CN101585662B - Etching liquid for flat panel display - Google Patents

Etching liquid for flat panel display Download PDF

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CN101585662B
CN101585662B CN2009100839345A CN200910083934A CN101585662B CN 101585662 B CN101585662 B CN 101585662B CN 2009100839345 A CN2009100839345 A CN 2009100839345A CN 200910083934 A CN200910083934 A CN 200910083934A CN 101585662 B CN101585662 B CN 101585662B
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etching liquid
etching
oxalic acid
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water
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CN101585662A (en
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冯卫文
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He Feimao rises Environmental Protection Technology Co., Ltd
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MIANYANG EXAX ELECTRONIC MATERIALS CO Ltd
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Abstract

The present invention discloses an etching liquid for the flat panel display. The etching liquid comprises oxalic acid, trifluoromethyl benzenesulfonic acid and water. The using amount of the oxalic acid is 1-10% of the total weight of the etching liquid. The using amount of the trifluoromethyl benzenesulfonic acid is 0.5-5% of the total weight of the etching liquid, and the balance is water. The invention provides the etching liquid for the flat panel display, which has the advantages of high efficiency, high etching precision and no pungent odour. The etching liquid is used for etching the ITO transparent conductive film. The adopted oxalic acid and the trifluoromethyl benzenesulfonic acid are organic acids. The compound composed of the two organic acids is not easily volatilized and hasexcellent wetting quality. When used as the ITO conductive film etching liquid, the etching liquid compound has the characteristics of excellent etching performance, no residue, less environmental po llution, etc.

Description

Etching liquid for flat panel display
Technical field
The present invention relates to a kind of etching liquid for flat panel display.
Background technology
In the flat pannel display field, comprise in plasma display (PDP), liquid-crystal display (LCD) and the organic electroluminescent preparation process such as (OLED), usually use tin indium oxide (ITO) as conducting film, because it is firmly hard that the ITO film has low-resistivity, high visible light transmissivity, rete, premium propertiess such as alkaline-resisting heat-resisting humidity.In preparation process,, need carry out etching to the nesa coating that ITO forms for obtaining the precise image of needed various pixels.
At present, the ITO etching method that is adopted in the flat pannel display field is mainly wet etching, and the common solution that adopts is various acidic solutions.As pointing out that in " liquid crystal and flat panel display " (press of Beijing University of Post ﹠ Telecommunication, 2007) book of Gao Hongjin, Dong Youmei chief editor what the ITO etching liquid adopted is the mixing solutions of hydrochloric acid and nitric acid, its proportioning is HCl: HNO 3: H 2O=1: 0.1: 1, under 40 ℃, its etch rate was 150nm/min; Having introduced the etching liquid that the ITO wet etching adopted in " manufacturing of thin film transistor LCD device, test in technical development " (China Machine Press, 2007) that Wang Dawei etc. writes is HCl+FeCl 3Or H 3PO 4+ HI etc.But continuous development along with technique of display, requirement to the etching speed of nesa coating is more and more higher, accuracy requirement to the conductive electrode that forms after the etching is also more and more meticulousr, and the requirement of the environmental pollution that irritating smell became that acidic substance are produced is also more and more stricter.In Japanese patent laid-open 5-102122 number, reported the acid etching liquid composition that constitutes by fluoric acid, nitric acid, acetic acid and water, can improve etching efficient, but acetic acid have must irritating smell.On this basis, the etching liquid composition that uses citric acid to replace acetic acid in the nitration mixture and form is disclosed for Japanese patent laid-open 10-130870 number, but because citric acid does not improve the effect of wettability, therefore the meticulous pattern edge shape of difficult acquisition causes the tractability of display pixel not enough.In Chinese patent CN1511338A, the etching liquid composition that a kind of use contains perfluoroalkyl phosphate cpd, oxalic acid and water has been proposed, use this etching liquid composition can precision good ito transparent electrode is carried out etching, and be difficult for producing residue, but this patent does not provide etching speed.In Chinese patent CN1253526C, proposed in oxalic acid to add one or more compound in poly-sulfoacid compound and the polyox-yethylene-polyoxypropylene block copolymer improving the foaminess of this etching liquid, and the residue that improves after the etching produces.In addition, Chinese patent CN101033549A and Chinese patent CN101003736A have also proposed some novel etching liquid compositions.
Summary of the invention
The purpose of this invention is to provide a kind of etching liquid for flat panel display.
Etching liquid for flat panel display provided by the invention comprises oxalic acid, trifluoromethyl Phenylsulfonic acid and water.
This etching liquid can only be made up of above-mentioned three kinds of components.
The present invention uses oxalic acid, not only has acidity, also has certain reductibility and complex ability, can effectively suppress the overetch of ito thin film in the etching process, the generation of inhibited oxidation thing residue.In the present invention, the usage quantity of oxalic acid is 1~10% weight ratio, and is preferred 1~5%, more preferably 2~5%.Can cause etching speed low when being lower than 1% weight ratio, etching is insufficient, and the figure burr is more; Oxalic acid is separated out easily when being higher than 10% weight ratio, is unfavorable for transportation and storage.
Among the present invention, the trifluoromethyl Phenylsulfonic acid helps improving etching speed because the existence of trifluoromethyl is not only by force acid, and good to the wetting property of ito glass.The weight ratio of trifluoromethyl Phenylsulfonic acid is 0.5~5%, and is preferred 1~5%, more preferably 1~3%.When being lower than 0.5% weight ratio, etching effect is not good, has the film slag to produce easily; When being higher than 5% weight ratio, can cause etching excessive, the pattern edge burr increases.
In addition, generally, the equal water of developing solution is as solvent, be characterized in hypotoxicity, do not have flammable, liquid waste disposal is easy and with low cost.
The method of the above-mentioned etching liquid for flat panel display of preparation provided by the invention, be with oxalic acid, trifluoromethyl Phenylsulfonic acid and water at 20~30 ℃ of mixings, obtain described etching liquid.
Etching liquid provided by the invention is the application in the tin indium oxide ITO conductive film in the etching flat pannel display, also belongs to protection scope of the present invention.
The invention provides the etching liquid for flat panel display of a kind of efficient, high etching precision, non-stimulated smell.This etching liquid is used for etching ITO nesa coating, and selected oxalic acid of this etching liquid and trifluoromethyl Phenylsulfonic acid are organic acid.Not volatile by the mixture that this two classes organic acid is formed, wetting property is good, when being used for ITO conducting film etching liquid, this etching liquid constituent has characteristics such as good, the no residue of etching performance, environmental pollution be little.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Among the present invention, etching liquid is estimated according to following method:
One, etching effect:
With the glass substrate is example, according to ordinary method glass substrate is carried out following processing successively, can obtain required image on glass substrate: 1) clean, dry; 2) with Freehand software design figure, the microchannel graphic width is designed to 80um, and it is standby that the laser high resolution is printed mask; 3) this glass substrate is placed the equal glue machine of KW-4A type, evenly be coated with one deck photoresist material with the even glue speed of 3500r/min; 4) it is stand-by glue-coated sheet glass oven dry cooling to be caused room temperature.Mask is placed on the sheet glass of optical cement protection, with the ultraviolet source exposure 25sec of 500W; 5) glass substrate that scribbles photoresist material after will exposing drops into to develop in the developing solution to the exposed portion optical cement and comes off fully, and distilled water flushing after drying up, obtains required image; 6) glass after will developing is put into substantially and is carried out etching in the etching liquid, obtains required electrode pattern after the ito glass etching that will not have photoresist material to cover.
Whether the pattern edge of observing on the substrate with 50 power microscopes after disposing is smooth behind over etching.
Zero: it is clean to be expressed as pattern edge, smooth no burr
*: it is unclean to be expressed as pattern edge, unfairness and burr are arranged
Two, residue:
Whether the figure position of observing after the aforesaid substrate etching is finished with 250 power microscopes has residue.
Zero: be expressed as no residue,
△: level of residue is few
*: level of residue is many
Embodiment 1,
With the glass substrate is example, according to ordinary method the ito glass substrate is carried out following processing successively, can obtain required image on glass substrate:
1) cleans, dries;
2) with Freehand software design figure, the microchannel graphic width is designed to 80um, and it is standby that the laser high resolution is printed mask;
3) this glass substrate sheet is placed the equal glue machine of KW-4A type, evenly be coated with one deck photoresist material with the even glue speed of 3500r/min;
4) it is stand-by glue-coated sheet glass oven dry cooling to be caused room temperature.Mask is placed on the sheet glass of optical cement protection, with the ultraviolet source exposure 25sec of 500W;
5) glass substrate that scribbles photoresist material after will exposing drops into to develop in the developing solution to the exposed portion optical cement and comes off fully, and distilled water flushing after drying up, obtains required image;
6) glass after will developing is put into substantially and is carried out etching in the etching liquid, and the ratio of etching liquid is an oxalic acid: the trifluoromethyl Phenylsulfonic acid: water=5: 1: 94.
In order to obtain the ratio of component of an optimum, select the etching liquid of Different Weight ratio to compare, shown in comparing embodiment.The preparation method of embodiment 2~6 and comparing embodiment 1~10 and the foregoing description 1 are identical, only the proportion of composing of the 6th step etching liquid are replaced according to table 1, and the gained result is as shown in table 2 after the etching.Embodiment 1~6 resulting etching liquid constituent all has no irritating odor, and is a kind of eco-friendly etching liquid.
As known from Table 2, the weight ratio of oxalic acid is preferably 1~5%, and most preferably 2~5%; The weight ratio of trifluoromethyl Phenylsulfonic acid is preferred 1~5%, and more preferably 1~3%.
Table 1, etching liquid ratio of component (weight ratio)
Figure G2009100839345D00031
Figure G2009100839345D00041
Table 2, each embodiment and comparative example experimental result
Figure G2009100839345D00042
Figure G2009100839345D00051

Claims (7)

1. etching liquid for flat panel display is made up of oxalic acid, trifluoromethyl Phenylsulfonic acid and water;
Described oxalic acid accounts for 1~10% of described etching liquid gross weight, and described trifluoromethyl Phenylsulfonic acid accounts for 0.5~5% of described etching liquid gross weight, and surplus is a water;
Described etching liquid is used for etching flat pannel display tin indium oxide ITO conductive film.
2. etching liquid according to claim 1 is characterized in that: described oxalic acid accounts for the 1-5% of described etching liquid gross weight; Described trifluoromethyl Phenylsulfonic acid accounts for 1~5% of described etching liquid gross weight.
3. etching liquid according to claim 2 is characterized in that: described oxalic acid accounts for 2~5% of described etching liquid gross weight; Described trifluoromethyl Phenylsulfonic acid accounts for 1~3% of described etching liquid gross weight.
4. a method for preparing the described etching liquid for flat panel display of claim 1 is with oxalic acid, trifluoromethyl Phenylsulfonic acid and water mixing, obtains described etching liquid;
Described oxalic acid accounts for 1~10% of described etching liquid gross weight; Described trifluoromethyl Phenylsulfonic acid accounts for 0.5~5% of described etching liquid gross weight; Surplus is a water;
The temperature of described mixing is 20-30 ℃.
5. method according to claim 4 is characterized in that: described oxalic acid accounts for the 1-5% of described etching liquid gross weight; Described trifluoromethyl Phenylsulfonic acid accounts for 1~5% of described etching liquid gross weight; Surplus is a water.
6. method according to claim 5 is characterized in that: described oxalic acid accounts for 2~5% of described etching liquid gross weight; Described trifluoromethyl Phenylsulfonic acid accounts for 1~3% of described etching liquid gross weight; Surplus is a water.
7. the described etching liquid of claim 1 application in the tin indium oxide ITO conductive film in the etching flat pannel display.
CN2009100839345A 2009-05-11 2009-05-11 Etching liquid for flat panel display Active CN101585662B (en)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880129A (en) * 2010-05-28 2010-11-10 合肥茂丰电子科技有限公司 Etching liquid for thinning glass substrate and preparation method and application thereof
CN102277573B (en) * 2011-08-19 2013-02-06 绵阳艾萨斯电子材料有限公司 Chromium etchant for liquid crystal display screens and preparation method thereof
CN102382657B (en) * 2011-10-11 2013-08-07 绵阳艾萨斯电子材料有限公司 Etching liquid for transparent conducting film and preparation method thereof
CN103755147B (en) * 2014-01-14 2016-03-30 清华大学 Etching solution and preparation method thereof and application
CN105087008B (en) * 2014-04-30 2017-09-26 重庆市中光电显示技术有限公司 The etching liquid etched for ito film
CN112048303A (en) * 2020-08-27 2020-12-08 福建天甫电子材料有限公司 Preparation process of electronic grade oxalic acid etching liquid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1511338A (en) * 2002-03-25 2004-07-07 长濑化成株式会社 Etching liquid composition
CN101003736A (en) * 2006-01-17 2007-07-25 厦门火炬福大显示技术有限公司 Etching liquid for preparing IT0 transparent electrodes in flat panel display
CN101245462A (en) * 2007-02-13 2008-08-20 峻科技有限公司 Etching liquid composition and etching method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1511338A (en) * 2002-03-25 2004-07-07 长濑化成株式会社 Etching liquid composition
CN101003736A (en) * 2006-01-17 2007-07-25 厦门火炬福大显示技术有限公司 Etching liquid for preparing IT0 transparent electrodes in flat panel display
CN101245462A (en) * 2007-02-13 2008-08-20 峻科技有限公司 Etching liquid composition and etching method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP特开2007-214190A 2007.08.23

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Patentee before: Mianyang Exax Electronic Materials Co., Ltd.