JP2007183577A - Aqueous alkali photoresist cleaning composition and usage of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous alkali photoresist cleaning composition having a simple composition, not containing an organic solvent harmful to a worker and the environment, and having excellent solvent power to photoresist used in a photo process of a semiconductor integrated circuit or a liquid crystal display or photoresist residue in a photoresist coating device and a developer piping system. <P>SOLUTION: The aqueous alkali photoresist cleaning composition contains 1-50 wt.% of at least one alkali compound, 0.1-20 wt.% of at least one diamine compound and 30-98.9 wt.% of water, based on the total weight of the composition and has a pH of >12. The photoresist scrubbing composition can be heated and/or diluted before use according to actual process conditions. Since the composition contains no organic solvent, it can safely be used in a regular work environment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is an aqueous alkaline photoresist cleaning that can be used to remove photoresist in photo processing of semiconductor integrated circuits or liquid crystal displays and can be used to clean residual photoresist from photoresist coating equipment and developer piping systems. Relates to the composition. The aqueous alkaline photoresist cleaning composition of the present invention is particularly suitable for processing a color photoresist used in a color filter process of a liquid crystal display.

  In the semiconductor and optoelectronic industries, the photo process is one of the most important steps. The line width, stacking mode, and resolution defined by the photo process are improving with the times. In the optoelectronic industry, usually a color photoresist is first coated on a glass substrate by spin coating or a different method in a photo process, followed by soft baking, exposure and development.

  Until now, the photoresist cleaning liquid for photo process in this industry has been mainly used for the following two applications. (1) Photoresist stripping; the photoresist needs to be washed and removed so as to obtain a wiring pattern after being subjected to a crosslinking reaction or acidification treatment in exposure and development; (2) Etching residue removal or Cleaning after ashing; the photoresist is ashed during plasma etching and remains on the substrate, so it must be cleaned.

  In addition to the photo process, the photoresist cleaning liquid has been used for cleaning residual photoresist from a photoresist coating apparatus and a developer piping system. In the optoelectronic industry, the consumption of the developer is increasing due to the increase in the size of the glass substrate. Currently, the developer used in this industry can be recovered for reuse after development. The cost of the liquid is reduced. However, during the color photoresist coating, some of the photoresist scatters from the glass substrate and remains inside the coater, resulting in a thick layer of photoresist residue on the coater wall after continuous mass production. It is formed. Furthermore, these photoresist residues pass through the developer recovery system and enter the developer piping system and barrel type bath, and as a result, the dried photoresist adheres throughout the coating apparatus and the developer piping system. Occurs. This photoresist residue enters the developer piping system after stripping and affects the efficiency of the filter core. If the photoresist residue is peeled off at the rear part of the filter core, the nozzle at the end of the outlet side of the developer is further blocked, which affects the developing process and causes an abnormal phenomenon during the process.

  Until now, most of the photoresist cleaning compositions used in the industry are organic solvents harmful to workers and the environment (for example, propylene glycol monomethyl ether ester (PGMEA), cyclohexanone, ethyl lactate, methyl isobutyl ketone (MIBK)). N-methylpyrrolidone (NMP), γ-butyrolactone, or combinations thereof).

  For example, Patent Document 1 discloses a photoresist removing composition containing tetramethylammonium hydroxide, a water-soluble amine, an alkylpyrrolidone, and a sugar or a sugar alcohol. In the composition, 10 to 90% by weight of N-methylpyrrolidone (NMP) is used as alkylpyrrolidone.

  Patent Document 2 describes alcohol amine, 0.01 to 100% by weight of amine, 5 to 80% by weight of water-soluble organic solvent, and 5 to 60% by weight of water (in the examples, the amount of water is 30% in all cases). Less), and a photoresist residue cleaning agent containing 1 to 35% by weight of an anticorrosive agent.

  Practitioners in the industry are working on research and development of photoresist cleaners that do not require the use of organic solvents that are harmful to workers and the environment.

  Patent document 3 is disclosing the aqueous cleaning liquid for removing polymer residues, such as a photoresist, a polyimide, a polyamic acid. The cleaning liquid contains an alkali metal hydroxide or a tetraalkylammonium hydroxide, an alcohol amine, a nonionic surfactant or an amphoteric surfactant, and a polybasic organic acid or a salt of a polybasic organic acid.

  Patent Document 4 discloses a cleaning method for removing a photoresist residue using an acidic photoresist cleaning composition having a pH of 2 to 6. The composition comprises water, an amine or tetraalkylammonium hydroxide, and acidic hydroxylamine. This photoresist cleaning composition needs to be used with an ozone water machine.

Patent Documents 5 and 6 disclose a cleaning method and a cleaning apparatus for removing photoresist particles from a printed wiring board (PWB). The photoresist cleaning composition used in the method is mainly composed of an organoamine represented by the general formula (R _k N) _n C _q R _m and a general formula [N _y R ′ _w ] ⁺ [A] ⁻ . And an ionic nitrogen compound represented by alkali metal or alkaline earth metal hydroxide. According to the disclosure of these specifications, the organoamine is preferably an alcohol amine compound.
US Pat. No. 6,440,326 US Pat. No. 6,638,694 US Pat. No. 6,635,118 US Pat. No. 6,245,155 US Pat. No. 5,599,444 US Pat. No. 5,531,889

  In this industry, the composition is simple, does not contain an organic solvent harmful to workers and the environment, and is used in a photo process of a semiconductor integrated circuit or a liquid crystal display, or a photoresist coating apparatus and a developer. There remains a need for aqueous photoresist cleaning compositions that have excellent solubility in piping system photoresist residues.

  The main object of the present invention is an aqueous alkaline photoresist cleaning composition, comprising at least one alkali compound in an amount of 1 to 50% by weight and at least one diamine compound in an amount of 0.1 to 0.1% based on the total weight of the composition. It is to provide a composition containing 20% by weight, 30-98.9% by weight of water and having a pH of more than 12.

  A further object of the present invention is a method for producing a color filter for a liquid crystal display, wherein the color photoresist film is removed from the glass substrate by bringing the aqueous alkaline photoresist cleaning composition of the present invention into contact with the color photoresist film. Providing a method comprising the steps of:

  A further object of the present invention is a method for cleaning a color photoresist residue from a color photoresist coating apparatus and a developer piping system, the aqueous alkaline photoresist cleaning composition of the present invention being used as a color photoresist coating apparatus and a developer. It is to provide a method comprising removing color photoresist residue from a color photoresist coating apparatus and developer piping system by contacting the piping system.

  The aqueous alkaline photoresist cleaning composition of the present invention comprises 1 to 50% by weight of at least one alkali compound, 0.1 to 20% by weight of at least one diamine compound, and 30 to 30% of water based on the total weight of the composition. It contains 98.9% by weight and the pH is more than 12, preferably more than 13.

  The alkali compound used in the present invention is an inorganic base or an organic base. The inorganic base is preferably selected from alkali metal hydroxide compounds such as sodium hydroxide, potassium hydroxide and mixtures thereof, and the organic base is preferably a quaternary ammonium hydroxide compound represented by the following formula: Selected from.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each independently represents alkyl or hydroxyalkyl having 1 to 6 carbon atoms).
More preferably, the organic base is tetramethylammonium hydroxide.

  The usage-amount of the alkali compound in this invention is the range of 1-50 weight% with respect to the composition total weight, Preferably it is 10-50 weight%, More preferably, it is 20-50 weight%.

The diamine compound used in the present invention is preferably selected from the group consisting of ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, phenylenediamine, diethylenediamine, triethylenediamine, tetraethylenediamine and mixtures thereof. However, ethylenediamine, diethylenediamine and mixtures thereof are more preferred.
The usage-amount of the diamine compound in this invention is the range of 0.1-20 weight% with respect to a composition total weight, Preferably it is 1-10 weight%, More preferably, it is 1-5 weight%.

  The water used in the present invention is preferably deionized water, and the amount thereof is in the range of 30 to 98.9% by weight, preferably 40 to 89% by weight, more preferably 45 to 79% by weight based on the total weight of the composition. %.

  The cleaning composition of the present invention optionally contains 0.01 to 3% by weight of at least one surfactant capable of making the surface tension of the cleaning composition less than 40 mN / m with respect to the total weight of the composition. Can be made. By adding a surfactant, the wet characteristics of the cleaning composition can be improved, the surface tension can be reduced, and the photoresist peeling action is improved. A suitable surfactant of the present invention is not particularly limited, but is an anionic, cationic or nonionic surfactant.

  The aqueous alkaline photoresist cleaning composition of the present invention has an excellent dissolving ability for a photoresist used in a photo process of a semiconductor integrated circuit or a liquid crystal display, or a photoresist residue of a photoresist coating apparatus and a developer piping system. . Thus, the compositions of the present invention can be used in photoprocesses to remove photoresist and can be used to clean photoresist residues from photoresist coating equipment and developer piping systems.

  In a preferred embodiment, the aqueous alkaline photoresist cleaning composition of the present invention is particularly suitable for the processing of color photoresists used as color filters for liquid crystal displays.

  Accordingly, the present invention further provides a method for producing a color filter for a liquid crystal display, the step of removing the color photoresist film from the glass substrate by bringing the aqueous alkaline photoresist cleaning composition of the present invention into contact with the color photoresist film. A method comprising:

  The present invention is also a method for cleaning a color photoresist residue from a color photoresist coating apparatus and a developer piping system, and the aqueous alkaline photoresist cleaning composition of the present invention is applied to a color photoresist coating apparatus and a developer piping system. A method is provided that includes removing color photoresist residues from the color photoresist coating apparatus and developer piping system by contacting.

  The aqueous alkaline photoresist cleaning composition of the present invention can be used as it is at a normal temperature, or can be used after being diluted with ultrapure water according to the conditions required for an actual process. Furthermore, since the aqueous alkaline photoresist cleaning composition of the present invention does not contain an organic solvent harmful to workers and the environment, it can be safely used in a normal working environment. Even if the process requirements require that the temperature be raised to improve dissolution, the operator need not pay attention to the toxic substances that can be caused by heating. Furthermore, the wastewater generated in the manufacturing process can be easily treated by a commonly used wastewater treatment with a neutral pH, and no additional wastewater treatment for the organic solvent is required.

  EXAMPLES Hereinafter, although an Example is given and this invention is further demonstrated, these Examples do not intend limiting the scope of the present invention. Any changes or modifications readily achieved by those skilled in the art are intended to be within the scope of the present invention.

Example 1
Method of Operation 50 mL of the cleaning liquid composition having the composition shown in the following table and 0.06 g of the photoresist polymer were stirred at room temperature. The time required to dissolve the photoresist polymer to less than 1 mm ² was measured.

Observation Results From the results in Table 1, it can be seen that when only an alkali compound was added, the color photoresist polymer could not be effectively dissolved in less than 1 mm ² in a short time.

  From the results shown in Table 2, the addition of a surfactant (BYK-Chemie GmbH, Germany; BYK-380N) in addition to the alkali compound can further shorten the dissolution time of the color photoresist polymer. It can be seen that the time required for dissolution of is still very long. This is because the addition of a surfactant is not intended to improve the dissolution efficiency, but to improve the stripping efficiency of the photoresist from the wall of the piping system by reducing the surface tension and improving the wettability. It is because it aims to make it. As can be seen by comparing Table 2 and Table 3, the dissolution time of the color photoresist can be greatly shortened only when a diamine compound is further added to the composition.

Example 2
Operation method The cleaning liquid composition having the composition shown in the following table was diluted to each magnification with deionized water. 50 mL of the cleaning liquid composition at each dilution ratio and 0.06 g of the photoresist polymer were stirred at 35 ° C. The time required to dissolve the photoresist polymer to less than 1 mm ² was measured.

Observation Result (1) From the results in Table 4, it can be seen that the cleaning composition according to the present invention has an excellent dissolving action on the red photoresist polymer even after dilution.

(2) From the results in Table 5, it can be seen that the cleaning composition according to the present invention has an excellent dissolving action on the green photoresist polymer even after dilution.

(3) From the results in Table 6, it can be seen that the cleaning composition according to the present invention has an excellent dissolving action on the blue photoresist polymer even after dilution.

Example 3
Operation method The cleaning liquid composition having the composition shown in the following table was diluted 1.3 times. 50 mL each of the diluted cleaning solution composition and 0.06 g of the photoresist polymer were stirred at different temperatures. The time required to dissolve the photoresist polymer to less than 1 mm ² was measured.

Observation Results As can be seen from the results in Table 7, the ability to dissolve the photoresist of the cleaning composition of the present invention can be significantly improved by raising the operating temperature.

Example 4
Method of Operation 50 mL of the cleaning liquid composition having the composition shown in the following table and 0.06 g of the photoresist polymer were stirred at room temperature. The time required to dissolve the photoresist polymer to less than 1 mm ² was measured.

Observation results As can be seen from the results in Table 8, the use of a diamine compound (diethylenediamine) in place of the alcoholamine compound (ie, ethanolamine or diethanolamine) disclosed in the prior art improves the photoresist dissolving ability of the cleaning composition. It can be significantly improved.

Claims (13)

An aqueous alkaline photoresist cleaning composition, relative to the total weight of the composition,
(A) 1 to 50% by weight of at least one alkali compound;
(B) 0.1-20 wt% of at least one diamine compound; and (c) 30-98.9 wt% of water,
A composition having a pH greater than 12.   The composition according to claim 1, wherein the alkali compound is an inorganic base or an organic base. The inorganic base is an alkali metal hydroxide compound, and the organic base has the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each independently represents alkyl or hydroxyalkyl having 1 to 6 carbon atoms). The composition of claim 2 which is an ammonium compound.   The composition according to claim 3, wherein the alkali metal hydroxide compound is sodium hydroxide or potassium hydroxide, and the quaternary ammonium hydroxide compound is tetramethylammonium hydroxide.   The composition of claim 1, wherein the diamine compound is selected from the group consisting of ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, phenylenediamine, diethylenediamine, triethylenediamine, and tetraethylenediamine.   The amount of alkali compound is in the range of 10 to 50 wt%, the amount of diamine compound is in the range of 1 to 10 wt%, and the amount of water is in the range of 40 to 89 wt%. Composition.   The amount of alkali compound is in the range of 20-50% by weight, the amount of diamine compound is in the range of 1-5% by weight, and the amount of water is in the range of 45-79% by weight. Composition.   2. The surfactant according to claim 1, further comprising at least one surfactant capable of bringing the surface tension of the cleaning composition to less than 40 mN / m in an amount of 0.01 to 3% by weight relative to the total weight of the composition. Composition.   9. A composition according to claim 8, wherein the surfactant is an anionic, cationic or nonionic surfactant.   The composition of claim 1, wherein the pH of the composition is greater than 13.   The composition according to claim 1, wherein the photoresist is a color photoresist used as a color filter of a liquid crystal display.   A method for producing a color filter for a liquid crystal display, comprising the step of removing the color photoresist film on a glass substrate by bringing the color photoresist film into contact with the aqueous alkaline photoresist cleaning composition according to claim 1.   Removing a color photoresist residue from the color photoresist coating apparatus and developer piping system by contacting the color photoresist coating apparatus and developer piping system with the aqueous alkaline photoresist cleaning composition of claim 1. A method for cleaning color photoresist residues from a color photoresist coating apparatus and developer piping system.