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WO2002007200A1 - Etching compositions - Google Patents

Etching compositions Download PDF

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Publication number
WO2002007200A1
WO2002007200A1 PCT/JP2001/006048 JP0106048W WO0207200A1 WO 2002007200 A1 WO2002007200 A1 WO 2002007200A1 JP 0106048 W JP0106048 W JP 0106048W WO 0207200 A1 WO0207200 A1 WO 0207200A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
etching
aqueous solution
weight
resist
Prior art date
Application number
PCT/JP2001/006048
Other languages
French (fr)
Japanese (ja)
Inventor
Satoshi Nanba
Taketo Maruyama
Hisaki Abe
Tetsuo Aoyama
Original Assignee
Mitsubishi Gas Chemical Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2000214232A external-priority patent/JP2002033304A/en
Priority claimed from JP2000214206A external-priority patent/JP2002033303A/en
Application filed by Mitsubishi Gas Chemical Company, Inc. filed Critical Mitsubishi Gas Chemical Company, Inc.
Priority to KR10-2003-7000347A priority Critical patent/KR20030021249A/en
Publication of WO2002007200A1 publication Critical patent/WO2002007200A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to an etching composition, and more particularly to an etching composition capable of etching a transparent conductive film under mild conditions and generating no residue.
  • Akita
  • Transparent conductive films such as ITO (indium monotin oxide) film are antistatic films
  • LCDs liquid crystal displays
  • transparent conductive films such as ITO are used as display electrodes for pixels, and are produced by etching using photolithography.
  • ferric chloride / hydrochloric acid aqueous solution iodic acid aqueous solution, phosphoric acid aqueous solution, hydrochloric acid / nitric acid aqueous solution (aqua regia) and the like have been used as an etching agent for the transparent conductive film such as the polycrystalline ITO.
  • the above-mentioned wet etching agent for the transparent conductive film, etc. corrosion to A1 etc. occurs, and selective etching proceeds from the grain boundaries, so that it is difficult to perform buttering with high accuracy.
  • An object of the present invention is to provide, as described above in the prior art, no etching residue at the time of wet etching of a transparent conductive film using an oxalic acid aqueous solution, and to perform etching under a mild condition.
  • An object of the present invention is to provide an etching agent capable of performing the following.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a phenolic hydroxyl group, or oxalic acid and a nitrogen-containing carboxylic acid. It has been found that an aqueous solution containing a salt of a nitrogen-containing carboxylic acid can be etched under mild conditions when etching the transparent conductive film, and that no residue is generated, and the present invention has been completed. I came to.
  • the present invention relates to an etching composition
  • an etching composition comprising an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a fininolic hydroxyl group, and oxalic acid and a salt of a nitrogen-containing carboxylic acid and / or a salt of a nitrogen-containing carboxylic acid. It is intended to provide an etching composition characterized by comprising an aqueous solution.
  • BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows the state after forming an insulating film of SiN on a glass substrate, further forming an amorphous ITO film, applying a resist on the amorphous ITO film, and developing. ⁇ in the figure.
  • FIG. 2 is a state diagram in which the resist has been stripped after etching the substrate of FIG. 1 with a conventional etchant.
  • concentration of oxalic acid used in the present invention 0. 0 1-1 0 weight 0/0 are preferred. 0. 0 1 wt% slower etching rate is less, and in 1 0 weight 0/6 or more, the etch ing rate does not improve, not advisable.
  • aromatic hydrocarbon compound having a phenolic hydroxyl group examples include the compounds described below. Any compound having a phenolic hydroxyl group directly bonded to an aromatic hydrocarbon in the molecule may be used. It is not particularly limited to these.
  • aromatic hydrocarbon compounds having only one hydroxyl group phenol, cresol, ethyl phenol, t-ethyl phenol, t-butyl phenol, methoxy phenol, salicyl alcohol, ethyl phenol, amino phenol
  • aromatic hydrocarbon compounds having two or more hydroxyl groups catechol, resorcinol, hydroquinone, 4-methylpyrocatechol, 2-methylhydroquinone, pyrogallol, 1,2,5-benzenetriol, 1 , 3,5-benzenetriol, 2-methylphloroglucinol, 2,4,6_phloroglucinol,
  • hydroxybenzophenones dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,6-dihydroxy-14-methoxybenzophenone, 2,2 ', 5,6, -tetra Examples include hydroxybenzophenone, 2,3,4,4,6,-pentahydroxybenzophenone.
  • hydroxybenzanilides include 0-hydroxybenzanilide.
  • hydroxyanil examples include glyoxalbis (2-hydroxyanyl).
  • hydroxybiphenyls examples include biphenyldiol, biphenyltriol, and biphenyltetraol.
  • Hydroxyquinones and derivatives thereof include 2,3-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, dihydroxyanthraquinone, 1,2-dihydroxy-13- (aminomethyl) anthraquinone N, N'-monoacetic acid [commonly known as Rizarin complexone], trihydroxyanthra Quinone and the like.
  • diphenyl or triphenylalkane derivatives diphenylmethane-2,2, -diol, 4,4 ', 4', triphenylmethanetriol, 4, 'dihydroxyfuchsone, 4,4' Dihydroxy-13-methylfuchsone, pyrocatechol violet [commonly known as PV], and the like.
  • Phenol derivatives of alkylamines such as ethylenediaminediolohydroxyphenylacetic acid [commonly known as EDDHA], N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid [commonly known as HBED], etc. are mentioned.
  • Alkenyl ether phenol derivatives include 3,3-ethylenedioxydiphenol.
  • Phenols having an azo group and derivatives thereof include 4,4′-bis (3,4-dihydroxyphenylazo) -1,2,2-stilbene disulfonic acid 2 ammonium [commonly known as stilbazo], 2 , 8-Dihydroxy-1- (8-hydroxy-3,6-disulfo-1-naphthylazo) -1,3,6-naphthylenedisulfonic acid, 0-0, dihydroxyazobenzene, 2-hydroxy-11 (2- Hydroxy-5-methylphenylazo) -14-naphthylenesulfonic acid [comcarmagite], chlorohydroxyphenylazinaphthol, 1,2,1-dihydroxy-6-nitro-2-nitro-1,2-nazonafrene -Sulfonic acid [commonly known as Eriochrome Black T], 2-hydroxy-11 (2-hydroxy-14-sulfo-11-naphthylazo) -1,3,6-naphthalenedisulfonic acid,
  • Heterocyclic compounds having a hydroxyl group and derivatives thereof include 8-quinolinol, 2-methyl-18-quinolinol, quinolinediol, 11- (2-pyridylazo) -12-naphthol, 2- Amino-4,6,7-pteridinetriol, 5,7,3 ', 4'-tetrahydroxyflavone [common name: luteolin], 3,3-bis [N, N-bis (carboxymethyl) aminomethyl] fluorescein [commonly known
  • Examples of the alicyclic compound having a hydroxyl group and derivatives thereof include cyclopentanol, croconic acid, cyclohexanol, cyclohexanediol, dihydroxydiquinol, trobolone, and 6- ⁇ -propylpropyltroborone.
  • the aromatic hydrocarbon compound having a phenolic hydroxyl group is preferably an aromatic hydrocarbon compound having two or more phenolic hydroxyl groups.
  • the above compounds may be used alone or in combination of two or more kinds, and the preferable concentration is 0.001 to 5% by weight in the whole etching composition.
  • the concentration of the aromatic hydrocarbon compound having Knoll hydroxyl group is zero. 0 0 0 1 weight 0/0 or less, at the time of etching, residue occurs at 5 weight 0/0 above, the ITO film E It is not preferable because the cutting speed is reduced or the dissolution is not sufficient.
  • nitrogen-containing carboxylic acid and its salt include those described below, but are not particularly limited thereto.
  • nitrogen-containing carboxylic acid having one carboxyl group and salts thereof examples include aminoacetic acid, dihydroxyethylglycine, and the like, and salts thereof.
  • Examples of the nitrogen-containing carboxylic acid having two kelpoxyl groups and salts thereof include imino diacetic acid, hydroxyethylimino diacetic acid, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, and salts thereof.
  • Examples of the nitrogen-containing carboxylic acid having three carboxyl groups and salts thereof include triacetic acid triacetate, hydroxyethylethylenediamine triacetic acid, tripropionic acid 3-propionic acid, and salts thereof.
  • nitrogen-containing carboxylic acids having four carboxyl groups and salts thereof include ethylenediamine 4 acetic acid, trans-1,2-cyclohexanediamine N, N, N, N,, N-tetraacetic acid, diaminopropanol 4 Acetic acid, glycol ether terdiamine tetraacetic acid, hexamethylene diamine mono N, N, N ', N'-tetraacetic acid, diaminopropane tetraacetic acid, and the like, and salts thereof.
  • Examples of the nitrogen-containing carboxylic acid having five carboxyl groups and salts thereof include diethylenetriaminepentaacetic acid and the like, and salts thereof.
  • Examples of the nitrogen-containing carboxylic acid having six or more carboxyl groups and salts thereof include triethylenetetramine hexaacetic acid and the like, and salts thereof.
  • Other similar compounds include amine compounds capable of forming a complex such as trienolamine and salts thereof.
  • the nitrogen-containing carboxylic acids and salts thereof may be used alone or in combination of two or more.
  • the preferred concentration is 0.0001 to 5% by weight.
  • Nitrogen-containing cal As the boric acid or its salt, those having four or less carboxyl groups are preferred.
  • the nitrogen-containing carboxylic acids and concentration of the salt is 000 1 wt 0/0 hereinafter 0., during etching, residue occurs, the 5 weight 0/0 or more, E Tsuchingu rate of I TO It is not preferable because it decreases or does not dissolve sufficiently.
  • the etching composition of the present invention is used according to an ordinary method, but the operating temperature is from normal temperature to 90 ° C., and the operating time is about 0.1 to 30 minutes.
  • the present invention is suitably used for wet etching of transparent conductive films such as IZO (indium monozinc oxide) and various semiconductors, in addition to amorphous ITO.
  • transparent conductive films such as IZO (indium monozinc oxide) and various semiconductors, in addition to amorphous ITO.
  • an insulating film Si 2 is formed on a glass substrate 1, an amorphous ITO 3 is further formed, and a resist is formed on the amorphous ITO film.
  • a cleaning solution containing 3.4% by weight of oxalic acid and 0.1% by weight of, 3-dihydroxybenzoic acid was used at 40 ° C for 2 minutes.
  • the resist 4 was stripped with a basic resist stripper, washed with water, and the surface was observed with a dried SEM (electron microscope). As a result, the amorphous ITO was etched well and the residue was removed. Was not observed at all.
  • Example 1 The substrate used in Example 1 was etched at 40 ° (: for 2 minutes with a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid, washed with water, and dried. After the resist 4 was peeled off with the liquid, the resist 4 was washed 7_ As a result of observation of S, the amorphous I ⁇ was etched, but a number of residues 5 were observed as shown in Fig. 1. Comparative Example Two The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning agent which was an aqueous solution containing 2,3-dihydroxybenzoic acid at a weight of 0.1 / 0 / o. After the resist 4 was stripped with a basic resist stripper, the resist 4 was washed 7 j and dried. As a result of SEM observation, amorphous IT ⁇ was hardly etched.
  • Example 1 The substrate used in Example 1 was washed at a temperature of 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.01% by weight of 2,3-dihydroxybenzaldehyde. After etching and washing with water, the resist 4 was stripped off with a basic resist stripping solution, washed 7j, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
  • Example 1 The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.3% by weight of 2,3-dihydroxybenzaldehyde. After washing with 7 7, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
  • a cleaning solution was an aqueous solution containing 3.4% by weight of oxalic acid and 0.3% by weight of 2,3-dihydroxybenzaldehyde.
  • oxalate 3.4 wt 0/0, 0.0 1 wt% of 2, 3 using the cleaning solution is an aqueous solution containing dihydroxybenzoic acid
  • the substrate used in Example 1 40 ° C. 2 minutes etching
  • the resist 4 was stripped off with a basic resist stripping solution, washed with water, and dried.
  • the amorphous ITO was etched well and no residue was observed.
  • oxalate 1.0 wt 0/0, 2 of 0.1 weight 0/0, 3-dihydroxybenzoic acid with a cleaning solution is an aqueous solution and containing not, the substrate used in Example 1 40 ° C. 4 min Etching was performed, and after 7 washes, the resist 4 was further stripped off with a basic resist stripping solution, followed by 7K washing and drying. As a result of SEM observation, the amorphous ITO was etched well and no residue was observed.
  • Example 1 The substrate used in Example 1 was subjected to 4 O; etching for 2 minutes using a cleaning solution that was an aqueous solution containing 5.5% by weight of oxalic acid and 0.1% by weight of 2,3-dihydroxybenzoic acid. After washing with zK, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
  • Acetic acid 5.5 weight 0/0, 2 of 0.1 weight 0/0, 3-dihydroxybenzoic acid with a cleaning solution is an aqueous solution you containing, Example 1 40 ° C. 2 minutes substrates used in After etching, washing with water, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SE.M observation, the amorphous IT ⁇ was hardly etched.
  • Example 1 The substrate used in Example 1 was etched at 40 ° (:, 2 minutes) using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of dihydroxy. After washing, the resist 4 was stripped off with a basic resist stripping solution, washed with water, and dried.As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed. Comparative Example 4
  • the cleaning agent is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0 / o
  • the substrate used in Example 1 performs 4 O. 2 minutes etching, washed with water, and et basic resist stripping After the resist was peeled off with the liquid, it was washed with water and dried. As a result of SEM observation, the amorphous ITO was hardly etched.
  • Example 1 The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of hydroxyethyliminodiacetic acid. After washing with 7_, the resist was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed.
  • oxalate 3.4 wt 0/0, 0.2 weight 0/0 of the two tri-port 3 using a cleaning solution is an aqueous solution containing acetic acid, 4 0 ° C the substrate used in Example 1, 2 minute etch After washing with water, the resist was stripped off with a basic resist stripping solution, then washed with 7 and dried. As a result of SEM observation, the amorphous ITO was etched well and no residue was observed.
  • Example 1 The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of ethylenediaminetetraacetic acid. After washing with water, the resist was stripped with a basic resist stripper, washed with water, and dried. As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed.
  • Example 1 The substrate used in Example 1 was etched at 40 ° C for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 2.0% by weight of dihydroxyethylglycine. After washing, the resist was stripped off with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
  • oxalic acid with a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/0, 4 0 ° the substrate used in Example 1 (:, 2 min Etsu quenching After washing with 7j, the resist was stripped with a basic resist stripping solution, washed with water and dried, and as a result of S ⁇ Observation, the amorphous I ⁇ 0 was well etched and no residue was observed.
  • a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/0, 4 0 ° the substrate used in Example 1 (:, 2 min Etsu quenching After washing with 7j, the resist was stripped with a basic resist stripping solution, washed with water and dried, and as a result of S ⁇ Observation, the amorphous I ⁇ 0 was well etched and no residue was observed.
  • a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/0,
  • Example 1 The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 5.5% by weight of oxalic acid and 0.2% by weight of dihydroxyethylglycine. After the resist was stripped with a basic resist stripper, the resist was washed 7 and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
  • Acetic 5. and 5 wt%, using a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/6, the substrate used in Example 1 carried out 40 ° C. 2 minutes Etsuchin grayed, 7j After washing, the resist was stripped off with a basic resist stripping solution, washed 7j, and dried. As a result of SEM observation, is amorphous ITO almost completely etched? Tsuta Industrial applicability
  • the transparent conductive film can be etched under mild conditions, and no residue is generated.

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Abstract

An etching composition which comprises an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a phenolic hydroxyl group; and an etching composition characterized by being an aqueous solution containing oxalic acid and a nitrogenous carboxylic acid and/or salt thereof. With the etchants, etching can be conducted under mild conditions without generating any etching residue.

Description

エッチング用組成物  Etching composition
技術分野 Technical field
本発明は、 エッチング用組成物に関し、特に、 温和な条件下で透明導電膜のェ ッチングが出来、 且つ残渣物が全く発生しないエツチング用組成物特に関するも のである。 明 田  The present invention relates to an etching composition, and more particularly to an etching composition capable of etching a transparent conductive film under mild conditions and generating no residue. Akita
背景技術 Background art
I TO (インジウム一錫酸化物） 膜をはじめとする透明導電膜は、 帯電防止膜 Transparent conductive films such as ITO (indium monotin oxide) film are antistatic films
、 熱反射膜、 光電変換素子や各種フラッ トパネルディスプレイの透明電極などの 電子デバイス分野に広く用いられてきた。 特に、 最近では、 ノート PCや小型 T V、 携帯用情報端末などの普及とともに、液晶ディスプレー （LCD) での需要 が增加している。 I TO等の透明導電膜は、 フラッ トパネルディスプレイの分野 においては、 画素の表示電極として使用され、 フォトリソグラフィ一のエツチン グにより作成される。 It has been widely used in the field of electronic devices such as heat reflection films, photoelectric conversion elements, and transparent electrodes for various flat panel displays. In particular, with the spread of notebook PCs, small TVs, and portable information terminals, demand for liquid crystal displays (LCDs) has recently increased. In the field of flat panel displays, transparent conductive films such as ITO are used as display electrodes for pixels, and are produced by etching using photolithography.
しかしながら、 液晶ディスプレイ （LCD) 、特に TFT— LCDの分野にお いては、 従来、 多結晶 I TOが使用されてきたが、基板サイズが大型化するほど 、 多結晶 I TOは均一化が難しくなつてきている。 また、 上記の表示電極の形成 方法としては、 透明導電膜上に、 フォトレジストを塗布し、露光、現像後、 フォ トレジストをマスクとしてエッチング剤を用いて、 エッチング後、 残存するフォ トレジストを剥離して形成される。  However, in the field of liquid crystal displays (LCDs), especially TFT-LCDs, polycrystalline ITOs have conventionally been used. However, as the substrate size increases, it becomes more difficult to achieve uniform polycrystalline ITOs. Is coming. In addition, as a method of forming the above display electrode, a photoresist is coated on a transparent conductive film, and after exposure and development, the remaining photoresist is removed after etching using an etching agent with the photoresist as a mask. Formed.
従来、 上記多結晶 I TO等の透明導電膜のエッチング剤として、塩化第二鉄/ 塩酸水溶液、 ヨウ素酸水溶液、 リン酸水溶液、 塩酸/硝酸水溶液 （王水） 等が用 いられてきた。 上記透明導電膜等のゥヱットエッチング剤は、 バタニーングの際 に A 1等への腐食が起こり、 また粒界から選択的エッチングが進行するため、 加 ェ精度良くバタ二一ングすることも困難である。 Conventionally, ferric chloride / hydrochloric acid aqueous solution, iodic acid aqueous solution, phosphoric acid aqueous solution, hydrochloric acid / nitric acid aqueous solution (aqua regia) and the like have been used as an etching agent for the transparent conductive film such as the polycrystalline ITO. The above-mentioned wet etching agent for the transparent conductive film, etc. In addition, corrosion to A1 etc. occurs, and selective etching proceeds from the grain boundaries, so that it is difficult to perform buttering with high accuracy.
以上の理由により、基板サイズの大型化、 T F Tパネルの大型化、 高精細化、 配線の A 1化などに伴つて、 画素表示電極として加工精度良く、 エツチングが可 能なエッチング剤の要求が高まっている。 これらの問題を解決するために、 最近 非晶質 I T 0を使用し、 弱酸、特にシュゥ酸水溶液で非晶質 I T 0をウエットェ ッチングする方法が提唱されている。  For the above reasons, as the size of the substrate increases, the size of the TFT panel increases, the resolution increases, and the wiring becomes A1, the demand for an etching agent that can be etched with high processing accuracy as a pixel display electrode is increasing. ing. In order to solve these problems, a method of using amorphous I T0 and wet-etching it with a weak acid, particularly oxalic acid aqueous solution, has recently been proposed.
しかしながら、 シユウ酸水溶液を使用し、非晶質 I T Oをゥヱットエッチング した際に、 エッチング残渣が発生する問題があり、 このエッチング残渣を発生し ないエッチング剤が望まれていた。 発明の開示  However, when wet etching of amorphous ITO using an aqueous solution of oxalic acid, there is a problem that an etching residue is generated, and an etchant that does not generate this etching residue has been desired. Disclosure of the invention
本発明の目的は、 従来技術における上記の如き、透明導電膜のシユウ酸水溶液 を用いたゥヱットエッチングの際に、 エッチング残渣を全く発生せず、 且つ、 温 和な条件下で、 エツチングが行えるエツチング剤を提供することにある。  SUMMARY OF THE INVENTION An object of the present invention is to provide, as described above in the prior art, no etching residue at the time of wet etching of a transparent conductive film using an oxalic acid aqueous solution, and to perform etching under a mild condition. An object of the present invention is to provide an etching agent capable of performing the following.
本発明者等は、 上記の問題を解決すべく鋭意検討を行った結果、 シユウ酸とフ エノ一ル性水酸基を有する芳香族炭化水素化合物を含有する水溶液、 もしくはシ ユウ酸と窒素含有カルボン酸および/または窒素含有カルボン酸の塩を含有する 水溶液が、透明導電膜のエッチングの際、温和な条件下でエッチングが出来、 且 っ残渣物が全く発生しない事を見い出し、 ここに本発明を完成するに至った。 すなわち、 本発明は、 シユウ酸とフニノール性水酸基を有する芳香族炭化水素 化合物とを含有する水溶液からなるエツチング用組成物、 並びにシユウ酸と窒素 含有カルボン酸および/または窒素含有カルボン酸の塩とを含有する水溶液であ ることを特徴とするエツチング用組成物を提供するものである。 図面の簡単な説明 図 1は、 ガラス基板上に、絶縁膜である S i Nを成膜し、 さらに非晶質 I T O を成膜し、 該非晶質 I T O膜上にレジストを塗布し、 現像を行った後の状態図で ¾ 。 The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a phenolic hydroxyl group, or oxalic acid and a nitrogen-containing carboxylic acid. It has been found that an aqueous solution containing a salt of a nitrogen-containing carboxylic acid can be etched under mild conditions when etching the transparent conductive film, and that no residue is generated, and the present invention has been completed. I came to. That is, the present invention relates to an etching composition comprising an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a fininolic hydroxyl group, and oxalic acid and a salt of a nitrogen-containing carboxylic acid and / or a salt of a nitrogen-containing carboxylic acid. It is intended to provide an etching composition characterized by comprising an aqueous solution. BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows the state after forming an insulating film of SiN on a glass substrate, further forming an amorphous ITO film, applying a resist on the amorphous ITO film, and developing.図 in the figure.
図 2は、 従来のエッチング液で、 図 1の基板をエッチング後、 レジストを剥離 した状態図である。 発明を実施するための最良の形態  FIG. 2 is a state diagram in which the resist has been stripped after etching the substrate of FIG. 1 with a conventional etchant. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明を詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明に使用されるシユウ酸の濃度は、 0 . 0 1〜 1 0重量0 /0が好ましい。 0 . 0 1重量％以下ではエッチング速度が遅く、 また 1 0重量0 /6以上では、 エッチ ング速度は向上せず、 得策ではない。 The concentration of oxalic acid used in the present invention, 0. 0 1-1 0 weight 0/0 are preferred. 0. 0 1 wt% slower etching rate is less, and in 1 0 weight 0/6 or more, the etch ing rate does not improve, not advisable.
フヱノール性水酸基を有する芳香族炭化水素化合物として、 具体的には、 以下 に記載のものが挙げられるが、 分子中に芳香族炭化水素に直接結合したフエノー ル性の水酸基を直接結合した化合物であれば、 特にこれらに限定されるものでは ない。  Specific examples of the aromatic hydrocarbon compound having a phenolic hydroxyl group include the compounds described below. Any compound having a phenolic hydroxyl group directly bonded to an aromatic hydrocarbon in the molecule may be used. It is not particularly limited to these.
( 1 ) 水酸基を 1つのみ有する芳香族炭化水素化合物として、 フエノール、 クレ ゾ一ル、 ェチルフエノール、 t一ェチルフエノール、 t一ブチルフエノール、 メ トキシフエノ一ル、 サリチルアルコール、 クロ口フエノール、 ァミノフエノール (1) As aromatic hydrocarbon compounds having only one hydroxyl group, phenol, cresol, ethyl phenol, t-ethyl phenol, t-butyl phenol, methoxy phenol, salicyl alcohol, ethyl phenol, amino phenol
、 アミノクレゾ一ル、 アミ ドール、 p— ( 2—アミノエチル） フヱノール、 サリ チル酸、 o—サリチルァニリ ド、 ナフトール、 ナフトールスルホン酸、 7—アミ ノ一 4—ヒドロキシ一 2—ナフタレンジスルホン酸などが挙げられる。 , Aminocresol, amidole, p- (2-aminoethyl) phenol, salicylic acid, o-salicylanilide, naphthol, naphtholsulfonic acid, 7-amino-4-hydroxy-12-naphthalenedisulfonic acid, etc. Can be
( 2 ) 水酸基を 2つ以上有する芳香族炭化水素化合物として、 カテコール、 レゾ ルシノール、 ヒドロキノン、 4—メチルピロカテコール、 2—メチルヒドロキノ ン、 ピロガロール、 1 , 2， 5—ベンゼントリオ一ル、 1， 3， 5—ベンゼン卜 リオ一ル、 2—メチルフロログルシノ一ル、 2， 4， 6 _フロログルシノール、 (2) As aromatic hydrocarbon compounds having two or more hydroxyl groups, catechol, resorcinol, hydroquinone, 4-methylpyrocatechol, 2-methylhydroquinone, pyrogallol, 1,2,5-benzenetriol, 1 , 3,5-benzenetriol, 2-methylphloroglucinol, 2,4,6_phloroglucinol,
1 , 2 , 3， 5—ベンゼンテトラオール、 ベンゼンへキサオール、 タイロン、 ァ ミノレゾルシノール、 ジヒドロキシゲイ皮酸、 2， 3—ジヒドロキシベンズアル デヒド、 2， 4ージヒドロキシベンズアルデヒド、 2， 5—ジヒドロキシベンズ アルデヒド、 2， 6—ジヒドロキシベンズアルデヒド、 3, 4—ジヒドロキシべ ンズアルデヒド、 3， 5—ジヒドロキシベンズアルデヒド、 2， 3—ジヒドロキ シ安息香酸、 2， 4—ジヒドロキシ安息香酸、 1, 5—ジヒドロキシ安息香酸、 2, 6—ジヒドロキシ安息香酸、 3, 4—ジヒドロキシ安息香酸、 3， 5—ジヒ ドロキシ安息香酸、 ジヒドロキシァセトフヱノン、 没食子酸、 2, 3， 4—トリ ヒドロキシ安息香酸、 2， 4ージヒドロキシー6—メチル安息香酸、 ナフ夕レン ジオール、 ナフタレントリオール、 二ト口ナフトール、 ナフタレンテトラオ一ル 、 ビナフチルジオール、 4, 5—ジヒドロキシ _ 2， 7ナフタレンジスルホン酸 、 1 , 8—ジヒドロキシー3， 6—ナフタレンジスルホン酸、 ジヒドロキシベン ゾトリアゾール、 1 , 1、 3—アンドラセントリオールなどが挙げられる。1,2,3,5-benzentetraol, benzenehexaol, tyrone, α Minoresorcinol, dihydroxy gay cinnamate, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3, 5-dihydroxybenzaldehyde, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 1,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5- Dihydroxybenzoic acid, dihydroxyacetophenone, gallic acid, 2,3,4-trihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, naphthylene diol, naphthalenetriol, naphthol naphthol, naphthalene tetra Ol, binaphthyldiol, 4,5-dihydro Xy-2,7-naphthalenedisulfonic acid, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid, dihydroxybenzotriazole, 1,1,3-andracentriol and the like.
(3) ヒドロキシベンゾフエノン類として、 ジヒドロキシベンゾフエノン、 2, 3， 4—トリヒドロキシベンゾフエノン、 2, 6—ジヒドロキシ一 4—メ トキシ ベンゾフエノン、 2, 2 ' , 5, 6， ーテトラヒドロキシベンゾフエノン、 2, 3， ， 4, 4， ， 6—ペンタヒドロキシベンゾフヱノンなどが挙げられる。(3) As hydroxybenzophenones, dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,6-dihydroxy-14-methoxybenzophenone, 2,2 ', 5,6, -tetra Examples include hydroxybenzophenone, 2,3,4,4,4,6-pentahydroxybenzophenone.
(4 ) ヒドロキシベンズァニリ ド類として、 0—ヒドロキシベンズァニリ ドなど が挙げられる。 (4) Examples of hydroxybenzanilides include 0-hydroxybenzanilide.
(5) ヒドロキシァニル類として、 グリオキサールビス （2—ヒドロキシァニル ) などが挙げられる。  (5) Examples of hydroxyanil include glyoxalbis (2-hydroxyanyl).
(6) ヒドロキシビフエニル類として、 ビフエニルジオール、 ビフエニルトリオ —ル、 ビフヱニルテトラオールなどが挙げられる。  (6) Examples of hydroxybiphenyls include biphenyldiol, biphenyltriol, and biphenyltetraol.
(7) ヒドロキシキノン類およびその誘導体として、 2， 3—ヒドロキシ一 1 , 4—ナフトキノン、 5—ヒドロキシー 1， 4一ナフトキノン、 ジヒドロキシアン トラキノン、 1 , 2—ジヒドロキシ一 3— （アミノメチル） アントラキノンー N ， N' 一 2酢酸 [通称：了リザリンコンプレクソン] 、 トリヒドロキシアントラ キノンなどが挙げられる。 (7) Hydroxyquinones and derivatives thereof include 2,3-hydroxy-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, dihydroxyanthraquinone, 1,2-dihydroxy-13- (aminomethyl) anthraquinone N, N'-monoacetic acid [commonly known as Rizarin complexone], trihydroxyanthra Quinone and the like.
( 8 ) ジフエ二ルまたはトリフエニルアルカン誘導体として、 ジフエ二ルメタン —2， 2， ージオール、 4， 4' ， 4' ， 一トリフエニルメタントリオ一ル、 4 ， ' ジヒドロキシフクソン、 4, 4' ージヒドロキシ一 3—メチルフクソン、 ピロカテコールバイオレッ ト [通称： PV] などが挙げられる。  (8) As diphenyl or triphenylalkane derivatives, diphenylmethane-2,2, -diol, 4,4 ', 4', triphenylmethanetriol, 4, 'dihydroxyfuchsone, 4,4' Dihydroxy-13-methylfuchsone, pyrocatechol violet [commonly known as PV], and the like.
( 9 ) アルキルアミンのフエノール誘導体として、 エチレンジァミンジオルトヒ ドロキシフエニル酢酸 [通称： EDDHA] 、 N, N—ビス （2—ヒドロキシべ ンジル） エチレンジァミン一 N， N— 2酢酸 [通称： HBED] などが挙げられ る。  (9) Phenol derivatives of alkylamines such as ethylenediaminediolohydroxyphenylacetic acid [commonly known as EDDHA], N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetic acid [commonly known as HBED], etc. Are mentioned.
(1 0) アルキルェ一テルのフエノール誘導体として、 3， 3—エチレンジォキ シジフエノールなどが挙げられる。  (10) Alkenyl ether phenol derivatives include 3,3-ethylenedioxydiphenol.
(1 1 ) ァゾ基を有するフエノール類及びその誘導体として、 4， 4' —ビス （ 3， 4ージヒドロキシフエ二ルァゾ） 一 2， 2—スチルベンジスルホン酸 2アン モニゥム [通称：スチルバゾ] 、 2， 8—ジヒドロキシ一 1一 （8—ヒドロキシ —3, 6—ジスルホー 1—ナフチルァゾ） 一 3 , 6—ナフ夕レンジスルホン酸、 0— 0， ージヒドロキシァゾベンゼン、 2—ヒドロキシー 1一 （ 2—ヒドロキシ 一 5—メチルフエニルァゾ） 一 4一ナフ夕レンスルホン酸 [通 カルマガイ ト ] 、 クロロヒドロキシフエ二ルァゾナフトール、 1， 2， 一ジヒドロキシー 6— ニトロ一し 2， 一ァゾナフ夕レン一 4ースルホン酸 [通称：エリオクロ一ムブ ラック T] 、 2—ヒドロキシー 1一 （ 2—ハイ ドロキシ一 4ースルホー 1一ナフ チルァゾ） 一 3, 6—ナフタレンジスルホン酸、 5—クロロー 2—ハイドロキシ —3— (2, 4—ジハイド口キシフヱニルァゾ） ベンゼンスルホン酸 [通称：ル モガリオン] 、 2—ヒドロキシ一 1一 （ 2—ヒドロキシー 4—スルホー 1一ナフ チルァゾ） 一 3—ナフ夕レン酸 [通称： NN] 、 1, 8—ジヒドロキシ一 2— ( 4一スルフオフェニルァゾ） 一 3, 6—ナフタレンジスルホン酸、 1， 8—ジヒ ドロキシ一 2, 7—ビス （ 5—クロ口一 2—ヒドロキシー 3—スルホフエニルァ ゾ） 一 3， 6—ナフタレンジスルホン酸、 1 , 8—ジヒドロキシ一 2， 7—ビス ( 2—スルホフェニルァゾ） 一3, 6—ナフタレンジスルホン酸、 2— 〔3— ( 2, 4—ジメチルフエニルァミノ力ルポキシ） 一 2—ヒドロキシー 1一ナフチル ァゾ〕 一 3—ヒドロキシベンゼンスルホン酸、 1— 〔3— （2， 4ージメチルフ ェニルァミノカルボキシ） 一 2—ヒドロキシー 1—ナフチルァゾ〕 フエノールな どが挙げられる。 (11) Phenols having an azo group and derivatives thereof include 4,4′-bis (3,4-dihydroxyphenylazo) -1,2,2-stilbene disulfonic acid 2 ammonium [commonly known as stilbazo], 2 , 8-Dihydroxy-1- (8-hydroxy-3,6-disulfo-1-naphthylazo) -1,3,6-naphthylenedisulfonic acid, 0-0, dihydroxyazobenzene, 2-hydroxy-11 (2- Hydroxy-5-methylphenylazo) -14-naphthylenesulfonic acid [comcarmagite], chlorohydroxyphenylazinaphthol, 1,2,1-dihydroxy-6-nitro-2-nitro-1,2-nazonafrene -Sulfonic acid [commonly known as Eriochrome Black T], 2-hydroxy-11 (2-hydroxy-14-sulfo-11-naphthylazo) -1,3,6-naphthalenedisulfonic acid, 5 Chloro-2-hydroxy-3- (2,4-dihydridoxylphenylazo) Benzenesulfonic acid [commonly known as lemogalion], 2-hydroxy-11- (2-hydroxy-4-sulfo-11-naphthylazo) -1,3-naphthylene Acid [commonly known as NN], 1,8-dihydroxy-12- (4-sulfophenylazo) -1,3-naphthalenedisulfonic acid, 1,8-dihydroxy-1,2,7-bis (5-chloro One 2-hydroxy-3-sulfophenyla Zo) 1,3,6-Naphthalenedisulfonic acid, 1,8-dihydroxy-1,2,7-bis (2-sulfophenylazo) 1,3,6-naphthalenedisulfonic acid, 2- [3- (2,4-dimethyl Phenylamino propyloxy) 1-hydroxy-1-naphthylazo] 1-3-hydroxybenzenesulfonic acid, 1- [3- (2,4-dimethylphenylaminocarboxy) 1-2-hydroxy-1-naphthylazo] phenol And so on.
( 1 2) 水酸基を有する複素環式化合物類及びその誘導体として、 8—キノリノ —ル、 2—メチル一 8—キノリノール、 キノリンジオール、 1一 （2—ピリジル ァゾ） 一 2—ナフトール、 2—アミノー 4, 6， 7—プテリジントリオール、 5 , 7, 3' , 4 ' ーテトラヒドロキシフラボン [通称：ルテオリン] 、 3, 3— ビス 〔N, N—ビス （カルボキシメチル） アミノメチル〕 フルォレセイン [通称 (12) Heterocyclic compounds having a hydroxyl group and derivatives thereof include 8-quinolinol, 2-methyl-18-quinolinol, quinolinediol, 11- (2-pyridylazo) -12-naphthol, 2- Amino-4,6,7-pteridinetriol, 5,7,3 ', 4'-tetrahydroxyflavone [common name: luteolin], 3,3-bis [N, N-bis (carboxymethyl) aminomethyl] fluorescein [commonly known
：カルセイン] 、 2， 3ヒドロキシピリジンなどが挙げられる。 : Calcein], 2,3-hydroxypyridine and the like.
( 1 3) 水酸基を有する脂環式化合物及びその誘導体として、 シクロペンタノ一 ル、 クロコン酸、 シクロへキサノール、 シクロへキサンジオール、 ジヒドロキシ ジキノィル、 トロボロン、 6—^ ίソプロピルトロボロンなどが挙げられる。  (13) Examples of the alicyclic compound having a hydroxyl group and derivatives thereof include cyclopentanol, croconic acid, cyclohexanol, cyclohexanediol, dihydroxydiquinol, trobolone, and 6-^-propylpropyltroborone.
フエノ一ル性水酸基を有する芳香族炭化水素化合物は、 フヱノール性水酸基を 2個以上有するものが好ましい。  The aromatic hydrocarbon compound having a phenolic hydroxyl group is preferably an aromatic hydrocarbon compound having two or more phenolic hydroxyl groups.
また、 上記化合物のなかで、 I, 3—ジヒドロキシ安息香酸、 2, 4—ジヒド ロキシ安息香酸、 2, 5—ジヒドロキシ安息香酸、 2， 6—ジヒドロキシ安息香 酸、 3， 4ージヒドロキシ安息香酸、 3， 5—ジヒドロキシ安息香酸、 2， 3— ジヒドロキシベンズアルデヒド、 2， 4ージヒドロキシベンズアルデヒド、 2， 5—ジヒドロキシベンズアルデヒド、 2， 6—ジヒドロキシベンズアルデヒド、 3， 4ージヒドロキシベンズアルデヒド、 3, 5—ジヒドロキシベンズアルデヒ ド等が好ましい。  Also, among the above compounds, I, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4 5-dihydroxybenzoic acid, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, etc. Is preferred.
また、 上記化合物は単独でも、 二種以上組み合せて使用しても良く、好ましい 濃度は、 エッチング用組成物全体中に 0. 000 1〜5重量％でぁる。 上記フエ ノール性水酸基を有する芳香族炭化水素化合物の濃度が 0 . 0 0 0 1重量0 /0以下 であると、 エッチング時の、残渣物が発生し、 5重量0 /0以上では、 I T O膜のェ ツチング速度が低下したり、 十分に溶解しなかったりし、好ましくない。 Further, the above compounds may be used alone or in combination of two or more kinds, and the preferable concentration is 0.001 to 5% by weight in the whole etching composition. Hue above If the concentration of the aromatic hydrocarbon compound having Knoll hydroxyl group is zero. 0 0 0 1 weight 0/0 or less, at the time of etching, residue occurs at 5 weight 0/0 above, the ITO film E It is not preferable because the cutting speed is reduced or the dissolution is not sufficient.
窒素含有カルボン酸およびその塩として、 具体的には、 以下に記載のものが挙 げられるが、 特にこれらに限定されるものではない。  Specific examples of the nitrogen-containing carboxylic acid and its salt include those described below, but are not particularly limited thereto.
( 1 ) カルボキシル基を 1つ有する窒素含有カルボン酸およびその塩として、 ァ ミノ酢酸、 ジヒドロキシェチルグリシンなど、 およびその塩などが挙げられる。 (1) Examples of the nitrogen-containing carboxylic acid having one carboxyl group and salts thereof include aminoacetic acid, dihydroxyethylglycine, and the like, and salts thereof.
( 2 ) 力ルポキシル基を 2つ有する窒素含有カルボン酸およびその塩として、 ィ ミノ 2酢酸、 ヒドロキシェチルイミノ 2酢酸、 エチレンジァミン 2酢酸、 ェチレ ンジァミン 2プロピオン酸など、 およびその塩などが挙げられる。 (2) Examples of the nitrogen-containing carboxylic acid having two kelpoxyl groups and salts thereof include imino diacetic acid, hydroxyethylimino diacetic acid, ethylenediamine diacetic acid, ethylenediamine dipropionic acid, and salts thereof.
( 3 ) カルボキシル基を 3つ有する窒素含有カルボン酸およびその塩として、 二 トリ口 3酢酸、 ヒドロキシェチルェチレンジアミン 3酢酸、 二トリ口 3プロピオ ン酸など、 およびその塩などが挙げられる。  (3) Examples of the nitrogen-containing carboxylic acid having three carboxyl groups and salts thereof include triacetic acid triacetate, hydroxyethylethylenediamine triacetic acid, tripropionic acid 3-propionic acid, and salts thereof.
( 4 ) カルボキシル基を 4つ有する窒素含有カルボン酸およびその塩として、 ェ チレンジァミン 4酢酸、 トランス一 1， 2—シクロへキサンジァミン一 N， N , N， ， N， ーテトラ酢酸、 ジァミノプロパノール 4酢酸、 グリコールェ一テルジ ァミン 4酢酸、 へキサメチレンジァミン一 N， N , N ' , N ' —テトラ酢酸、 ジ アミノプロパン 4酢酸など、 およびその塩などが挙げられる。  (4) Examples of nitrogen-containing carboxylic acids having four carboxyl groups and salts thereof include ethylenediamine 4 acetic acid, trans-1,2-cyclohexanediamine N, N, N, N,, N-tetraacetic acid, diaminopropanol 4 Acetic acid, glycol ether terdiamine tetraacetic acid, hexamethylene diamine mono N, N, N ', N'-tetraacetic acid, diaminopropane tetraacetic acid, and the like, and salts thereof.
( 5 ) カルボキシル基を 5つ有する窒素含有カルボン酸およびその塩として、 ジ エチレン卜リアミン 5酢酸など、 およびその塩などが挙げられる。  (5) Examples of the nitrogen-containing carboxylic acid having five carboxyl groups and salts thereof include diethylenetriaminepentaacetic acid and the like, and salts thereof.
( 6 ) カルボキシル基を 6つ以上有する窒素含有カルボン酸およびその塩として 、 トリエチレンテトラミン 6酢酸など、 およびその塩などが挙げられる。  (6) Examples of the nitrogen-containing carboxylic acid having six or more carboxyl groups and salts thereof include triethylenetetramine hexaacetic acid and the like, and salts thereof.
( 7 ) その他類似化合物として、 トリエ夕ノールァミンなどの錯体形成能力のあ るアミン化合物おょぴその塩などが挙げられる。  (7) Other similar compounds include amine compounds capable of forming a complex such as trienolamine and salts thereof.
上記窒素含有カルボン酸およびその塩は単独でも、 二種以上組み合せて使用し ても良く、好ましい濃度は、 0 . 0 0 0 1〜5重量％である。 上記窒素含有カル ボン酸おょぴその塩は、 好ましくは、 カルボキシル基を 4つ以下有するものが挙 げられる。 上記窒素含有カルボン酸およびその塩の濃度が 0. 000 1重量0 /0以 下であると、 エッチング時の、 残渣物が発生し、 5重量0 /0以上では、 I TOのェ ツチング速度が低下したり、 十分に溶解しなかったりし、 好ましくない。 The nitrogen-containing carboxylic acids and salts thereof may be used alone or in combination of two or more. The preferred concentration is 0.0001 to 5% by weight. Nitrogen-containing cal As the boric acid or its salt, those having four or less carboxyl groups are preferred. When the nitrogen-containing carboxylic acids and concentration of the salt is 000 1 wt 0/0 hereinafter 0., during etching, residue occurs, the 5 weight 0/0 or more, E Tsuchingu rate of I TO It is not preferable because it decreases or does not dissolve sufficiently.
本発明のエッチング用組成物は、 常法に従って、 使用されるが、使用温度は、 常温から 90°Cまでであり、 使用時間は、 0. 1〜30分程度である。  The etching composition of the present invention is used according to an ordinary method, but the operating temperature is from normal temperature to 90 ° C., and the operating time is about 0.1 to 30 minutes.
また、 本発明は、 非晶質 I TOの他に、 I ZO (インジウム一亜鉛酸化物） 等 の透明導電膜や種々の半導体のウエットエツチングにも好適に使用される。 以下、 本発明の実施例を説明するが、 本発明は実施例に限定されるものではな い。  Further, the present invention is suitably used for wet etching of transparent conductive films such as IZO (indium monozinc oxide) and various semiconductors, in addition to amorphous ITO. Hereinafter, examples of the present invention will be described, but the present invention is not limited to the examples.
実施例 1 Example 1
図 1に示した基板は、 ガラス基板 1上に、 絶縁膜である S i 2 を成膜し、 さ らに非晶質 I T03 を成膜し、非晶質 I TO膜上にレジストを塗布し、 現像を行 つた後の状態である。 図 1に示した基板を使用し、 3. 4重量％のシユウ酸と、 0. 1重量％の、 , 3—ジヒドロキシ安息香酸を含有する水溶液である洗浄液 を使用し、 40°C、 2分間エッチングを行い水洗後、 さらに塩基性レジスト剥離 液でレジスト 4を剥離した後、 水洗し、 乾燥した SEM (電子顕微鏡） で表面を 観察した結果、 非晶質 I TOは良好にエッチングされ、 残渣物は全く観察されな かった。 In the substrate shown in FIG. 1, an insulating film Si 2 is formed on a glass substrate 1, an amorphous ITO 3 is further formed, and a resist is formed on the amorphous ITO film. This is the state after coating and development. Using the substrate shown in Fig. 1, a cleaning solution containing 3.4% by weight of oxalic acid and 0.1% by weight of, 3-dihydroxybenzoic acid was used at 40 ° C for 2 minutes. After etching and washing with water, the resist 4 was stripped with a basic resist stripper, washed with water, and the surface was observed with a dried SEM (electron microscope). As a result, the amorphous ITO was etched well and the residue was removed. Was not observed at all.
比較例 1 Comparative Example 1
実施例 1で用いた基板を、 3. 4重量％のシユウ酸を含有する水溶液である洗 浄液で 40° (：、 2分間エッチングを行い、水洗後、 乾燥した。 さらに塩基性レジ スト剥離液でレジスト 4を剥離した後、 7_洗した。 S ΕΜ観察の結果、 非晶質 I Τ〇はェッチングされていたが、 図 1に示す如く多数の残渣物 5が観察された。 比較例 2 0. 1重量0 /oの、 2， 3—ジヒドロキシ安息香酸を含有する水溶液である洗浄 剤を用い、 実施例 1で使用した基板を 4 0°C. 2分間エッチングを行い、 7_洗後 、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 7j洗し、 乾燥した。 S E M観察の結果、非晶質 I T〇はほとんどエッチングされていなかった。 The substrate used in Example 1 was etched at 40 ° (: for 2 minutes with a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid, washed with water, and dried. After the resist 4 was peeled off with the liquid, the resist 4 was washed 7_ As a result of observation of S, the amorphous I ェ was etched, but a number of residues 5 were observed as shown in Fig. 1. Comparative Example Two The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning agent which was an aqueous solution containing 2,3-dihydroxybenzoic acid at a weight of 0.1 / 0 / o. After the resist 4 was stripped with a basic resist stripper, the resist 4 was washed 7 j and dried. As a result of SEM observation, amorphous IT〇 was hardly etched.
実施例 1 Example 1
シユウ酸 3. 4重量％と、 0. 0 1重量％の、 2， 3—ジヒドロキシベンズァ ルデヒドを含有する水溶液である洗浄液を用い、実施例 1で使用した基板を 4 0 °C、 2分間エッチングを行い、 水洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 7j洗し、 乾燥した。 S EM観察の結果、 非晶質 I TOは良好にエツ チングされ、 残渣物も全く観察されなかった。  The substrate used in Example 1 was washed at a temperature of 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.01% by weight of 2,3-dihydroxybenzaldehyde. After etching and washing with water, the resist 4 was stripped off with a basic resist stripping solution, washed 7j, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
実施例 3 Example 3
シユウ酸 3. 4重量％と、 0. 3重量％の 2， 3—ジヒドロキシベンズアルデ ヒドを含有する水溶液である洗浄液を用い、 実施例 1で使用した基板を 40°C、 2分間エッチングを行い、 7_Κ洗後、 さらに塩基性レジスト剥離液でレジスト 4を 剥離後、 水洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエツチン グされ、 残渣物も全く観察されなかった。  The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.3% by weight of 2,3-dihydroxybenzaldehyde. After washing with 7 7, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
実施例 4 Example 4
シユウ酸 3. 4重量0 /0と、 0. 0 1重量％の2， 3—ジヒドロキシ安息香酸を 含有する水溶液である洗浄液を用い、 実施例 1で使用した基板を 40°C. 2分間 エッチングを行い、 洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後 、 水洗し、 乾燥した。 SEM観察の結果、非晶質 I TOは良好にエッチングされ 、 残渣物も全く観察されなかった。 And oxalate 3.4 wt 0/0, 0.0 1 wt% of 2, 3 using the cleaning solution is an aqueous solution containing dihydroxybenzoic acid, the substrate used in Example 1 40 ° C. 2 minutes etching After washing, the resist 4 was stripped off with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well and no residue was observed.
実施例 5 Example 5
シユウ酸 3. 4重量0 /0と、 0. 3重量0 /0の 2， 3—ジヒドロキシ安息香酸を含 有する水溶液である洗浄液を用い、 実施例 1で使用した基板を 40 °C、 2分間ェ ツチングを行い、 洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 水洗し、 乾燥した。 S E M観察の結果、 非晶質 I T 0は良好にェッチングされ、 残渣物も全く観察されなかった。 And oxalate 3.4 wt 0/0, 0.3 weight 0/0 of 2, 3-dihydroxybenzoic acid with a cleaning solution is an aqueous solution and containing not, the substrate used in Example 1 40 ° C, 2 minutes After performing etching, washing, and then removing resist 4 with a basic resist removing solution, Washed and dried. As a result of SEM observation, the amorphous IT0 was etched well, and no residue was observed.
実施例 β Example β
シユウ酸 1. 0重量0 /0と、 0. 1重量0 /0の 2， 3—ジヒドロキシ安息香酸を含 有する水溶液である洗浄液を用い、 実施例 1で使用した基板を 40°C. 4分間ェ ツチングを行い、 7 洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 7K洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残渣物も全く観察されなかった。 And oxalate 1.0 wt 0/0, 2 of 0.1 weight 0/0, 3-dihydroxybenzoic acid with a cleaning solution is an aqueous solution and containing not, the substrate used in Example 1 40 ° C. 4 min Etching was performed, and after 7 washes, the resist 4 was further stripped off with a basic resist stripping solution, followed by 7K washing and drying. As a result of SEM observation, the amorphous ITO was etched well and no residue was observed.
実施例 7 Example 7
シユウ酸 5. 5重量％と、 0. 1重量％の 2, 3—ジヒドロキシ安息香酸を含 有する水溶液である洗浄液を用い、実施例 1で使用した基板を 4 O ；、 2分間ェ ツチングを行い、 zK洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 水洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残澄物も全く観察されなかつた。  The substrate used in Example 1 was subjected to 4 O; etching for 2 minutes using a cleaning solution that was an aqueous solution containing 5.5% by weight of oxalic acid and 0.1% by weight of 2,3-dihydroxybenzoic acid. After washing with zK, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
比較例 3 Comparative Example 3
酢酸 5. 5重量0 /0と、 0. 1重量0 /0の 2, 3—ジヒドロキシ安息香酸を含有す る水溶液である洗浄液を用い、実施例 1で使用した基板を 40°C. 2分間エッチ ングを行い、 水洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 水洗 'し、 乾燥した。 SE.M観察の結果、 非晶質 I T〇はほとんどエッチングされてい なかった。 Acetic acid 5.5 weight 0/0, 2 of 0.1 weight 0/0, 3-dihydroxybenzoic acid with a cleaning solution is an aqueous solution you containing, Example 1 40 ° C. 2 minutes substrates used in After etching, washing with water, the resist 4 was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SE.M observation, the amorphous IT〇 was hardly etched.
実施例 δ Example δ
シユウ酸 3. 4重量％と、 0. 2重量％のジヒドロキ.シェチルグリシンを含有 する水溶液である洗浄液を用い、 実施例 1で使用した基板を 40° (：、 2分間エツ チングを行い、 洗後、 さらに塩基性レジスト剥離液でレジスト 4を剥離後、 水 洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残 渣物も全く観察されなかった。 比較例 4 The substrate used in Example 1 was etched at 40 ° (:, 2 minutes) using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of dihydroxy. After washing, the resist 4 was stripped off with a basic resist stripping solution, washed with water, and dried.As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed. Comparative Example 4
0. 2重量0 /oのジヒドロキシェチルグリシンを含有する水溶液である洗浄剤を 用い、 実施例 1で使用した基板を 4 O . 2分間エッチングを行い、 水洗後、 さ らに塩基性レジスト剥離液でレジス卜を剥離後、 水洗し、 乾燥した。 S E M観察 の結果、 非晶質 I T 0はほとんどエッチングされていなかった。 Using the cleaning agent is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0 / o, the substrate used in Example 1 performs 4 O. 2 minutes etching, washed with water, and et basic resist stripping After the resist was peeled off with the liquid, it was washed with water and dried. As a result of SEM observation, the amorphous ITO was hardly etched.
実施例 9 Example 9
シユウ酸 3. 4重量0 /0と、 0. 2重量0 /oのィミノ 2酢酸を含有する水溶液であ る洗浄液を用い、実施例 1で使用した基板を 4 0°C、 2分間エッチングを行い、 水洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 7j洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残渣物も全く観察さ れなかった。 And oxalate 3.4 wt 0/0, using the Ru solution der cleaning liquid containing Imino 2 acetic acid 0.2 weight 0 / o, the 4 0 ° C, 2 min etch the substrate used in Example 1 After washing with water, the resist was stripped with a basic resist stripping solution, washed with 7j, and dried. As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed.
実施例 1 0 Example 10
シユウ酸 3. 4重量％と、 0. 2重量％のヒドロキシェチルイミノ 2酢酸を含 有する水溶液である洗浄液を用い、 実施例 1で使用した基板を 4 0°C. 2分間ェ ツチングを行い、 7_洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 水 洗し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残 渣物も全く観察されなかった。  The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of hydroxyethyliminodiacetic acid. After washing with 7_, the resist was further stripped with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed.
実施例 1 1 Example 1 1
シユウ酸 3. 4重量0 /0と、 0. 2重量0 /0の二トリ口 3酢酸を含有する水溶液で ある洗浄液を用い、実施例 1で使用した基板を 4 0°C、 2分間エッチングを行い 、 水洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 7 洗し、 乾燥した 。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残渣物も全く観察 されなかった。 And oxalate 3.4 wt 0/0, 0.2 weight 0/0 of the two tri-port 3 using a cleaning solution is an aqueous solution containing acetic acid, 4 0 ° C the substrate used in Example 1, 2 minute etch After washing with water, the resist was stripped off with a basic resist stripping solution, then washed with 7 and dried. As a result of SEM observation, the amorphous ITO was etched well and no residue was observed.
実施例 1 2 Example 1 2
シユウ酸 3. 4重量％と、 0. 2重量％のエチレンジァミン 4酢酸を含有する 水溶液である洗浄液を用い、実施例 1で使用した基板を 4 0°C. 2分間エツチン グを行い、 水洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 水洗し、 乾燥した。 SEM観察の結果、非晶質 I TOは良好にエッチングされ、 残渣物も 全く観察されなかった。 The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 0.2% by weight of ethylenediaminetetraacetic acid. After washing with water, the resist was stripped with a basic resist stripper, washed with water, and dried. As a result of SEM observation, the amorphous ITO was favorably etched, and no residue was observed.
実施例 1 3 Example 13
シユウ酸 3. 4重量％と、 2. 0重量％のジヒドロキシェチルグリシンを含有 する水溶液である洗浄液を用い、 実施例 1で使用した基板を 4 0°C、 2分間エツ チングを行い、 7 洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 水洗 し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残渣 物も全く観察されなかった。  The substrate used in Example 1 was etched at 40 ° C for 2 minutes using a cleaning solution that was an aqueous solution containing 3.4% by weight of oxalic acid and 2.0% by weight of dihydroxyethylglycine. After washing, the resist was stripped off with a basic resist stripping solution, washed with water, and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
実施例 1 4 Example 14
シユウ酸 1. 0重量％と、 0. 2重量0 /0のジヒドロキシェチルグリシンを含有 する水溶液である洗浄液を用い、実施例 1で使用した基板を 4 0° (：、 2分間エツ チングを行い、 7j洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 水洗 し、 乾燥した。 S Ε Μ観察の結果、 非晶質 I Τ 0は良好にェッチングされ、 残渣 物も全く観察されなかった。 1. and 0 wt% oxalic acid, with a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/0, 4 0 ° the substrate used in Example 1 (:, 2 min Etsu quenching After washing with 7j, the resist was stripped with a basic resist stripping solution, washed with water and dried, and as a result of SΕObservation, the amorphous IΤ0 was well etched and no residue was observed. Was.
実施例 1 5 Example 15
シユウ酸 5. 5重量％と、 0. 2重量％のジヒドロキシェチルグリシンを含有 する水溶液である洗浄液を用い、実施例 1で使用した基板を 40°C. 2分間エツ チングを行い、 水洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 7 洗 し、 乾燥した。 SEM観察の結果、 非晶質 I TOは良好にエッチングされ、 残渣 物も全く観察されなかった。  The substrate used in Example 1 was etched at 40 ° C. for 2 minutes using a cleaning solution that was an aqueous solution containing 5.5% by weight of oxalic acid and 0.2% by weight of dihydroxyethylglycine. After the resist was stripped with a basic resist stripper, the resist was washed 7 and dried. As a result of SEM observation, the amorphous ITO was etched well, and no residue was observed.
比較例 5 Comparative Example 5
酢酸 5. 5重量％と、 0. 2重量0 /6のジヒドロキシェチルグリシンを含有する 水溶液である洗浄液を用い、 実施例 1で使用した基板を 40°C. 2分間エツチン グを行い、 7j洗後、 さらに塩基性レジスト剥離液でレジストを剥離後、 7j洗し、 乾燥した。 SEM観察の結果、非晶質 I TOはほとんどエッチングされていなか つた 産業上の利用可能性 Acetic 5. and 5 wt%, using a cleaning solution is an aqueous solution containing dihydroxy E chill glycine 0.2 weight 0/6, the substrate used in Example 1 carried out 40 ° C. 2 minutes Etsuchin grayed, 7j After washing, the resist was stripped off with a basic resist stripping solution, washed 7j, and dried. As a result of SEM observation, is amorphous ITO almost completely etched? Tsuta Industrial applicability
本発明のェッチング用組成物を使用すると、 温和な条件下で透明導電膜のェッ チングが出来、 且つ残渣物が全く発生しない。  When the etching composition of the present invention is used, the transparent conductive film can be etched under mild conditions, and no residue is generated.

Claims

請求の範囲 The scope of the claims
1 . シユウ酸とフユノール性水酸基を有する芳香族炭化水素化合物とを含有する 水溶液からなるエツチング用組成物。 1. An etching composition comprising an aqueous solution containing oxalic acid and an aromatic hydrocarbon compound having a phenolic hydroxyl group.
2 . フユノール性水酸基を有する芳香族炭化水素化合物がフェノ一ル性水酸基を 2個以上有するものである請求項 1に記載のェッチング用組成物。  2. The etching composition according to claim 1, wherein the aromatic hydrocarbon compound having a phenolic hydroxyl group has two or more phenolic hydroxyl groups.
3 . シユウ酸と窒素含有カルボン酸および/または窒素含有カルボン酸の塩とを 含有する 7 溶液であることを特徴とするエツチング用組成物。  3. A composition for etching, which is a 7-solution containing oxalic acid and a nitrogen-containing carboxylic acid and / or a salt of a nitrogen-containing carboxylic acid.
4 . 窒素含有カルボン酸のカルボキシル基の数が 4以下である請求項 3記載のェ ツチング用組成物。  4. The etching composition according to claim 3, wherein the number of carboxyl groups of the nitrogen-containing carboxylic acid is 4 or less.
5 . 透明導電膜のゥヱットエッチング用組成物である請求項 1記載のエッチング 用組成物。  5. The composition for etching according to claim 1, which is a composition for wet etching of a transparent conductive film.
6 . 透明導電膜のゥエツトエッチング用組成物である請求項 3記載のエッチング 用組成物。  6. The etching composition according to claim 3, which is a composition for wet etching of a transparent conductive film.
7 . 透明導電膜がィンジゥムー錫酸化物膜である請求項 5記載のエッチング用組 成物。  7. The etching composition according to claim 5, wherein the transparent conductive film is an aluminum tin oxide film.
8 . 透明導電膜がィンジゥム一錫酸化物膜である請求項 6記載のエツチング用組 成物。  8. The composition for etching according to claim 6, wherein the transparent conductive film is an aluminum tin oxide film.
PCT/JP2001/006048 2000-07-14 2001-07-12 Etching compositions WO2002007200A1 (en)

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JP5431014B2 (en) * 2009-05-01 2014-03-05 関東化学株式会社 Indium oxalate solubilizer composition
KR102324275B1 (en) * 2018-05-03 2021-11-09 삼성에스디아이 주식회사 Etching composition for silicone nitride and method for etching using the same
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JPH0448631A (en) * 1990-06-14 1992-02-18 Fujitsu Ltd Etching method for transparent conductive film
JPH0562966A (en) * 1991-09-04 1993-03-12 Fujitsu Ltd Etching method of transparent conductive film
JPH07141932A (en) * 1993-11-18 1995-06-02 Kanto Chem Co Inc Etching liquid composition for transparent conductive film
JPH11162916A (en) * 1997-11-28 1999-06-18 Nec Corp Cleaning method and cleaning solution for substrate
JP2000150457A (en) * 1998-11-09 2000-05-30 Mitsubishi Gas Chem Co Inc Method for etching transparent conductive film
JP2001176864A (en) * 1999-12-20 2001-06-29 Toshiba Electronic Engineering Corp Composition of etching liquid for transparent conductive film

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Publication number Priority date Publication date Assignee Title
JPH0448631A (en) * 1990-06-14 1992-02-18 Fujitsu Ltd Etching method for transparent conductive film
JPH0562966A (en) * 1991-09-04 1993-03-12 Fujitsu Ltd Etching method of transparent conductive film
JPH07141932A (en) * 1993-11-18 1995-06-02 Kanto Chem Co Inc Etching liquid composition for transparent conductive film
JPH11162916A (en) * 1997-11-28 1999-06-18 Nec Corp Cleaning method and cleaning solution for substrate
JP2000150457A (en) * 1998-11-09 2000-05-30 Mitsubishi Gas Chem Co Inc Method for etching transparent conductive film
JP2001176864A (en) * 1999-12-20 2001-06-29 Toshiba Electronic Engineering Corp Composition of etching liquid for transparent conductive film

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