WO2008032728A1 - Composition de solution d'attaque - Google Patents

Composition de solution d'attaque

Info

Publication number
WO2008032728A1
WO2008032728A1 PCT/JP2007/067710 JP2007067710W WO2008032728A1 WO 2008032728 A1 WO2008032728 A1 WO 2008032728A1 JP 2007067710 W JP2007067710 W JP 2007067710W WO 2008032728 A1 WO2008032728 A1 WO 2008032728A1
Authority
WO
WIPO (PCT)
Prior art keywords
etching solution
etching
water
acid
solution composition
Prior art date
Application number
PCT/JP2007/067710
Other languages
English (en)
Japanese (ja)
Inventor
Takafumi Yamabe
Yoshitaka Nishijima
Hidekuni Yasue
Yoshihiro Mukai
Original Assignee
Nagase Chemtex Corporation
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39183784&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2008032728(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nagase Chemtex Corporation filed Critical Nagase Chemtex Corporation
Priority to JP2008534357A priority Critical patent/JP4674704B2/ja
Priority to KR1020097003619A priority patent/KR101409638B1/ko
Publication of WO2008032728A1 publication Critical patent/WO2008032728A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers

Definitions

  • the present invention relates to an etching solution for a transparent conductive film used in a display device such as a liquid crystal display (LCD) or an electro-luminescence (EL) display.
  • a display device such as a liquid crystal display (LCD) or an electro-luminescence (EL) display.
  • LCD liquid crystal display
  • EL electro-luminescence
  • a transparent conductive film is used for a display electrode of a pixel.
  • an indium oxide-based transparent conductive film such as an indium tin oxide (ITO) film
  • ITO film is formed on a substrate such as glass by using a film forming process such as sputtering.
  • a resist or the like By etching the ITO film using a resist or the like as a mask, an electrode pattern is formed on the substrate. In this etching process, there are wet and dry processes, and an etchant is used in the wet process.
  • wet etching of a polycrystalline ITO film is usually performed using a hydrochloric acid-based strong acid. During etching, corrosion of aluminum wiring or the like occurs, and the ITO grain boundary force is also selectively selected. As etching progresses, it is difficult to pattern with high processing accuracy.
  • Patent Document 1 discloses an etching solution comprising oxalic acid, dodecyl benzene sulfonic acid, and water. ing.
  • etching residue is less likely to be formed, but the foaming of the etching solution becomes remarkable. If foaming is significant, bubbles may push up the substrate.If bubbles are generated on the substrate, contact with the etchant will be hindered, and etching will be performed accurately in either case. This causes a defect in the wiring pattern.
  • An etching solution in which a perfluoroalkyl group-containing phosphate ester salt is added to an aqueous oxalic acid solution is also known (see, for example, Patent Document 2). According to this technique, foaming may be suppressed, but the residue removal capability may not always be sufficient.
  • a base film such as a nitride nitride film is formed on the substrate.
  • An amorphous ITO film is formed thereon.
  • a planarized film is formed and an amorphous ITO film is formed thereon.
  • an etching residue is generated as compared with the case where the ITO film is formed on the substrate without using the base film, and the conventional etching liquid is formed immediately. In this case, it may be difficult to remove sufficient residues.
  • Patent Document 3 is a combination of an aqueous solution of oxalic acid, a polysulfonic acid compound, and a polyoxyethylene-polyoxypropylene block copolymer.
  • the ITO film formed on the base film can also be etched well and the foaming is small. .
  • amorphous ITO is etched using such an etching solution, there is a problem that a salt of oxalic acid and indium precipitates as a solid as the etching progresses. The appearance of this precipitate is thought to be because the soluble concentration of indium is about 200 ppm in a general oxalic acid-based etching solution, and the excess appears as a precipitate.
  • Patent Document 4 describes an ITO film removing solution containing 0.5 to 15% by weight of hydrochloric acid, phosphoric acid and carboxylic acid, a surfactant, and a polyamine.
  • the main purpose of this ITO film removal solution is to remove the ITO film on the metal mask, and the residue removal ability that is important in the etching for which patterning is the object is insufficient.
  • Patent Document 1 JP-A-7-141932
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-11654
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-164332
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-309888
  • the present invention eliminates etching residue not only for a transparent conductive film formed on a substrate without a base film but also for a transparent conductive film formed on a base film on the substrate.
  • An object of the present invention is to provide an etching solution composition which is excellent in leaving performance, can suppress foaming, and has a longer liquid life than conventional products without precipitation of solid matter.
  • the present invention comprises (a) oxalic acid, (b) naphthalenesulfonic acid condensate or salt thereof, (c) at least one of hydrochloric acid, sulfuric acid, water-soluble amine and salts thereof, and (d) An etching solution composition for a transparent conductive film characterized by containing water.
  • the present invention suppresses foaming while containing a surfactant. Therefore, the present invention can be suitably applied to the etching step in the manufacturing process of a substrate with a transparent conductive film.
  • the present invention can also be applied to an ITO film formed on a glass substrate by the above-described configuration, or an ITO film formed on a base film such as a silicon nitride film. Since a good residue removing ability can be exhibited, high-quality etching of the ITO film on the base film, which has been relatively difficult in the past, is possible.
  • the present invention suppresses precipitation of salt of oxalic acid and indium, which is a cause of the conventional etching solution being exchanged while maintaining the etching performance, so that the frequency of liquid exchange is less than that of the conventional product. It is possible to provide a long-life etching solution that can be used.
  • the etching solution composition of the present invention comprises (a) oxalic acid (hereinafter also referred to as component (a)), (b) naphtha Ren sulfonic acid condensate or salt thereof (hereinafter also referred to as component (b)), (c) hydrochloric acid, sulfuric acid, water-soluble amine and at least one of these salts (hereinafter also referred to as component (c)), and (D) Contains water (hereinafter also referred to as component (d)) as an essential component.
  • component (a) oxalic acid
  • component (b) naphtha Ren sulfonic acid condensate or salt thereof
  • component (c) hydrochloric acid, sulfuric acid, water-soluble amine and at least one of these salts
  • component (d) Contains water
  • the amount of oxalic acid (a) used in the present invention is preferably 15% by weight or less as long as it is within the solubility in water in the etching solution composition, and the lower limit is in view of etching rate. Therefore, when the total amount of the components (a) to (d) is 100% by weight, it is preferably 0.5% by weight or more. If it is less than 5% by weight, the etching rate may be slow. More preferably;! ⁇ 5 wt%.
  • the naphthalenesulfonic acid condensate or salt (b) used in the present invention is a condensate obtained by condensing / 3-naphthalenesulfonic acid or a salt thereof with, for example, formaldehyde, and has a molecular weight of 1000 to About 5000.
  • the sulfonic acid moiety may be in any form such as acid, sodium salt, potassium salt, ammonium salt, monoethanolamine salt, triethanolamine salt, and the like.
  • Daiichi Kogyo Seiyaku Co., Ltd. Labelin FM-P, Labelin FH-P, Kao Corporation MX-2045L, Lion Corporation Politi N-100K, etc. As the component (b), one type may be used or two or more types may be combined! /.
  • the amount of component (b) is preferably 0.005 to 5% by weight when the total amount of components (a) to (d) is 100% by weight. If the amount is less than this range, the residue removing ability may be insufficient. On the other hand, if the amount exceeds this range, the residue removing ability will not be improved so much. . More preferably, it is 0.01 to ⁇ !% By weight.
  • the component (c) is hydrochloric acid, sulfuric acid, water-soluble amine, or a salt thereof. These may be used alone or in combination, for example, hydrochloric acid and sulfuric acid, hydrochloric acid and water-soluble amine, sulfuric acid and water-soluble amine, or hydrochloric acid and sulfuric acid and water-soluble amine, or water-soluble amine.
  • a salt of any of these components such as a soluble amine salt may be used.
  • an effect of preventing volatilization of the acid can be obtained by forming a salt by adding an amine or the like.
  • the water-soluble amine is preferably at least one of alkanolamines, quaternary alkyl ammoniums, ammonia, alkylamines and salts thereof, specifically monoethanolamine.
  • the Ammonium Hydrochloride, sulfate, carbonate, etc. The Ammonium Hydrochloride, sulfate, carbonate, etc.), and one of
  • the amount of hydrochloric acid is preferably 0.01 when the total amount including the components (a) to (d) is 100% by weight. -0. 3% by weight. If it is less than this range, the ability to prevent the salt of oxalic acid and indium from precipitating may be unsatisfactory. On the other hand, if it exceeds this range, there will be a problem in residue removability. More preferably, it is 0.05 to 0. 1% by weight.
  • the total amount of the above components (a) to (d) is 100% by weight. In some cases, it is preferably 0.5 to 20% by weight. If it is less than this range, the ability to prevent the salt of oxalic acid and indium from precipitating may be insufficient. On the other hand, if it exceeds this range, the residue removal performance will be inconvenient or etching may occur. There is a risk of lowering the rate. More preferably 1 to 10% by weight.
  • the amount of water (d) used in the present invention is the amount of the components (a) to (c) when the total amount of the components (a) to (d) is 100% by weight. The remainder of the quantity.
  • the etching solution composition of the present invention has other components as long as it does not interfere with the object of the present invention.
  • a fluorinated alkyl group-containing phosphoric acid surfactant or an alkylalkylene surfactant can be appropriately blended as necessary.
  • the required amounts of the above components are mixed by a conventional method (at room temperature). It can be prepared by mixing with stirring).
  • the etching solution composition of the present invention is used for etching a transparent conductive film (such as an indium oxide film) formed on a substrate (such as glass).
  • a transparent conductive film such as an indium oxide film
  • a substrate such as glass
  • it can be used for patterning by etching an ITO film formed on a substrate by sputtering or the like.
  • it can be suitably used for etching an ITO film formed on a substrate with a base film formed thereon.
  • the base film refers to a film formed on the substrate, below the ITO film, prior to the formation of the ITO film, and on which the ITO film is formed. It may be a (SiN) film or the like.
  • the etching composition of the present invention is heated at room temperature or heated.
  • the time required for etching varies depending on the film thickness of the ITO film. In general, for example, it is about! After the etching, it can be cleaned in a rinsing step as necessary.
  • NPA N-Propanolamine
  • TMAH Tetramethylammonium hydride mouth oxide
  • NSFM Naphthalenesulfonic acid formaldehyde condensate MEA salt 50% aqueous solution
  • PFP Perfluoroalkyl group-containing phosphate ester surfactant
  • the substrate on which the ITO film was formed on the glass substrate was etched for 1.4 times the just etching time calculated from the etching rate. After washing with water and nitrogen blowing, the treated sample was observed with an electron microscope! / And the residue after etching was evaluated.
  • a silicon nitride film was formed on a glass substrate, and the substrate on which the ITO film was formed was etched for 1.4 times the just etch time calculated from the etching rate. After washing with water and blowing with nitrogen, the treated sample was observed with an electron microscope, and the residue after etching was evaluated. The following evaluations of foaming and indium solubility were not performed for those that failed the residue removability in this evaluation. Passes are ⁇ and ⁇ .
  • Example 1 3.4% 0.5% 0.1%--Remainder
  • Example 2 3.4% 0.5% 0.3%--Remainder
  • Example 3 3.4% 0.5% 0.1% Sulfuric acid 1% Remainder
  • Example 4 3.4% 0.5% 0.1% Sulfuric acid 7% Remainder
  • Example 5 3.4% 0.5% 0.1% Sulfuric acid 20% remainder
  • Example 6 3.4% 0.5% ⁇ MEA 1% remainder
  • Example 1 3.4% 0.5% ⁇ Sulfuric acid 3% remainder
  • Example 8 3.4% 0.5% 0.1% MEA 1% remainder
  • Example 9 7.8% 0.5% 0.1% MEA 3% balance
  • Example 10 10.6% 0.5% 0.1% MEA 5% balance
  • Example 1 3.4% 0.5% 0.1% MIPA 1% balance
  • Example 12 3.4% 0.5% 0.1% NPA 1% balance
  • Example 13 3.4% 0.5% 0.1% TMAH n balance
  • Example 14 3.4% 0.5% 0.1% struggle A 1% balance
  • Example 15 3.4% 0.5% 0.1% DEA 1% balance
  • Example 16 3.4% 0.5% 0.1 % 1% Re
  • the present invention has improved residue removal capability and low foamability as compared with the prior art, can contribute to improved patterning yield and accuracy, and is extremely useful in the manufacture of electronic components.
  • the etching solution can be used longer than the conventional product, the amount of chemical solution used can be reduced, which is highly advantageous in terms of both cost and environment.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Weting (AREA)
  • Liquid Crystal (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

La présente invention concerne une composition de solution d'attaque pour un film conducteur transparent d'oxyde stannique d'indium comprenant au moins un élément sélectionné parmi l'acide oxalique, un condensat d'acide sulfonique de naphtalène ou un sel de celui-ci, l'acide chlorhydrique, l'acide sulfurique et un amine soluble dans l'eau, ainsi que de l'eau. La composition de solution d'attaque peut présenter une excellente capacité à supprimer un résidu d'attaque sur un film conducteur transparent qui est formé sur un substrat sans film de sous-couche, ainsi qu'un film conducteur transparent qui est formé sur un film de sous-couche formé sur un substrat ; la composition de solution d'attaque peut également empêcher la formation de mousse, ne provoque pas de précipitation de matériau solide et dispose ainsi d'une durée de vie de solution plus longue qu'une composition de solution d'attaque traditionnelle.
PCT/JP2007/067710 2006-09-13 2007-09-12 Composition de solution d'attaque WO2008032728A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2008534357A JP4674704B2 (ja) 2006-09-13 2007-09-12 エッチング液組成物
KR1020097003619A KR101409638B1 (ko) 2006-09-13 2007-09-12 에칭액 조성물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006247697 2006-09-13
JP2006-247697 2006-09-13

Publications (1)

Publication Number Publication Date
WO2008032728A1 true WO2008032728A1 (fr) 2008-03-20

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PCT/JP2007/067710 WO2008032728A1 (fr) 2006-09-13 2007-09-12 Composition de solution d'attaque

Country Status (5)

Country Link
JP (2) JP4674704B2 (fr)
KR (1) KR101409638B1 (fr)
CN (1) CN101517712A (fr)
TW (1) TWI421937B (fr)
WO (1) WO2008032728A1 (fr)

Cited By (8)

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CN101649202A (zh) * 2008-08-14 2010-02-17 关东化学株式会社 透明导电膜用腐蚀液组合物
JP2010261070A (ja) * 2009-05-01 2010-11-18 Kanto Chem Co Inc しゅう酸インジウム溶解剤組成物
KR20140086826A (ko) 2012-12-28 2014-07-08 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 적어도 인듐 및 갈륨을 포함하는 산화물의 에칭액 및 에칭 방법
KR20160077028A (ko) 2013-10-30 2016-07-01 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 아연, 주석 및 산소로 실질적으로 이루어진 산화물의 에칭액 및 에칭방법
KR20160105777A (ko) 2014-01-07 2016-09-07 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 아연과 주석을 포함하는 산화물의 에칭액 및 에칭방법
KR20160122715A (ko) 2014-02-17 2016-10-24 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 인듐과 아연과 주석 및 산소로 이루어진 산화물의 에칭용 액체 조성물 및 에칭방법
JP2017216444A (ja) * 2016-05-31 2017-12-07 ナガセケムテックス株式会社 エッチング液
JP2018174309A (ja) * 2017-03-31 2018-11-08 ナガセケムテックス株式会社 エッチング液

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WO2014010471A1 (fr) * 2012-07-09 2014-01-16 攝津製油株式会社 Fluide de gravure, agent de récupération de force de gravure, procédé de fabrication d'un substrat semi-conducteur destiné à une cellule solaire, et substrat semi-conducteur destiné à une cellule solaire
JP6261926B2 (ja) 2013-09-18 2018-01-17 関東化學株式会社 金属酸化物エッチング液組成物およびエッチング方法
CN105087009B (zh) * 2014-04-30 2017-06-30 东莞市钜升金属科技有限公司 一种用于ito膜刻蚀的工艺
US10168805B2 (en) 2014-08-18 2019-01-01 3M Innovative Properties Company Conductive layered structure and methods of making same
CN108780747B (zh) * 2016-03-24 2022-09-30 株式会社Adeka 蚀刻液组合物和蚀刻方法
CN106701085A (zh) * 2016-12-28 2017-05-24 杭州格林达化学有限公司 一种ito返工蚀刻液及其制备方法
JP6795543B2 (ja) * 2018-04-27 2020-12-02 株式会社Ｊｏｌｅｄ 半導体装置の製造方法
CN109233837A (zh) * 2018-10-29 2019-01-18 苏州博洋化学股份有限公司 面板显示阵列制程用新型草酸系ito蚀刻液

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KR101680758B1 (ko) 2008-08-14 2016-11-29 간토 가가꾸 가부시키가이샤 투명 도전막용 에칭액 조성물
JP2010045253A (ja) * 2008-08-14 2010-02-25 Kanto Chem Co Inc 透明導電膜用エッチング液組成物
CN101649202A (zh) * 2008-08-14 2010-02-17 关东化学株式会社 透明导电膜用腐蚀液组合物
JP2010261070A (ja) * 2009-05-01 2010-11-18 Kanto Chem Co Inc しゅう酸インジウム溶解剤組成物
KR20140086826A (ko) 2012-12-28 2014-07-08 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 적어도 인듐 및 갈륨을 포함하는 산화물의 에칭액 및 에칭 방법
US9217106B2 (en) 2012-12-28 2015-12-22 Mitsubishi Gas Chemical Company, Inc. Etchant and etching process for oxides containing at least indium and gallium
KR20160077028A (ko) 2013-10-30 2016-07-01 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 아연, 주석 및 산소로 실질적으로 이루어진 산화물의 에칭액 및 에칭방법
KR20160105777A (ko) 2014-01-07 2016-09-07 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 아연과 주석을 포함하는 산화물의 에칭액 및 에칭방법
US9824899B2 (en) 2014-01-07 2017-11-21 Mitsubishi Gas Chemical Company, Inc. Etching liquid for oxide containing zinc and tin, and etching method
KR20160122715A (ko) 2014-02-17 2016-10-24 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 인듐과 아연과 주석 및 산소로 이루어진 산화물의 에칭용 액체 조성물 및 에칭방법
US10023797B2 (en) 2014-02-17 2018-07-17 Mitsubishi Gas Chemical Company, Inc. Liquid composition for etching oxides comprising indium, zinc, tin, and oxygen and etching method
JP2017216444A (ja) * 2016-05-31 2017-12-07 ナガセケムテックス株式会社 エッチング液
JP2018174309A (ja) * 2017-03-31 2018-11-08 ナガセケムテックス株式会社 エッチング液
JP7252712B2 (ja) 2017-03-31 2023-04-05 ナガセケムテックス株式会社 エッチング液

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JP4674704B2 (ja) 2011-04-20
CN101517712A (zh) 2009-08-26
JPWO2008032728A1 (ja) 2010-01-28
TW200826193A (en) 2008-06-16
JP2011049602A (ja) 2011-03-10

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