Spraying plate efficient chemical film removing agent based on synergistic stripping and base material protection and film removing method

Abstract

The invention discloses a spraying plate efficient chemical film removing agent based on synergistic stripping and base material protection and a film removing method. According to the invention, a'synergistic stripping system 'and a'dual corrosion inhibition mechanism' are introduced, and cross-linked polymerized residual films on the surface of a spraying plate and in micropores are efficiently removed through a staged targeting action mechanism. The method not only can prevent macroscopic corrosion, but also can inhibit microcosmic damage such as intergranular corrosion and the like, so that the precision part is better protected.

Description

Technical Field

[0001] This invention belongs to the field of specialty chemicals and surface treatment technology, specifically relating to a high-efficiency chemical film remover for spray plates based on synergistic peeling and substrate protection, as well as a film removal method. Background Technology

[0002] Spray plates are key components in the manufacturing processes of semiconductors, flat panel displays, and solar cells. Their surface and numerous micropores are used to uniformly distribute and spray special gases or chemical liquids. During use, a hard polymer film or other chemical residues (hereinafter referred to as "residual film") gradually deposits and forms on the surface and inside the pores of the spray plate. This residual film can clog the spray holes, alter the airflow or liquid flow path, and severely affect process uniformity and product yield.

[0003] Currently, the industry primarily relies on physical methods for removing film from spray plates, such as dry ice cleaning, laser cleaning, and sandblasting. Among these, sandblasting is a commonly used method. However, this method has several inherent drawbacks:

[0004] (1) High cost: It requires expensive sandblasting equipment and consumes a lot of consumables (such as sand) and energy.

[0005] (2) Single formulation and poor adaptability: Ordinary acid, alkali or solvent formulations are effective for specific types of residual films (such as fluorocarbon polymers and silicate deposition), but they are powerless against complex mixed residual films generated in modern processes.

[0006] (3) The contradiction between penetration and corrosion: strong chemical agents are often highly corrosive to the substrate, while mild agents are difficult to penetrate into the deep pores, resulting in the awkward situation of "clean surface, blocked pores".

[0007] (4) Incomplete cleaning: For micropores, blind holes or complex geometric structures with high aspect ratios, the impact force of sandblasting is difficult to reach, resulting in the inability to remove the residual film inside the hole, which poses a hidden danger for subsequent processes.

[0008] Therefore, the industry urgently needs a spray plate film removal technology that can overcome the above-mentioned shortcomings. Chemical film removal is theoretically an ideal solution, but conventional acids, alkalis or organic solvents are ineffective at peeling off specific, highly cross-linked residual films (such as plasma-enhanced fluorocarbon polymers, silicides, photoresist residues, etc.) on spray plates, and may corrode the spray plate substrate or be environmentally unfriendly. Summary of the Invention

[0009] This invention addresses the shortcomings of existing technologies by providing a highly efficient chemical film-removing agent and method for spray plates based on synergistic exfoliation and substrate protection. This invention introduces a "synergistic exfoliation system" and a "dual corrosion inhibition mechanism," efficiently removing cross-linked polymerized residual film from the surface and micropores of the spray plate through a staged targeted action mechanism. This invention not only prevents macroscopic corrosion but, more importantly, inhibits microscopic damage such as intergranular corrosion, thereby better protecting precision components.

[0010] This invention relates to a highly efficient chemical film remover for spray plates based on synergistic peeling and substrate protection. It consists of two components: Agent A (swelling and penetrating agent) and Agent B (reactive peeling agent). When used, they are mixed in proportion to achieve phased targeted action.

[0011] The A agent comprises, by mass percentage: 60%-85% primary penetrating solvent, 1%-5% metal chelating agent, 0.5%-3% high-efficiency penetrating surfactant, 0.5%-2% corrosion inhibitor, and the balance being deionized water. The function of the A agent is to preferentially wet, penetrate, and physically swell the residual film, disrupting its dense structure and creating channels and spaces for the reaction of the B agent.

[0012] The primary permeation solvent is selected from one or more of N-methylpyrrolidone and dimethyl sulfoxide.

[0013] The metal chelating agent is selected from sodium gluconate or sodium citrate. Its function is to complex the metal ion crosslinking points in the residual membrane, thereby dismantling the membrane skeleton from the inside.

[0014] The highly efficient penetrating surfactant is selected from isomeric alcohol ethers (such as isomeric decacarbon alcohol polyoxyethylene ether) and fluorocarbon surfactants. Its function is to greatly reduce surface tension, ensuring that the drug solution can quickly penetrate into micron-sized pores.

[0015] The corrosion inhibitor A is selected from benzotriazole, benzothiazole, and benzimidazole. Its function is to provide initial protection to the substrate during the first penetration step.

[0016] The B agent comprises, by mass percentage: 20%-40% alkaline component, 5%-25% oxidant, 2%-8% corrosion inhibitor, and the balance being deionized water. The function of the B agent is to chemically decompose the loosened residual film after the action of the A agent, breaking it down into smaller molecules and allowing it to peel off.

[0017] The alkaline component is selected from organic or inorganic bases, preferably from one or more of monoethanolamine (MEA), hydroxylamine, potassium hydroxide (KOH), and sodium hydroxide (NaOH). This component is used to hydrolyze and saponify chemical bonds such as ester and amide bonds in the residual film.

[0018] The oxidant is selected from organic or inorganic peroxides, preferably one or more of hydrogen peroxide (H2O2), peracetic acid, and ammonium persulfate. This component is used to oxidize and decompose the carbon chains and cross-linked structures in the residual film, transforming them into easily soluble small molecules.

[0019] The B-type corrosion inhibitor is composed of one or more adsorption / precipitation type corrosion inhibitors such as sodium molybdate and rare earth metal salts (e.g., cerium nitrate). Its function is to provide stronger targeted protection during the violent reaction phase, forming a dual protection system with the A-type corrosion inhibitor.

[0020] The film removal method based on the high-efficiency chemical film remover for spray plates of the present invention includes the following steps:

[0021] Step 1: First Stage

[0022] Immerse the spray plate to be treated completely in Agent A at room temperature to 40°C, and then perform ultrasonic treatment for 10-30 minutes. The key to this stage is physical penetration and swelling; the low temperature can prevent the residual film from undergoing a cross-linking reaction too early, making it more difficult to remove.

[0023] Step 2: Second Stage

[0024] Transfer the spray plate to a preheated mixture of agents A and B, and sonicate at 50℃-80℃ for 0.5-3 hours. The core of this stage is chemical decomposition and exfoliation, and the temperature increase significantly accelerates the reaction.

[0025] After the treatment is completed, remove the spray plate, rinse it with deionized water under high pressure, and finally blow it dry with high-purity nitrogen and vacuum dry it.

[0026] In the mixture of agent A and agent B, the volume ratio of agent A to agent B is 3:1 to 1:1.

[0027] The mixture of agent A and agent B can be newly prepared, or it can be obtained by adding agent B to agent A in step 1 and mixing.

[0028] The beneficial effects of this invention are reflected in:

[0029] 1. High efficiency and thoroughness: Through the triple synergistic effect of swelling of the main solvent, hydrolysis of alkaline components and oxidative decomposition of oxidant, it can efficiently and thoroughly remove stubborn residual film on the surface of the spray plate and inside the micropores, solving the problem that sandblasting cannot clean the inside of the holes.

[0030] 2. Protecting the substrate: The unique dual corrosion inhibitor in the formula can form an effective protective layer on the surface of the spray plate substrate, minimizing the corrosion of the precision metal substrate by the chemical solution and extending the service life of the spray plate.

[0031] 3. Improve efficiency and reduce costs: The combination of chemical soaking and ultrasonic methods can achieve automated batch processing, greatly reducing manual operation, improving film removal efficiency, and the overall cost is significantly lower than that of sandblasting.

[0032] 4. Environmentally friendly: Compared with the sandblasting method, which generates a large amount of dust and waste, the chemical waste liquid of the present invention is easy to centrally treat, and the formulation preferably contains environmentally friendly components. Attached Figure Description

[0033] Figure 1 The static contact angle between the membrane remover in Example 1 and ultrapure water after membrane removal is <5° (uniform).

[0034] Figure 2 The static contact angle between the membrane remover and ultrapure water after membrane removal in Example 2 is <5° (uniform).

[0035] Figure 3 The static contact angle between the membrane remover and ultrapure water after membrane removal in Example 3 is <5° (uniform).

[0036] Figure 4 The static contact angle between the membrane remover in Comparative Example 1 and ultrapure water after membrane removal is 10°-25° (non-uniform).

[0037] Figure 5 The static contact angle between the membrane remover in Comparative Example 2 and ultrapure water after membrane removal is >60° (severely non-uniform). Detailed Implementation

[0038] The present invention will be further illustrated by the following examples, but the scope of protection of the present invention is not limited thereto.

[0039] Example 1:

[0040] Agent A formulation: 78% N-methylpyrrolidone, 2% sodium gluconate, 1.5% isomeric decacarbonyl polyoxyethylene ether, 1% BTA, with the remainder being deionized water.

[0041] Agent B formulation: 45% hydroxylamine (50%), 20% hydrogen peroxide (30%), 5% sodium molybdate, with the remainder being deionized water.

[0042] Instructions for use: First, sonicate in Agent A at 35℃ for 20 minutes, then add 1 / 2 volume of Agent B, mix, and then heat to 65℃ and continue sonicating for 90 minutes.

[0043] Example 2:

[0044] Agent A formulation: 70% dimethyl sulfoxide, 10% N-methylpyrrolidone, 3% sodium citrate, 1% fluorocarbon surfactant, 1.5% BTA, with the remainder being deionized water.

[0045] Agent B formulation: 30% monoethanolamine, 30% peracetic acid (15%), 4% cerium nitrate, with the remainder being deionized water.

[0046] Instructions for use: First, sonicate in Agent A at room temperature for 30 minutes, then transfer to a 1:1 mixture of Agent A and Agent B at 60°C and sonicate for 2 hours.

[0047] Example 3:

[0048] Agent A formulation: 65% N-methylpyrrolidone, 4% sodium gluconate, 2% isomeric decacarbonyl polyoxyethylene ether, 2% BTA, with the remainder being deionized water.

[0049] Agent B formulation: 35% hydroxylamine (50%) and monoethanolamine (mixed in a 1:1 mass ratio), 15% hydrogen peroxide (30%), 6% sodium molybdate and cerium nitrate (mixed in a 1:1 mass ratio), with the remainder being deionized water.

[0050] Instructions for use: First, sonicate in agent A at 40℃ for 15 minutes, then add an equal volume of agent B, raise the temperature to 70℃, and sonicate for 1 hour.

[0051] Comparative Example 1: Single-component formulation

[0052] Formulation: All components of Agent A and Agent B in Example 1 are premixed into a single-component film remover.

[0053] Instructions for use: Heat directly to 65℃ and sonicate for 110 minutes.

[0054] Comparative Example 2: Order Reversed

[0055] The same agents A and B as in Example 1 were used, but in reverse order: the spray plate was first treated with agent B at 65°C for 90 minutes, and then treated with agent A at 35°C for 20 minutes.

[0056] After the processing of the above embodiments and comparative examples is completed, the spray plate is removed, rinsed with high-pressure deionized water, and finally dried with high-purity nitrogen and dried in a vacuum oven at 80°C for 30 minutes.

[0057] Effect verification:

[0058] Visual inspection revealed that the residual film on the surface of the spray plate and within all micropores had been completely removed, exposing the metal substrate, which was smooth and free of visible corrosion. Flow testing showed that the flow rate of all spray holes recovered to over 98% of that of a new plate, demonstrating excellent film removal performance.

[0059] The following performance evaluations were performed on the spray panels of the embodiments and comparative examples:

[0060]

Claims

1. A high-efficiency chemical defilming agent for spray plate based on synergistic stripping and substrate protection, characterized in that: the high-efficiency chemical defilming agent for spray plate comprises A agent and B agent; the A agent comprises, by mass percentage, 60-85% of main penetrating solvent, 1-5% of metal chelating agent, 0.5-3% of high-efficiency penetrating surfactant, 0.5-2% of A agent corrosion inhibitor, and the balance of deionized water; and the B agent comprises, by mass percentage, 20-40% of alkaline component, 5-25% of oxidizing agent, 2-8% of B agent corrosion inhibitor, and the balance of deionized water.

2. The high-efficiency chemical defilming agent for spray plate according to claim 1, characterized in that: in the A agent, the main penetrating solvent is selected from one or more of N-methyl pyrrolidone and dimethyl sulfoxide; the metal chelating agent is selected from sodium gluconate or sodium citrate; the high-efficiency penetrating surfactant is selected from isomeric alcohol ethers or fluorocarbon surfactants; and the A agent corrosion inhibitor is selected from one or more of benzotriazole, benzothiazole and benzimidazole.

3. The high-efficiency chemical defilming agent for spray plate according to claim 1, characterized in that: in the B agent, the alkaline component is selected from organic bases or inorganic bases; the oxidizing agent is selected from organic peroxides or inorganic peroxides; and the B agent corrosion inhibitor is selected from sodium molybdate or rare earth metal salts.

4. The high-efficiency chemical defilming agent for spray plate according to claim 3, characterized in that: the alkaline component is selected from one or more of monoethanolamine, hydroxylamine, potassium hydroxide and sodium hydroxide.

5. The high-efficiency chemical defilming agent for spray plate according to claim 3, characterized in that: the oxidizing agent is selected from one or more of hydrogen peroxide, peroxyacetic acid and ammonium persulfate.

6. A defilming method comprising the following steps: step 1: first stage completely immersing the spray plate to be treated in the A agent, supplemented by ultrasonic treatment; step 2: second stage transferring the spray plate to a mixed solution of the A agent and the B agent which has been preheated, and ultrasonic treatment.

7. The defilming method according to claim 6, characterized in that: after the treatment is completed, the spray plate is removed, washed with high-pressure spraying of deionized water, and finally blown dry with high-purity nitrogen and vacuum dried.

8. The defilming method according to claim 6, characterized in that: in step 1, the system temperature during ultrasonic treatment is room temperature to 40°C, and the ultrasonic treatment time is 10-30 minutes.

9. The defilming method according to claim 6, characterized in that: in the mixed solution of the A agent and the B agent, the volume ratio of the A agent to the B agent is 3:1 to 1:

1.

10. The defilming method according to claim 6, characterized in that: in step 2, the system temperature during ultrasonic treatment is 50-80°C, and the ultrasonic treatment time is 0.5-3 hours. ​ ​ ​ ​ ​ ​ ​ ​ ​ 6. The method for removing film based on the high-efficiency chemical film remover of any one of claims 1-5, characterized in that ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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