A cleaning agent for TFT panel after dry etching

Abstract

This invention discloses a cleaning agent for use after dry etching of TFT panels. The raw materials, by weight percentage (100%), include: 3%-10% oxidant, 0.1%-5% organic alkali, 1%-10% water-miscible organic solvent, 0.1%-2% copper ion complexing agent, 0.1%-2% copper corrosion inhibitor, 0.5%-3% wetting and dispersing agent, with the remainder being water. This cleaning agent employs a ternary synergistic mechanism of "oxidation-complexation-corrosion inhibition," effectively cleaning photoresist residues, polymers, and copper oxide on the surface of copper electrodes generated after dry etching during TFT panel production. It exhibits low corrosivity to copper electrodes, does not damage the silicon nitride and other media at the edges of the copper electrodes, and does not affect the pore size of the copper electrodes. It can resolve the triple contradiction of organic residue, CuO and Cu corrosion in one step, achieving second-level non-destructive cleaning.

Description

Technical Field

[0001] This invention belongs to the field of cleaning agent technology, specifically relating to a cleaning agent for use after dry etching of TFT panels. Background Technology

[0002] The TFT-LCD array process is the most precise and crucial front-end process in panel manufacturing, serving as the starting point of the entire process flow. Its core involves creating millions of thin-film transistors (TFTs) and precision circuits on a glass substrate through a "thin-film-patterning-etching" cycle to control each pixel. In TFT LCD panel production, etching is the key process for applying circuit patterns to the glass substrate, directly determining the final shape and performance of millions of micron-sized TFTs. It is one of the fundamental guarantees for achieving high-resolution, high-definition displays.

[0003] Etching uses photoresist as a mask to selectively remove thin films, precisely etching the designed TFT array and circuit patterns onto a glass substrate. Etching is mainly divided into wet etching and dry etching. Dry etching, utilizing plasma, has significant advantages in controlling linewidth and trench morphology, and is key to achieving nanoscale fine patterns in the future. With the continuous innovation of TFT LCD panels, copper, with its lower resistivity, has replaced aluminum as the new electrode material, and high-selectivity, low-damage etching technologies are constantly developing. However, even the most advanced etching techniques cannot completely avoid the damage to copper electrodes caused by the plasma in dry etching, resulting in copper oxide on the copper electrode surface. Furthermore, the dry etching process causes surrounding photoresist debris to adhere to the copper electrode surface, leading to poor contact in the copper electrode circuitry. Therefore, cleaning the glass panel after dry etching is crucial for ensuring product yield.

[0004] Currently, TFT LCD panel manufacturers primarily use a mixture of high-concentration hydrogen peroxide and ammonia for cleaning after dry etching. While this method effectively removes organic residues and copper oxide from the copper electrode surface, it easily leads to further corrosion of the copper electrode. Furthermore, the pungent odor of ammonia is detrimental to the health of production workers. Therefore, developing a novel cleaning agent that can simultaneously remove photoresist residues, polymers, and copper oxide from the copper electrode surface after dry etching without corroding the copper electrode or the surrounding medium is crucial. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a cleaning agent capable of removing photoresist residues, polymers, and copper oxide from the surface of copper electrodes generated after dry etching of TFT panels, without corroding the copper electrodes or the surrounding medium.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A cleaning agent for use after dry etching of TFT panels, wherein the total mass percentage of each raw material is 100%, and the mass percentage of each raw material is as follows: oxidant 3%-10%, organic base 0.1%-5%, water-miscible organic solvent 1%-10%, copper ion complexing agent 0.1-2%, copper corrosion inhibitor 0.1%-2%, wetting and dispersing agent 0.5%-3%, and the remainder is water.

[0007] Preferably, based on a total mass percentage of 100%, the mass percentage of each raw material in the cleaning agent is as follows: oxidant 4%-6%, organic base 1%-2%, water-miscible organic solvent 3%-4%, copper ion complexing agent 0.5-1%, copper corrosion inhibitor 0.1%-0.5%, wetting and dispersing agent 0.5%-2%, and the remainder is water.

[0008] Furthermore, the oxidant is hydrogen peroxide.

[0009] Furthermore, the organic base is one or more of monoethanolamine, diethanolamine, triethanolamine, diethylene glycolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, isopropanolamine, N-butyldiethanolamine, pyridine, etc.

[0010] Furthermore, the water-miscible organic solvent is one or more of the following: dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl ether, propylene glycol, and dipropylene glycol butyl ether.

[0011] Furthermore, the copper ion complexing agent is one or more of gluconic acid, ethylenediaminetetraacetic acid, glycine, hypozinotriacetic acid, hydroxyethylidene diphosphate, ethylenediaminetetramethylene phosphate, and diethylenetriaminepentamethylene phosphate.

[0012] Further, the copper corrosion inhibitor is one or more of the following: 2-mercaptobenzothiazole, benzotriazole, methylbenzotriazole, benzimidazole, 2-aminobenzothiazole, 3-amino-1,2,4-triazole, heptadecanylaminoethylimidazoline quaternary ammonium salt, cocoyl hydroxyethylimidazoline, 3-mercapto-1,2,4-triazole.

[0013] Furthermore, the wetting and dispersing agent is one or more of fatty alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, alkyl glycoside, polyethylene glycol, polypropylene glycol, etc.

[0014] The cleaning method using the cleaning agent involves spraying the TFT panel after dry etching with the cleaning agent to achieve cleaning.

[0015] Furthermore, the spray temperature is 35-45℃, and the spraying time is 30-120s.

[0016] Furthermore, after cleaning the TFT panel after dry etching with the cleaning agent, it is then rinsed with pure water for 40 seconds.

[0017] The beneficial effects of this invention are as follows: (1) The combination of oxidant, organic base and organic solvent in this invention can enhance the cleaning ability of the solution to residual organic matter, thereby quickly and effectively removing photoresist residue, polymer and other residues.

[0018] (2) The combination of oxidant, copper ion complexing agent, and copper corrosion inhibitor in this invention achieves a synergistic mechanism of simultaneous oxidation, complexation, and protection. Hydrogen peroxide, as the oxidant, oxidizes excess Cu and Cu2O on the copper electrode surface into more readily reacting CuO. The copper ion complexing agent then complexes with CuO to form a water-soluble copper complex, preventing copper ions from re-depositing. The copper corrosion inhibitor protects the copper electrode from excessive oxidation by hydrogen peroxide, preventing corrosion. The synergistic effect of these three components ensures that the copper electrode remains smooth and bright after cleaning.

[0019] (3) The addition of wetting and dispersing agent in this invention allows the cleaning agent to spread rapidly when sprayed onto the panel, especially to wet the surface of the copper electrode with a pore size of only 10 micrometers, thus achieving uniform and rapid cleaning.

[0020] (4) The cleaning agent for dry etching in TFT panel production provided by the present invention has a reasonable formula and a simple cleaning method, and has good prospects for promotion and application. Detailed Implementation

[0021] A cleaning agent for use after dry etching of TFT panels, wherein the total mass percentage of each raw material is 100%, and the mass percentage of each raw material is as follows: oxidant 3%-10%, organic base 0.1%-5%, water-miscible organic solvent 1%-10%, copper ion complexing agent 0.1-2%, copper corrosion inhibitor 0.1%-2%, wetting and dispersing agent 0.5%-3%, and the remainder is water.

[0022] The oxidant is hydrogen peroxide.

[0023] The organic base is one or more of the following: monoethanolamine, diethanolamine, triethanolamine, diethylene glycolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, isopropanolamine, N-butyldiethanolamine, pyridine, etc.

[0024] The water-miscible organic solvent is one or more of the following: dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl ether, propylene glycol, and dipropylene glycol butyl ether.

[0025] The copper ion complexing agent is one or more of the following: gluconic acid, ethylenediaminetetraacetic acid, glycine, hypozinotriacetic acid, hydroxyethylidene diphosphate, ethylenediaminetetramethylene phosphate, and diethylenetriaminepentamethylene phosphate.

[0026] The copper corrosion inhibitor is one or more of the following: 2-mercaptobenzothiazole, benzotriazole, methylbenzotriazole, benzimidazole, 2-aminobenzothiazole, 3-amino-1,2,4-triazole, heptadecanylaminoethylimidazoline quaternary ammonium salt, cocoyl hydroxyethylimidazoline, 3-mercapto-1,2,4-triazole.

[0027] The wetting and dispersing agent is one or more of fatty alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, alkyl glycoside, polyethylene glycol, and polypropylene glycol.

[0028] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0029] The technical solutions in the embodiments of the present invention have been clearly and completely described. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Examples and Comparative Examples Add each raw material to a clean, sealed production tank according to the formula in Table 1, and stir for 60-120 minutes at room temperature to obtain a uniform mixed solution, which is the cleaning agent.

[0031] Table 1

[0032] Effect verification 1) Clean the glass after TFT production array segment etching using a cleaning agent, and verify the corrosion of the copper electrodes on the glass surface by the cleaning agent.

[0033] 2) Heat the cleaning agent to 40°C, spray it to clean a glass plate of similar size after etching for 30 seconds, then rinse it with pure water and blow it dry. Observe the surface of the copper hole with a metallographic microscope to see if there are any residual organic substances after etching.

[0034] 3) Heat the cleaning agent to 40°C and spray it onto etched glass plates of similar size for 30 seconds. Then rinse with pure water and dry. Test the water droplet angle on the glass surface after cleaning to check whether the oil stains on the glass plate surface are clean. A water droplet angle of less than 30° is acceptable.

[0035] 4) Heat the cleaning agent to 40°C and spray it to clean the etched glass plates of similar size for 30 seconds. Then rinse them with pure water and blow them dry. Observe the surface of the copper electrode for corrosion using a metallographic microscope and observe the changes in the pore size of the copper electrode and the cross-section of the copper electrode for corrosion using SEM.

[0036] The test results are shown in Table 2.

[0037] Table 2

[0038] As can be seen from the test results in Table 1, the cleaning agents in Comparative Examples 1-3, which do not contain hydrogen peroxide, organic alkali, or organic solvents, have significantly insufficient ability to remove organic residues. Compared with Comparative Examples 1-3, the cleaning agents prepared in Examples 1-11 and Comparative Examples 4 and 5 can remove residual organic matter on the copper electrode surface and oil stains on the glass surface within 30 seconds. However, Comparative Examples 4 and 5 have the problems of failing to remove copper oxide on the copper electrode surface and causing severe corrosion to the copper electrode, respectively. Comparative Example 6, due to the lack of surfactant, has insufficient wettability of the solution on the glass surface, resulting in insufficient cleaning ability. The above experiments show that the synergistic effect of oxidants, organic solvents, organic alkalis, and surfactants can better meet the cleaning requirements, and under the protection of corrosion inhibitors, can effectively remove copper oxide generated on the copper electrode surface due to etching without causing excessive damage to the copper electrode.

[0039] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0040] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A cleaning agent for use after dry etching of TFT panels, characterized in that, Based on a total mass percentage of 100%, the mass percentage of each raw material in the cleaning agent is as follows: oxidant 3%-10%, organic base 0.1%-5%, water-miscible organic solvent 1%-10%, copper ion complexing agent 0.1-2%, copper corrosion inhibitor 0.1%-2%, wetting and dispersing agent 0.5%-3%, and the remainder is water.

2. The cleaning agent for TFT panel dry etching according to claim 1, characterized in that, Based on a total mass percentage of 100%, the mass percentage of each raw material in the cleaning agent is as follows: oxidant 4%-6%, organic base 1%-2%, water-miscible organic solvent 3%-4%, copper ion complexing agent 0.5-1%, copper corrosion inhibitor 0.1%-0.5%, wetting and dispersing agent 0.5%-2%, and the remainder is water.

3. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The oxidant is hydrogen peroxide.

4. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The organic base is one or more of monoethanolamine, diethanolamine, triethanolamine, diethylene glycolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, isopropanolamine, N-butyldiethanolamine, and pyridine.

5. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The water-miscible organic solvent is one or more of dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol, ethylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl ether, propylene glycol, and dipropylene glycol butyl ether.

6. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The copper ion complexing agent is one or more of gluconic acid, ethylenediaminetetraacetic acid, glycine, hypozinotriacetic acid, hydroxyethylidene diphosphate, ethylenediaminetetramethylene phosphate, and diethylenetriaminepentamethylene phosphate.

7. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The copper corrosion inhibitor is one or more of the following: 2-mercaptobenzothiazole, benzotriazole, methylbenzotriazole, benzimidazole, 2-aminobenzothiazole, 3-amino-1,2,4-triazole, heptadecanylaminoethylimidazoline quaternary ammonium salt, cocoyl hydroxyethylimidazoline, and 3-mercapto-1,2,4-triazole.

8. The cleaning agent for TFT panel dry etching according to claim 1 or 2, characterized in that, The wetting and dispersing agent is one or more of fatty alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, alkyl glycoside, polyethylene glycol, and polypropylene glycol.

9. A method for cleaning using the cleaning agent for dry etching of TFT panels as described in claim 1 or 2, characterized in that, The cleaning agent is used to clean the TFT panel after dry etching.

10. The method according to claim 9, characterized in that, The spray temperature is 35-45℃ and the time is 30-120s.

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