure.

[0029] Phytic acid or its salts, as specific corrosion inhibitors for aluminum, copper, and molybdenum metal circuits, are added in controlled amounts. to Within a certain weight percentage range, phytic acid molecules possess a cyclic structure and twelve dissociable protons, enabling them to form a monomolecular chemisorption film on metal surfaces. This invention, through the aforementioned specific weight ratio limitation, allows phytic acid molecules to be pre-loaded onto surfactant micelles in the cleaning solution. During the pure water rinsing stage after cleaning, as the surfactant concentration in the bulk solution is rapidly diluted below the critical micelle concentration, the originally stable associated micelle structure disintegrates. The monomolecular phytic acid film, lacking the synergistic support of the hydrophobic tail chains, is easily desorbed and carried away by pure water. This concentration-sensitive reversible adsorption mechanism ensures that the cleaned glass and metal surfaces exhibit extremely high hydrophilicity, resulting in a low total organic carbon residue. Less than Micrograms per square meter to avoid subsequent film formation defects caused by organic residues; organic amines are used to provide a stable alkaline environment and hydrolyze silanol groups on the glass surface, selected from at least one of monoethanolamine, diethylene glycolamine, triethanolamine, or isopropanolamine, with an addition amount of [missing information]. to The amount of organic amine added needs to be precisely titrated to maintain the pH value of the cleaning agent at a certain level. to Between these pH values, the absolute value of the Zeta potential on the surface of glass fragments and cerium oxide particles was maintained at [value missing]. Above millivolts, strong electrostatic repulsion is used to prevent secondary redeposition of particles on the substrate surface. If the pH value is below... The compression of the electric double layer on the particle surface leads to a decrease in the repulsive barrier, resulting in a reduction in decontamination efficiency; if the pH value is higher than... The corrosion potential of aluminum or copper metals drops sharply, and even with corrosion inhibitors, it is difficult to completely suppress pitting corrosion. In a preferred embodiment, a compound system of monoethanolamine and triethanolamine is used, with a mass ratio of [missing information]. to The strong alkalinity of monoethanolamine provides a pH buffer, while the steric hindrance effect of triethanolamine helps stabilize phytic acid molecules.

[0030] Alcohol ether solvents are used to penetrate and swell the wax and organic residues introduced during the polishing process. They are selected from ethylene glycol monobutyl ether or diethylene glycol monobutyl ether, and the addition amount is... to This component, in conjunction with the N-acyl amino acid salt, further reduces the dynamic surface tension of the cleaning agent. The solution reaches equilibrium within milliseconds, ensuring rapid spread and penetration of the drug solution into submicron-level surface micropores and scratches. Deionized water is used as the solvent to replenish the balance. To ensure the system's tolerance to metal ions and prevent the introduction of additional contamination, the deionized water used is... The resistivity at Celsius must be greater than Megohm-cm, and the individual content of metal ion impurities such as iron, copper, nickel, and chromium must all be less than [amount missing]. The present invention also provides a standardized preparation method for the cleaning agent after thinning and polishing of the above-mentioned TFT substrate, comprising the following strictly controlled process steps: adding a calculated amount of deionized water to a mixing tank equipped with a temperature control and frequency conversion stirring device, and starting the stirring, setting the rotation speed to [missing information]. Rotate per minute to Stir at a constant speed of 1000 rpm; slowly add the weighed N-acyl amino acid salt, controlling the feeding rate to avoid excessive foaming, and continue stirring until the solid is completely dissolved and the solution is clear; then add the organic amine and alcohol ether solvents in sequence, stirring continuously. minutes to To ensure thorough mixing, the system temperature should be controlled within minutes during this period. Celsius Between degrees Celsius; while maintaining stirring, slowly add an aqueous solution of phytic acid or its salt using a precision metering pump, controlling the dropping rate at a rate of approximately [missing value]% of the total mass added per minute. to To prevent excessively high local concentrations from causing uneven associative micelle structures, stirring should continue after the addition is complete. minutes to The system was allowed to reach thermodynamic equilibrium within minutes; finally, the resulting mixed solution was passed through a pore size of [missing information]. micrometers to The cleaning agent is obtained by circulating filtration through a micron-sized polytetrafluoroethylene or polypropylene filter membrane until the particle size of insoluble particles in the filtrate meets the detection standard. This preparation process ensures that the components achieve full association and dispersion at the microscopic level, guaranteeing the batch stability of the final product.

[0031] Example 1: In the single-piece rotary cleaning application scenario of the G8.5 generation TFT-LCD panel manufacturing line, the cleaning process after substrate thinning and polishing faces an extremely narrow process window. This process is typically carried out at a rotation speed of... Rotate per minute to The cleaning process is carried out under high shear conditions of 1000 rpm, which compresses the effective residence time of the cleaning solution on the substrate surface to a minimum. Instant Seconds, under these conditions, the cleaning system at a pH value of to The system operates in a strongly alkaline environment to ensure sufficient electrostatic repulsion between cerium oxide particles and the glass substrate. However, the diffusion rate of hydroxide ions to the surface of aluminum or copper metal circuits is extremely high under this alkaline environment. Conventional organophosphonic acid corrosion inhibitors are limited by the solvation layer, and the interfacial adsorption rate lags behind the corrosion reaction initiation time, resulting in nanoscale pitting or transient flash corrosion with excessive root mean square roughness on the metal circuit surface. This embodiment adopts the cleaning agent technology solution defined in the aforementioned specific embodiments, wherein the weight ratio of N-acyl amino acid salt to phytic acid or its salt is set to... The ratio is at to Within a specific window, dynamic light scattering tests showed that the average hydrodynamic radius of the micelles remained stable at [value missing]. The nanometer-sized particles indicate that phytic acid molecules have been saturated and loaded into a micelle fence layer formed by N-acyl amino acid salts through multi-point hydrogen bonding and electrostatic interactions, constructing stable phytic acid-surfactant associated micelles. When this cleaning agent is atomized through a nozzle and impacts the substrate surface at high speed, the N-acyl amino acid salt component utilizes its amphiphilic structure to dominate the rapid wetting process at the gas-liquid-solid three-phase interface, and the dynamic surface tension is... Within milliseconds, the temperature drops to the equilibrium value. During this wetting process, the associated micelles act as the dynamic carriers of phytic acid molecules, dragging the originally slow-diffusion phytic acid molecules to the metal interface at the migration rate of surfactants.

[0032] Once the carrier micelles come into contact with the positively charged aluminum or copper oxide film surface, the strong electrostatic field of the interfacial double layer disrupts the hydrogen bond balance within the micelles, inducing phytic acid molecules to rapidly dissociate from the micelle surface and preferentially occupy high-energy active sites on the metal surface. This mechanism allows a dense monomolecular chemisorption film to form synchronously within milliseconds before hydroxide ion-induced electrochemical corrosion, thus eliminating the time difference between adsorption and corrosion at the kinetic level. Simultaneously, free N-acyl amino acid salt molecules in the solution use long-chain alkyl groups to insert into the gaps between submicron-sized glass fragments and the substrate. Combined with the alkaline environment provided by organic amines, this induces the zeta potential on the particle surface to negative. Below millivolt levels, particles are detached and suspended in the liquid phase using electrostatic repulsion and the steric hindrance effect of micelles. During the pure water rinsing stage, as the cleaning agent is rapidly diluted by deionized water, the concentration of N-acyl amino acid salts in the system drops below the critical micelle concentration, causing the associated micelle structure to disintegrate. The phytic acid monolayer, having lost its synergistic stabilizing effect from the hydrophobic tail chains, rapidly desorbs from the metal surface and dissolves into the rinsing water flow, ensuring that no hydrophobic organic film remains on the substrate surface after cleaning. Final test results show that the root mean square roughness variation of the TFT substrate metal circuit surface treated by this process is controlled within [specific value missing]. Within nanometers, there are no visible pitting corrosion pits, and the total residual organic carbon content on the glass surface is less than [amount missing]. Micrograms per square meter, meeting the stringent requirements of atomic-level cleanliness and hydrophilicity for subsequent photoresist coating processes.

[0033] Example 2: To verify the effectiveness of the above technical solution in addressing the core contradiction of high-alkaline corrosion and particle residue during TFT substrate cleaning, this experiment established a simulation verification platform based on a real industrial scenario. The experimental platform setup and data acquisition were standardized. This experiment used an experimental device simulating a single-wafer rotary cleaning machine from a G8.5 generation line. This device was equipped with a rotating stage capable of precisely controlling the rotation speed (rotation speed error...). (Revolutions per minute) and a pressure-adjustable fan-shaped nozzle (pressure error) (MPa), the test substrate was selected with surface sputtering Nano-thick aluminum film and Standard for nano-thick copper films millimeters Millimeter-sized glass samples were used to simulate the structure of real TFT metal electrodes. To simulate polishing residues in actual production, the sample surface was pre-coated with a layer containing particles with an average particle size of [missing information]. Nano-sized cerium oxide particles and Standard contaminant slurry of micron-sized glass debris, and through Baking at Celsius Curing time: minutes; test data collection strictly follows the following specifications: microstructure and roughness of the metal surface ( ) using atomic force microscopy (AFM, scanning range micrometer Characterized by micrometers; the metal corrosion rate was obtained by measuring polarization curves using an electrochemical workstation, and the corrosion current density (μm) was also measured. The core quantitative indicator is the number of residual particles on the surface, measured by a laser surface defect detector (detection limit). The contact angle of the cleaning agent is measured using a dynamic contact angle measuring instrument (micrometers). Measurements were performed under constant temperature conditions of 100 degrees Celsius. All electrochemical measurements involving noise interference were conducted within a Faraday shielded box to filter out environmental electromagnetic interference and ensure that the signal-to-noise ratio of the data was greater than 100%. decibel.

[0034] The decision-making logic for setting key parameters: In this experiment, the cleaning time was set as follows. seconds, spray pressure set to MPa, speed set to The selection of this set of parameters, measured in revolutions per minute, is not arbitrary but rather an engineering decision based on a trade-off between cleaning efficiency and the risk of mechanical damage. Excessive pressure or rotation speed, while increasing physical peeling force, also increases the risk of mechanical impact on metal circuits and chemical splashing. Too short a time cannot guarantee sufficient chemical reaction, while too long a time affects production line capacity. Therefore, this parameter combination represents a typical process window in actual production that balances efficiency and yield. Experimental group design and nonlinear effect verification: To comprehensively evaluate the technical effects and the rationality of the formulation range of this invention, the experimental design includes a multi-dimensional control system comprising the present invention sample group, a partially missing control group, and an out-of-range control group. The present invention sample group (S1-S3): uses N-acyl amino acid salt and phytic acid in a mass ratio of... , , The cleaning agent, the concentration of other components and pH value ( The control group (D1, missing type): contains only N-acyl amino acid salts, without phytic acid, and is used to evaluate the baseline corrosion level under conditions without corrosion inhibitors; the control group (D2, missing type): contains only phytic acid, without N-acyl amino acid salts, and is used to verify the corrosion inhibition efficiency in the absence of surfactant carriers; the control group (D3, out of range type): has a mass ratio of... (Excess phytic acid) was used to verify performance degradation when the ratio was below the lower limit; Control group 4 (D4, out-of-range type): mass ratio was (Excess surfactant) is used to verify the performance degradation when the ratio is higher than the upper limit; Test process and data interpretation: After the test is started, each group of cleaning agents performs single-piece rotation cleaning on the pre-contaminated sample under the same working conditions, followed by rinsing with pure water and drying with nitrogen. During the test, it was observed that the sample group of the present invention forms a uniform liquid film immediately upon contact with the substrate, while the liquid film of the D2 group spreads more slowly and shows local shrinkage. The key test data are shown in Table 1 below.

[0035] Table 1: Test Results of Key Performance Indicators for Each Test Group

[0036]

[0037] In-depth data analysis and mechanism verification: As can be seen from the data in Table 1, the corrosion current density of the sample groups (S1-S3) of this invention... Lower than all control groups, and the surface roughness increment of the aluminum film was controlled within Particles smaller than nanometers have a removal rate close to [percentage missing]. The physical reason for this superior performance lies in the A:B mass ratio being at a certain level. to When the interval is reached, the system forms a hydrodynamic radius of approximately to Nano-sized swollen micelles (compared to pure surfactant micelles in group D1) (Nano-scale), confirming that phytic acid molecules were successfully loaded onto micelles. Compared with the data from group D2, although phytic acid was present, the lack of a surfactant carrier... Still as high as Furthermore, the particle removal rate was extremely low, proving that relying solely on phytic acid cannot avoid diffusion kinetic lag and particle redeposition problems. More importantly, the two out-of-range control groups, D3 and D4, showed a clear performance inflection point: when the proportion was lower than At (D3), the micelle size did not increase, indicating that the excess phytic acid failed to enter the micelle structure and remained mainly in a free state. This not only reduced the corrosion inhibition effect but also caused the particle removal rate to plummet due to competitive adsorption. When the ratio is higher than At (D4), although the particle removal rate is acceptable, the micelle loading efficiency is reduced and the protective film coverage on the metal surface is insufficient, resulting in an increase in corrosion current.

[0038] Example 3: This example combines Figures 1 to 3 This document describes a cleaning agent for TFT substrate thinning and polishing, and its preparation method. Figure 1 As shown, this process flow demonstrates the component dissolution and environment construction stages. By mixing N-acyl amino acid salts, organic amines, and alcohol ether solvents while controlling the pH between 10.5 and 12.5, phytic acid or its salts are added dropwise. Under conditions of a weight ratio of 2.0:1 to 4.0:1, a phytic acid surfactant associative system is formed through hydrogen bond network self-assembly, thereby constructing a micelle hydrodynamic radius. A stable, associative micelle system with a saturated loading of corrosion inhibitor molecules, ranging from 8.0 nm to 12.0 nm, functions as a carrier for directional transport under high-speed spray conditions during high-shear single-piece rotary cleaning. The micelles facilitate the rapid migration of phytic acid to the interface, overcoming the Brownian motion limitation of the corrosion inhibitor. Upon contact with the metal interface, electrostatic induction release of phytic acid is achieved, resulting in a transient synchronous protection where the adsorption film formation rate exceeds the corrosion rate, thus eliminating flash corrosion. Simultaneously, long-chain alkyl penetration and Zeta potential modulation form a synergistic decontamination system, using electrostatic repulsion to prevent particle redeposition. Finally, during the concentration dilution stage of pure water rinsing, the concentration falls below the critical micelle concentration (CMC), causing micelle disintegration and desorption of the monomolecular phytic acid film, resulting in a product with no organic residue and a TOC < 10. A highly clean hydrophilic surface with a root mean square roughness variation of less than 0.5 nm.

[0039] like Figure 2 As shown, the horizontal axis represents the temperature range, and the vertical axis represents the average hydrodynamic radius of the micelles. The three curves correspond to the evolution trajectories of the micelle radius when the mass ratio of N-acyl amino acid salt to phytic acid is 2.5:1, 3.0:1, and 3.5:1, respectively. The data shows that within the temperature range of 0 to 40 degrees Celsius, the micelle radius under all three ratios remains stable in the range of approximately 9 nm to 10 nm, indicating that the associated structure is not destroyed by thermal fluctuations. However, when the temperature rises to 50 degrees Celsius and 60 degrees Celsius, the micelle radius shows a significant decreasing trend. Figure 3 As shown, the system consists of an intelligent liquid preparation unit, a core operating area, an online quality monitoring unit, and a central logic control PLC forming a closed loop. The intelligent liquid preparation unit is responsible for constant temperature variable frequency mixing, 0.1-micron precision filtration, and dynamic calibration of CMC concentration. The treated clean liquid is transported to a single-plate rotary cleaning machine in the core operating area for high-speed shearing, transient film formation, and particle removal. The system performs real-time conductivity detection, total organic carbon (TOC) analysis, and impurity exceedance warnings on the circulating sampled liquid entering the online quality monitoring unit. The generated parameter deviation signals are transmitted to the central logic control PLC to calculate the lifespan management model and trigger automatic liquid replenishment. Finally, the system generates execution correction instructions and feeds them back to the intelligent liquid preparation unit, realizing dynamic and precise control throughout the entire process from liquid preparation to production line application.

[0040] Example 4: To address the potential reliance on experience in determining the key parameter of the weight ratio of N-acyl amino acid salt to phytic acid or its salt in the previous examples, this example constructs a standardized engineering calibration procedure. The core of this procedure lies in revealing the balance point between the two mutually restrictive factors of micellar loading capacity and system stability, setting the basic conditions for the calibration experiment, and conducting the test at a constant temperature. In a dust-free experimental environment with a constant pH value, a series of samples were prepared. The basic cleaning solution, in which the concentration of N-acyl amino acid salt, taking sodium lauroyl sarcosinate as an example, is fixed at [value missing]. The concentrations of organic amines and alcohol ether solvents were added according to the aforementioned preferred ratios; secondly, a gradient addition and dynamic monitoring were performed, adding the solvents to the aforementioned basic cleaning solution as follows: The amount of phytic acid added is gradually increased by a mass percentage gradient, so that the weight ratio of N-acyl amino acid salt to phytic acid (denoted as ) is . ) Coverage from to Over a wide range, at each gradient point, the average hydrodynamic radius of the micelles in the system was measured using a dynamic light scattering (DLS) instrument. ), and used a UV-Vis spectrophotometer monitoring system in Transmittance at the nanometer level ( ( ), to characterize the microstructural changes and macroscopic stability of the system.

[0041] Finally, parameters are defined based on experimental data, when Greater than hour, Maintain at nanometer to The low position of the nanoparticles indicates that phytic acid molecules mainly exist in a free state and have failed to effectively enter the micelle structure. At this point, although the light transmittance is low... near However, the transient corrosion rate of metal surfaces is high; with the increase of phytic acid content, Enter to Within the range, observed It increased sharply and then stabilized. nanometer to Nano, and Still in This indicates the formation of phytic acid surfactant-associated micelles and the thermodynamic stability of the system; when Further reduced to The following times, although It continues to increase, but The precipitate begins to decrease, and even visible turbidity appears, indicating that excessive phytic acid has caused the micelle structure to break down or phase separation, thus compromising the system's stability. This procedure will... In nanometer to nano and Corresponding interval, i.e. to This was confirmed as the optimal process window that balances load efficiency and system stability.

[0042] Example 5: Given that fluctuations in thermodynamic conditions in industrial production environments may cause nonlinear interference to the stability of the core micro-associative structure of this invention, to ensure that the cleaning agent maintains a highly efficient loading configuration between phytic acid and N-acyl amino acid salt throughout the entire process from storage and transportation to the spraying terminal, a thermodynamic stability boundary calibration procedure based on light scattering dynamics is established. This requires that before the cleaning agent is put into mass production, samples are placed in a dynamic light scattering detection unit equipped with a precision temperature control system. Continuous temperature scanning is performed within a range covering the extreme ambient temperature of the production line, and the average hydrodynamic radius of the micelles in the system is recorded in real time. and polydispersity coefficient By analyzing the second derivative of the evolution curve with temperature, the critical temperature threshold for thermal dissociation or phase separation of associated micelles can be identified, defining a strict thermodynamically stable operating window within which... The value was empirically confirmed to remain at nanometer to Within the effective functional range of nanometers, the temperature boundary parameters output by this procedure will be directly solidified as the set value of the temperature control unit of the production line chemical supply system.

[0043] Furthermore, considering that the differences in rotation speed and spray pressure of single-wafer cleaning machines in different generations of TFT panel production lines can directly lead to changes in the fluid shear stress field on the substrate surface, potentially disrupting the kinetic balance of the corrosion-inhibiting adsorption film, a fluid dynamics compatibility calibration procedure based on rotating disk electrode technology is performed before introducing the cleaning agent into a specific machine. Working electrodes are fabricated using aluminum or copper metal, the same material as the substrate to be cleaned, and the Reynolds number generated by the fluid on the substrate surface during the cleaning process is simulated by adjusting the angular velocity of the rotating disk. The distribution of shear stress on the wall surface was monitored, and the corrosion current density at the metal interface was simultaneously monitored using a potentiostat. The dynamic response, by constructing a correlation model between shear stress and corrosion rate, can accurately pinpoint the upper limit of the critical rotational speed. Below this limit, the phytic acid molecular film peeling rate caused by the shear flow field is confirmed to be significantly lower than the replenishment adsorption rate driven by carrier micelles. This calibration result directly serves as the highest safety constraint for determining the cleaning process parameters of this machine, ensuring that the transient protection mechanism of the metal circuit surface can maintain positive kinetic redundancy under any high shear conditions. The weight ratio of N-acyl amino acid salt to phytic acid or salt is limited. to Range, lower limit of ratio in accordance with The polydispersity coefficient of associated micelle size in cleaning agents using dynamic light scattering instrument Monitoring results confirm that the ratio is lower than hour Value by The following rises sharply to Above, the carrier micelle structure is destroyed; upper limit in accordance with , Corrosion current density of the working electrode of the lower aluminum film The inhibition efficiency curve has been determined, and the ratio exceeds hour The marginal gain of inhibition efficiency approaches zero, and phytic acid molecules reach adsorption saturation at the metal interface; alcohol ether solvents and The effectiveness of the permeation dispersion system formed by -acyl amino acid salts was measured by a dynamic surface tension meter. Quantization within a time window, dynamic surface tension in Internal reduction to to The equilibrium zone enables rapid penetration into the interface of submicron-sized glass debris. α-Acyl amino acid salt raw material batch fluctuations, based on critical micelle concentration. The standardized incoming calibration and formula modification procedures are carried out using the conductivity method. The following linear fitting was performed on the raw material aqueous solution, and the real-time conductivity measurement value was converted into... Estimated value, for The actual feed amount of acyl amino acid salts is linearly compensated and corrected to stabilize micelle formation capability; the cleaning agent is compatible with the fluid shear stress environment of different generations of production lines, and the fluid dynamics compatibility calibration procedure uses a rotating disk electrode. Technical quantification calibration, adjusting the disk angular velocity Convert the shear flow field on the electrode surface into the Reynolds number. Determine the critical point Value, here Value of metal electrode The measured value showed a sustained Irreversible upward fluctuations This serves as the highest engineering safety constraint for setting specific cleaning machine process parameters (spray pressure, substrate rotation speed).

[0044] Example 6: To address the potential differences in purity and hydrophobic chain length distribution among different batches of N-acyl amino acid salt raw materials, this invention establishes a standardized raw material calibration and dynamic formulation revision procedure based on critical micelle concentration (CMC). This procedure uses the measured CMC value of actual raw materials to inversely deduce the content of effective active ingredients and micelle-forming ability, compensating for adjustments in production feed rates and eliminating the impact of raw material fluctuations on the stability of the final associated micelle structure. For each batch of N-acyl amino acid salt raw material entering the warehouse, samples need to be prepared into a series of aqueous solutions with varying concentrations, and then subjected to constant... Under Celsius conditions, the isotherm of surface tension as a function of concentration was measured using a fully automated surface tension meter. The measured CMC value of the batch of raw materials was accurately calculated by linearly fitting the abrupt change point of surface tension. If the measured CMC value deviates from the benchmark value, such as the standard CMC of sodium lauroyl sarcosinate, it is set at [value missing]. The range of millimoles per liter exceeds If the batch variation is found, then the raw material is determined to have batch differences, and a correction formula needs to be applied. Automatically calculates the actual amount of materials used in production. ,in This is the standard formulation dosage, ensuring that the number of effective surfactant molecules capable of forming micelles in each batch of finished cleaning agent remains within the design window.

[0045] Furthermore, to address the performance degradation of cleaning agents during production line recycling due to component consumption and impurity accumulation, a system for online monitoring and lifespan management of the bath solution based on a dual-parameter coupling of conductivity and total organic carbon (TOC) was developed, setting the initial conductivity of newly prepared bath solutions. and initial TOC value As a baseline, the instantaneous conductivity of the tank solution is collected in real time by online sensors during the operation of the cleaning machine. and total organic carbon content When detected Compared to The decline exceeded When the system detects that the ionic components (phytate and N-acyl amino acid salts) that play a major role in conductivity have been consumed, the system automatically triggers a replenishment logic, quantitatively adding concentrated replenishment solution until the conductivity returns to the baseline range; when it detects... Rise to of When the concentration of organic pollutants in the system exceeds 10 times the solubility limit of surfactant micelles, it is determined that the total amount of dissolved or suspended organic pollutants in the system is close to the solubility limit of surfactant micelles, and there is a risk of particle redeposition. The system issues a liquid replacement alarm and stops substrate feeding. This dual-parameter closed-loop control strategy realizes the transformation from passive timed liquid replacement to active on-demand maintenance.

[0046] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention.

[0047] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A cleaning agent for TFT substrate thinning and polishing, characterized in that, This cleaning agent is a homogeneous liquid system composed of the following components by weight percentage: 0.5% to 5.0% of an N-acyl amino acid salt, wherein the N-acyl amino acid salt is selected from at least one of sodium lauroyl sarcosinate, sodium cocoyl glutamate, or sodium lauroyl glutamate; 0.1% to 2.0% phytic acid or its salt; 1.0% to 8.0% of organic amines, wherein the organic amines are selected from at least one of monoethanolamine, diethylene glycolamine, triethanolamine or isopropanolamine; The cleaning agent contains 3.0% to 8.0% alcohol ether solvents, selected from ethylene glycol monobutyl ether or diethylene glycol monobutyl ether; and is supplemented to 100% deionized water. The content of organic amines maintains the pH value of the cleaning agent in the range of 10.5 to 12.

5. The weight ratio of N-acyl amino acid salt to phytic acid or its salt is strictly limited to the range of 2.0:1 to 4.0:

1. This weight ratio range limits the average hydrodynamic radius of the micelles in the cleaning agent to be in the range of 8 nm to 12 nm under pH conditions, while limiting the time for the dynamic surface tension of the cleaning agent to drop from the initial value to the equilibrium value to be less than 50 milliseconds, and the resistivity of the cleaning agent at 25 degrees Celsius to be less than 100 ohm·cm. The micelle structure formed by the N-acyl amino acid salt has a saturated loading capacity for phytic acid or its salt within the weight ratio range, thereby establishing a synchronous adsorption layer of surfactant and corrosion inhibitor at the moment the cleaning agent contacts the metal surface.

2. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The N-acyl amino acid salt is sodium lauroyl sarcosinate, the organic amine is diethylene glycol amine, and the alcohol ether solvent is ethylene glycol monobutyl ether. The pH value of the cleaning agent is controlled between 11.0 and 12.

0. At this pH value and component concentration, the absolute value of the zeta potential of the cleaning agent to cerium oxide particles is maintained above 40 mV, and the kinematic viscosity of the cleaning agent at 25 degrees Celsius is 1.0 mm² / s to 1.5 mm² / s.

3. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, Phytic acid or its salts are in a completely dissociated state in a system with a pH value of 10.5 to 12.5 and are loaded in the hydrophilic barrier layer of N-acyl amino acid salt micelles; the cleaning agent has critical micelle concentration-dependent dissociation characteristics, and when the cleaning agent is diluted with pure water to below the critical micelle concentration of N-acyl amino acid salt, the contact angle of the residue of the cleaning agent on the glass substrate surface is less than 10 degrees.

4. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The cleaning agent is free of silicate and phosphate inorganic corrosion inhibitors and benzotriazole organic corrosion inhibitors; the surface tension of the cleaning agent is 25 mN / m to 30 mN / m in the temperature range of 20°C to 60°C; the long-chain alkyl structure of N-acyl amino acid salt and alcohol ether solvent together constitute a penetrating dispersion system for submicron glass debris and polishing residues.

5. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, Weight percentage concentration of N-acyl amino acid salts weight percentage concentration of phytic acid or its salt Satisfy the following regarding dynamic loading factor Relationship: Among them, dynamic loading factor Define the microscopic loading capacity boundary of a unit mass of surfactant micelles for corrosion inhibitor molecules, when When within the specified range, the corrosion current density of the cleaning agent on the aluminum or copper metal surface is less than 0.1 microamps per square centimeter, and the thickness of the adsorbed film formed by the cleaning agent on the metal surface is 1 nanometer to 3 nanometers.

6. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The resistivity of deionized water at 25 degrees Celsius is greater than 18 megohm-cm, and the individual content of iron, copper, nickel, and chromium metal ion impurities in the cleaning agent is less than 10 ppb; the cleaning agent is filtered through a 0.1-micron pore size filter, and the particle size of the insoluble particles in the cleaning agent is less than 0.1 microns.

7. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The organic amine is a mixture of monoethanolamine and triethanolamine, wherein the mass ratio of monoethanolamine to triethanolamine is 1:1 to 2:1; the mixture forms a solubilizing system against phytic acid or its salts in the cleaning agent, and no crystals precipitate in the cleaning agent within a storage temperature range of 0°C to 40°C.

8. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The density of the cleaning agent is 1.01 g / cm³ to 1.05 g / cm³ at 25°C; the spreading speed of the cleaning agent on the glass substrate surface is greater than 500 mm / s under spray conditions with a pressure of 0.1 MPa to 0.3 MPa; the cleaning agent is suitable for cleaning TFT glass substrates containing aluminum, copper or molybdenum metal electrodes; during a single-piece rotation cleaning process with a cleaning time of 10 to 30 seconds, the root mean square roughness change of the metal electrode surface is controlled within 0.5 nm, and the total organic carbon residue on the substrate surface after cleaning is less than 10 micrograms per square meter.

9. The cleaning agent for TFT substrate thinning and polishing according to claim 1, characterized in that, The N-acyl amino acid salt is sodium cocoyl glutamate, and the phytic acid or its salt is sodium phytate; the weight ratio of the N-acyl amino acid salt to sodium phytate remains constant within a dilution ratio not exceeding 100 times, and the pH value of the cleaning agent varies by no more than 0.5 units.

10. A method for preparing a cleaning agent after thinning and polishing a TFT substrate, characterized in that, The cleaning agent for TFT substrate thinning and polishing is prepared by the cleaning agent for TFT substrate thinning and polishing as described in claim 1.

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