CN107168021B - Stripping liquid for photoresist and preparation method and application thereof - Google Patents
Stripping liquid for photoresist and preparation method and application thereof Download PDFInfo
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- CN107168021B CN107168021B CN201710549836.0A CN201710549836A CN107168021B CN 107168021 B CN107168021 B CN 107168021B CN 201710549836 A CN201710549836 A CN 201710549836A CN 107168021 B CN107168021 B CN 107168021B
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- quaternary ammonium
- ammonium hydroxide
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- stripping
- ester
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a stripping liquid for photoresist, which comprises, by weight, 5-28% of ester quaternary ammonium hydroxide, 50-65% of water-soluble organic solvent, 0.5-2% of nonionic surfactant and the balance of deionized water. The invention can control the alkalinity change, so that the alkalinity change is in a very small stable range, which is beneficial to the continuous and effective operation of the stripping work; in addition, the invention can also slow down the corrosion process of copper and ensure that the panel is not damaged.
Description
Technical Field
The invention relates to an electronic chemical technology in the industries of liquid crystal display thin film transistors and touch screens, in particular to a stripping liquid for photoresist and a preparation method and application thereof.
Background
The production process of the liquid crystal panel is roughly as follows: the front-end Array process mainly comprises four major parts of thin film, yellow light, etching and stripping. Firstly, an ITO film layer is required to be deposited on TFT glass, so that a smooth and uniform ITO film is formed on the whole TFT glass. Then, the ITO glass was washed with ionized water and ready for the next step. Then, photoresist is coated on the glass on which the ITO film is deposited, and a uniform photoresist layer is formed on the ITO glass. And then baking for a period of time to volatilize the solvent part of the photoresist and increase the adhesion degree of the photoresist material and the ITO glass. And irradiating the surface of the photoresist by ultraviolet light (UV) through a prefabricated electrode pattern mask to enable the irradiated photoresist layer to react, covering the photoresist mask on the glass coated with the photoresist, and selectively exposing the photoresist under an ultraviolet lamp.
In the process of coating the photoresist layer, coating defects are easily generated, and after the number of defects reaches a certain number, the substrate must be reworked. In the continuous use process of the stripping liquid in the prior art, the reaction temperature is higher, moisture and organic components are continuously evaporated, the reaction environment changes more and more, the alkalinity of the stripping liquid is greatly changed, the stripping environment changes violently and can not be used as regeneration of a substrate in a COA (chemical on board) process, a Cu/Al circuit and a PV layer on the substrate need to be reserved due to the regeneration of the substrate in the COA process, the stripping liquid which is widely used in the prior art and needs to be used at the higher reaction temperature can corrode the Cu/Al circuit and the PV layer which need to be reserved, and therefore the substrate can not be reused.
For example, CN102944986A discloses a polyimide stripping solution for chips, which is prepared by mixing pyrrolidone, sulfoxide, alcohol ether, quaternary ammonium, alkali and water in a certain proportion.
As disclosed in CN 102216855B, a photoresist stripping composition for manufacturing LCD, relates to an aqueous combined photoresist stripping composition as a weakly basic complex, said composition comprising a tertiary alkanolamine, water and an organic solvent.
The stripping composition needs to be added with water continuously in the using process, otherwise, the alkalinity of the stripping liquid can be changed greatly along with the lapse of time, so that the stripping time of the photoresistance is shortened, the photoresistance is not dissolved in time, and the conditions of equipment blockage and the like are generated, which is not beneficial to continuous production.
Disclosure of Invention
The invention aims to provide a stripping liquid for photoresist, which can control the alkalinity change of the stripping liquid environment without adding water, so that the stripping capability of the stripping liquid in the long-time production process is kept unchanged, and the Cu/Al and PV layers required to be reserved on a substrate are not corroded while the required stripping efficiency and quality are kept. Also discloses a preparation method and application.
The invention is realized by the following technical scheme:
a stripping liquid for photoresist comprises 5-28% of ester quaternary ammonium hydroxide, 50-65% of water-soluble organic solvent, 0.5-2% of nonionic surfactant and the balance of deionized water by weight.
The ester-based quaternary ammonium hydroxide is one or two of monoester-based quaternary ammonium hydroxide and diester-based quaternary ammonium hydroxide,
as shown in the formula I,
R1and R3Are all selected from C1-C5 alkyl, R2Selected from C1-C5 alkyl or C1-C5 ester group, n is any integer of 1-5, R4Is an alkyl group.
The ester quaternary ammonium hydroxide accounts for 15-25% by weight.
The water-soluble organic solvent is 55-60% by weight.
The nonionic surfactant is 0.8-1.2% by weight.
The water-soluble quaternary ammonium salt water-based paint consists of ester-based quaternary ammonium hydroxide, a water-soluble organic solvent, a nonionic surfactant and deionized water.
The monoester quaternary ammonium hydroxide is one of methyl ethanolamine carbomethoxy quaternary ammonium hydroxide, methyl ethanolamine ethosulfate quaternary ammonium hydroxide, methyl alcohol amine carbomethoxy quaternary ammonium hydroxide, methyl ethyl alcohol amine carbomethoxy quaternary ammonium hydroxide, methyl alcohol amine ethosulfate quaternary ammonium hydroxide, methyl alcohol amine carbomethoxy quaternary ammonium hydroxide and methyl butanol amine carbomethoxy quaternary ammonium hydroxide.
The diester quaternary ammonium hydroxide is one of methyldiethanolamine methyl ester quaternary ammonium hydroxide, methyldiethanolamine ethyl ester quaternary ammonium hydroxide and methyldiethanolamine propyl ester quaternary ammonium hydroxide.
The preparation method of the stripping liquid for the photoresist is prepared by uniformly mixing ester quaternary ammonium hydroxide, water-soluble organic solvent, non-surface ionic active agent and deionized water.
The use of the stripping liquid for photoresist in stripping photoresist is described.
The water-soluble organic solvent is one or the mixture of dihydric alcohol and glycol ether. Such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and the like.
In the invention, the nonionic surfactant can be an organic silicon defoamer, sucrose ester and the like.
The invention is different from the prior art: in the use process of the newly developed liquid medicine, all components in the liquid medicine are organic components, the evaporation process is that all components are evaporated compared with the existing stripping liquid with high reaction temperature, meanwhile, quaternary ammonium hydroxide adopted in the reaction process has certain loss in the stripping process of the photoresist, and the alkalinity change rate of the liquid medicine is only 0.3% -0.4%, so that the stripping speed and the stripping state of the photoresist by the liquid medicine are not greatly changed, in the continuous production of a production line, only new liquid needs to be periodically supplemented, and the monitoring and operation difficulty of the liquid medicine in the production process is greatly reduced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention can control the alkalinity change, so that the alkalinity change is in a very small stable range, which is beneficial to the continuous and effective operation of the stripping work; in addition, the invention can also slow down the corrosion process of copper and ensure that the Cu/Al circuit and the PV layer which need to be reserved during the regeneration of the panel are not damaged.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
All of the following materials are commercially available.
Example 1
5 parts of ethylene glycol, 50 parts of non-ionic surfactant and 44.5 parts of deionized water.
In the embodiment, the monoester-based quaternary ammonium hydroxide is prepared by firstly generating methylethanolamine ethosulfate quaternary ammonium salt from methylethanolamine, acetic acid and chloromethane, and then reacting the methylethanolamine ethosulfate quaternary ammonium salt with potassium hydroxide to obtain the corresponding methylethanolamine ethosulfate quaternary ammonium hydroxide.
Example 2
15 parts of ethylene glycol, 65 parts of non-ionic surfactant and 18.5 parts of deionized water.
Example 3
28 parts of ethylene glycol, 60 parts of non-ionic surfactant and 10 parts of deionized water.
Example 4
15 parts of propylene glycol, 65 parts of non-ionic surfactant and 18.5 parts of deionized water. In this embodiment, the diester-based quaternary ammonium hydroxide is obtained by reacting methyldiethanolamine, acetic acid and methyl chloride to generate methyldiethanolamine ethyl-based quaternary ammonium salt, and then reacting the methyldiethanolamine ethyl-based quaternary ammonium salt with potassium hydroxide.
Example 5
12 parts of (a) to (b),
15 parts of ethylene glycol, 55 parts of non-ionic surfactant, 2.0 parts of deionized water and 16 parts of deionized water.
Example 6
20 parts of (by weight), and mixing the components,
5 parts of ethylene glycol, 55 parts of glycol, 2.0 parts of nonionic surfactant and 16 parts of deionized water.
Example 7
10 parts of (a) to (b),
18 parts of ethylene glycol, 55 parts of non-ionic surfactant, 2.0 parts of deionized water and 16 parts of deionized water.
In order to further illustrate the beneficial effects of the invention, several sets of comparative experiments were carried out. The control groups were as follows:
comparative group 1:
15 parts of KOH, 65 parts of ethylene glycol, 1.5 parts of nonionic surfactant and 18.5 parts of deionized water.
The performance of the stripping liquid of the present invention was examined in examples 1 to 7 and comparative example 1. The experimental contents are as follows:
and (3) putting the substrate into a stripping solution at 78 ℃, testing the corrosion time of copper of the substrate and the evaporation speed of the stripping solution, and measuring the alkalinity change of the stripping solution after soaking for 12 h.
First, test of copper corrosion rate
TABLE 1
Second, alkalinity variation control experiment
The experimental contents are as follows:
TABLE 2
| Evaporation Rate (wt%/h) | Alkalinity change pH | |
| Example 1 | 2.12 | 0.40 |
| Example 2 | 2.05 | 0.36 |
| Example 3 | 2.05 | 0.32 |
| Example 4 | 2.0 | 0.33 |
| Example 5 | 1.9 | 0.32 |
| Example 6 | 2.0 | 0.35 |
| Example 7 | 1.8 | 0.32 |
| Comparative example 1 | 5.2 | 2.1 |
In conclusion, it can be seen that the stripping effect of examples 1 to 7 is better than that of comparative example 1, the change of the alkalinity of the present invention is small with the progress of the stripping process, the change is only 0.3 to 0.4 within 12 hours, and no corrosion to copper can be maintained within 2 hours, while the change of the alkalinity of the comparative example is 2.1 or more within 12 hours, and no corrosion to copper can be maintained within 0.5 hours, and over 0.5 hours, the corrosion to copper is obviously caused.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The stripping liquid for the photoresist is characterized by comprising 5-28% of ester quaternary ammonium hydroxide, 50-65% of water-soluble organic solvent, 0.5-2% of nonionic surfactant and the balance of deionized water by weight; the ester quaternary ammonium hydroxide is one or two of monoester quaternary ammonium hydroxide and diester quaternary ammonium hydroxide,
as shown in the formula I,
， R1and R3Are all selected from C1-C5 alkyl, R2Selected from C1-C5 alkyl or C1-C5 ester group, n is any integer of 1-5, R4Is an alkyl group.
2. The stripping solution for photoresist according to claim 1, characterized in that the ester quaternary ammonium hydroxide is 15-25% by weight.
3. The stripping solution for photoresist according to claim 1, characterized in that the water-soluble organic solvent is 55-60% by weight.
4. The stripping solution for photoresist according to claim 1, characterized in that the nonionic surfactant is 0.8-1.2% by weight.
5. The stripping solution for resist according to claim 1, characterized in that the monoester-based quaternary ammonium hydroxide is one of methylethanolamine carbomethoxy quaternary ammonium hydroxide, methylethanolamine ethylester quaternary ammonium hydroxide, methylethanolamine carbomethoxy quaternary ammonium hydroxide, methylethylethanolamine carbomethoxy quaternary ammonium hydroxide, methylethanolamine ethylester quaternary ammonium hydroxide, methylethylethanolamine ethylester quaternary ammonium hydroxide, methylpropanolamine carbomethoxy quaternary ammonium hydroxide and methylbutanolamine carbomethoxy quaternary ammonium hydroxide.
6. The stripping solution for photoresist according to claim 1, characterized in that diester quaternary ammonium hydroxide is one of methyldiethanolamine methylester quaternary ammonium hydroxide, methyldiethanolamine ethylester quaternary ammonium hydroxide and methyldiethanolamine propyl ester quaternary ammonium hydroxide.
7. The process for producing a stripping solution for resists according to any one of claims 1 to 6, characterized in that the quaternary ammonium hydroxide ester, the water-soluble organic solvent, the nonionic surfactant and the deionized water are uniformly mixed.
8. Use of the stripping solution for photoresist according to any one of claims 1 to 6 for stripping photoresist.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107966887A (en) * | 2017-11-24 | 2018-04-27 | 无锡南理工新能源电动车科技发展有限公司 | A kind of molybdenum aluminium photoresist stripper in transistor liquid crystal touch-screen |
| CN112764330B (en) * | 2021-01-08 | 2022-08-02 | 绵阳艾萨斯电子材料有限公司 | PFA photoresist regeneration stripping liquid and preparation method and application thereof |
| CN112947015A (en) * | 2021-02-08 | 2021-06-11 | 绵阳艾萨斯电子材料有限公司 | PR (photoresist) stripping liquid and application thereof in liquid crystal panel process regeneration |
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