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WO2012015088A1 - Procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides - Google Patents

Procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2012015088A1
WO2012015088A1 PCT/KR2010/005019 KR2010005019W WO2012015088A1 WO 2012015088 A1 WO2012015088 A1 WO 2012015088A1 KR 2010005019 W KR2010005019 W KR 2010005019W WO 2012015088 A1 WO2012015088 A1 WO 2012015088A1
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WO
WIPO (PCT)
Prior art keywords
copper
weight
metal film
based metal
etching
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2010/005019
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English (en)
Korean (ko)
Inventor
이석
최용석
윤영진
이우람
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongwoo Fine Chem Co Ltd
Original Assignee
Dongwoo Fine Chem Co Ltd
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
Application filed by Dongwoo Fine Chem Co Ltd filed Critical Dongwoo Fine Chem Co Ltd
Priority to PCT/KR2010/005019 priority Critical patent/WO2012015088A1/fr
Priority to CN201080068296.0A priority patent/CN103026293B/zh
Publication of WO2012015088A1 publication Critical patent/WO2012015088A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells

Definitions

  • the present invention relates to a method of manufacturing an array substrate for a liquid crystal display device.
  • the process of forming a metal wiring on a substrate in a semiconductor device is composed of a metal film forming process, a photoresist forming process and an etching process in a selective region by photoresist coating, exposure and development.
  • the process of forming the said metal wiring includes the washing
  • the etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask.
  • a dry etching using a plasma or the like or a wet etching using an etchant composition is usually used.
  • An object of the present invention is to provide an etching liquid composition for a copper-based metal film in which a tapered profile excellent in linearity is formed upon etching the copper-based metal film and no residue is left.
  • an object of the present invention is to provide an etching liquid composition for a copper-based metal film which can be collectively etched with respect to a gate electrode and a gate wiring, a source / drain electrode and a data wiring.
  • the etchant composition in steps 1) and 5) comprises: a) hydrogen peroxide (H 2 O 2 ) 5 based on the total weight of the composition; To 25 weight percent; b) 0.1 to 5% by weight sulfuric acid; c) 0.01 to 1.0 wt% of a fluorine-containing compound; d) 0.1 to 5% by weight of azole compounds; e) 0.1 to 5%
  • the present invention comprises the steps of: a) forming a copper-based metal film on the substrate; B) selectively leaving a photoreactive material on the copper-based metal film; And c) etching the copper-based metal film using an etchant composition, wherein the etchant composition comprises: a) 5 to 25 weight percent hydrogen peroxide (H 2 O 2 ) based on the total weight of the composition; b) 0.1 to 5% by weight sulfuric acid; c) 0.01 to 1.0 wt% of a fluorine-containing compound; d) 0.1 to 5% by weight of azole compounds; e) 0.1 to 5% by weight of imidazole compounds; And f) provides an etching method of the copper-based metal film comprising a residual amount of water.
  • the etchant composition comprises: a) 5 to 25 weight percent hydrogen peroxide (H 2 O 2 ) based on the total weight of the composition; b) 0.1 to 5% by weight sulfuric acid; c)
  • the present invention relates to a composition
  • a composition comprising a) 5 to 25 weight percent hydrogen peroxide (H 2 O 2 ), based on the total weight of the composition; b) 0.1 to 5% by weight sulfuric acid; c) 0.01 to 1.0 wt% of a fluorine-containing compound; d) 0.1 to 5% by weight of azole compounds; e) 0.1 to 5% by weight of imidazole compounds; And f) provides a copper-based metal film etching liquid composition comprising a residual amount of water.
  • H 2 O 2 hydrogen peroxide
  • the etching liquid composition according to the present invention may implement a taper profile excellent in linearity when etching the copper-based metal film.
  • etching the copper-based metal film with the etchant composition according to the present invention no residue is generated, thereby preventing problems such as electrical shorts, wiring defects, and reduced luminance.
  • etchant composition according to the present invention it is possible to collectively etch the gate electrode and gate wiring, the source / drain electrode and the data wiring, so that the process is very simplified to maximize the process yield have.
  • the etchant composition according to the present invention is used for etching low-resistance copper or copper alloy wirings, a large screen, high brightness circuit can be realized, and an environmentally friendly array substrate for a liquid crystal display device can be manufactured.
  • Example 1 is a scanning electron micrograph of the etching cross-section after etching the Cu / Mo-Ti double layer using the etchant composition according to Example 1 of the present invention
  • FIG. 2 is a scanning electron micrograph of etching Cu / Mo-Ti double layer using an etchant composition according to Example 1 of the present invention and then observing an overall etching profile;
  • Example 3 is an electron scanning microscope photograph of a copper wiring peripheral surface to confirm that no etching residue remains after etching the Cu / Mo-Ti double layer using the etchant composition according to Example 1 of the present invention.
  • FIG. 4 is a scanning electron micrograph of etching Cu / Mo-Ti double layer using an etchant composition according to Comparative Example 1 of the present invention and then observing an overall etching profile;
  • FIG. 5 is a scanning electron micrograph of etching Cu / Mo-Ti double layer using an etchant composition according to Comparative Example 2 of the present invention, and then observing an overall etching profile.
  • FIG. 5 is a scanning electron micrograph of etching Cu / Mo-Ti double layer using an etchant composition according to Comparative Example 2 of the present invention, and then observing an overall etching profile.
  • the present invention provides a composition
  • a composition comprising a) 5 to 25 weight percent hydrogen peroxide (H 2 O 2 ), based on the total weight of the composition; b) 0.1 to 5% by weight sulfuric acid; c) 0.01 to 1.0 wt% of a fluorine-containing compound; d) 0.1 to 5% by weight of azole compounds; e) 0.1 to 5% by weight of imidazole compounds; And f) provides an etchant composition of the copper-based metal film comprising a residual amount of water.
  • H 2 O 2 hydrogen peroxide
  • the copper-based metal film includes copper as a constituent of the film, and is a concept including a multilayer film such as a single film and a double film.
  • a copper molybdenum film, a copper molybdenum alloy film, etc. are contained as a single film
  • the copper molybdenum film may include a molybdenum film and a copper film formed on the molybdenum film
  • the copper molybdenum alloy film may include a molybdenum alloy film and a copper film formed on the molybdenum alloy film.
  • the molybdenum alloy film is an alloy of molybdenum and at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium (In) and the like. Means.
  • A) Hydrogen peroxide (H 2 O 2 ) included in the etchant composition of the present invention is a main component for etching the copper-based metal film.
  • the a) hydrogen peroxide (H 2 O 2 ) is preferably included in 5 to 25% by weight, 10 to 20% by weight relative to the total weight of the composition. If it is less than the above-mentioned range, a copper metal film will not be etched or an etching speed will become very slow. In addition, when the above range is exceeded, the etching rate is generally increased, so that it is difficult to control the process.
  • B) sulfuric acid contained in the etchant composition of the present invention serves to create an environment in which the copper-based metal film can be etched by adjusting the pH, and lowers the pH to inhibit decomposition of hydrogen peroxide.
  • B) Sulfuric acid is included in an amount of 0.1 to 5% by weight, and 0.5 to 3% by weight based on the total weight of the composition. When included below the above range, the effect of adjusting the pH is insufficient, so that the etching rate of copper is too slow, and at the same time there is a problem that hydrogen peroxide decomposition is accelerated. If it exceeds the above-mentioned range, there is a disadvantage that the etching rate of copper is faster.
  • the etching rate of the molybdenum or molybdenum alloy is lowered, thereby increasing CD loss.
  • the probability of occurrence of molybdenum or molybdenum alloy residues increases.
  • the fluorine-containing compound included in the etchant composition of the present invention refers to a compound capable of dissociating in water to give F ions.
  • the c) fluorine-containing compound serves to remove the residue that is inevitably generated in the solution for etching the copper molybdenum film or copper molybdenum alloy film.
  • the c) fluorine-containing compound is preferably included in an amount of 0.01 to 1.0% by weight, and 0.1 to 0.5% by weight, based on the total weight of the composition. When included in less than the above-described range, an etching residue may occur. When included beyond the above range, there is a disadvantage that the glass substrate etching rate is increased.
  • the fluorine-containing compound is a substance used in the art, and is not particularly limited as long as it is a compound capable of dissociating into fluorine ions or polyatomic fluoride ions in a solution, ammonium fluoride (NH 4 F), sodium fluoride (sodium fluoride: NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 FHF), sodium bifluoride (NaFHF), and potassium bifluoride (KFHF) It is preferable that it is 1 type, or 2 or more types chosen from.
  • D) azole compounds included in the etchant composition of the present invention controls the etching rate of the copper film or copper alloy film and serves to increase the process margin by reducing the CD loss of the pattern.
  • the content of the d) azole compounds is included in 0.1 to 5% by weight, and 0.5 to 3% by weight based on the total weight of the composition. If it is included below the above range, the etching speed may be high, and the cisidross may be generated too large.
  • the molybdenum or molybdenum alloy film may be over-etched to generate undercuts.
  • the d) azole compound is one or two selected from the group consisting of aminotetrazole, benzotriazole, tolytriazole, pyrazole and pyrrole It is preferable that it is above.
  • the e) imidazole compound included in the etchant composition of the present invention chelates the copper surface when etching copper, thereby uniformly etching the entire surface of the copper substrate, and controlling the etching rate of copper.
  • the e) imidazole compound is contained in 0.1 to 5% by weight, preferably 1 to 4% by weight. When included in the above-described range, the copper etching uniformity is lowered, the CDOS is uneven, and the copper etching speed is too high.
  • the etching speed of copper is lowered, and the etching rate with respect to the molybdenum or molybdenum alloy film is faster, so that the taper angle is increased when applied to the copper molybdenum film or copper molybdenum alloy film.
  • the e) imidazole compounds are imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-aminoimidazole, 4-methylimidazole, 4-ethylimidazole. It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of a sol and 4-propylimidazole.
  • the remaining amount of f) water contained in the etchant composition of the present invention is included, and the kind thereof is not particularly limited, but deionized water is preferable. More preferably, deionized water having a specific resistance value of the water (that is, the degree to which ions are removed in the water) is 18 kV / cm or more is preferably used.
  • the etchant composition of the present invention is characterized in that it does not contain a separate carboxylic acid and phosphate.
  • the phosphate salt serves to increase the pH since the alkali cation is included. Therefore, the etchant composition of the present invention is characterized in that it does not contain the phosphate.
  • the etchant composition of the present invention may further include a surfactant.
  • the surfactant serves to decrease the surface tension to increase the uniformity of the etching.
  • the surfactant is not particularly limited as long as it can withstand the etching liquid composition of the present invention and is compatible, but is not limited to anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, and polyhydric alcohol type surfactants. It is preferably one or two or more selected from the group consisting of.
  • a conventional additive may be further added, and as the additive, a metal ion blocking agent, a corrosion inhibitor, or the like may be used.
  • the a) hydrogen peroxide (H 2 O 2 ), the b) sulfuric acid, the c) fluorine-containing compound, d) azole compounds, e) imidazole compounds used in the present invention can be prepared by conventionally known methods And it is preferable to have the purity for a semiconductor process.
  • the gate electrode, the gate wiring, the source / drain electrode and the data wiring of the liquid crystal display device made of the copper-based metal may be collectively etched.
  • the present invention (a) forming a copper-based metal film on the substrate; B) selectively leaving a photoreactive material on the copper-based metal film; And c) etching the copper-based metal film using the etchant composition of the present invention.
  • the photoreactive material is preferably a conventional photoresist material, and may be selectively left by conventional exposure and development processes.
  • the present invention comprises the steps of: 1) etching the copper-based metal film located on the substrate with an etching liquid composition to form a gate electrode; 2) forming a gate insulating layer that insulates the gate electrode; 3) forming a semiconductor layer on the gate insulating layer; 4) forming an insulating layer to insulate the semiconductor layer; 5) forming a copper-based metal film on the insulating layer to insulate the semiconductor layer and etching the copper-based metal film with an etchant composition to form source / drain electrodes; And 6) forming a pixel electrode electrically connected to the drain electrode, wherein the etchant composition in steps 1) and 5) is an etchant composition of the present invention. It provides a manufacturing method.
  • the array substrate for a liquid crystal display device may be a thin film transistor (TFT) array substrate.
  • TFT thin film transistor
  • An etching process of the copper-based metal film (Cu single layer and Cu / Mo-Ti double layer) was performed using the etching solution compositions of Examples 1 to 6.
  • the temperature of the etchant composition was about 30 ° C., but the proper temperature may be changed as needed by other process conditions and other factors.
  • the etching time may vary depending on the etching temperature, but usually proceeds about 30 to 180 seconds.
  • the profile of the copper-based metal film etched in the etching process was examined using a cross-sectional SEM (Model S-4700, manufactured by Hitachi), and the results are shown in Table 2.
  • the etching rate of the copper-based metal film using the etching solution composition of Examples 1 to 6 was found to be appropriate.
  • the copper-based metal film etched with the etchant composition of Example 1 showed a good etching profile. 3, when the copper film-based metal film was etched with the etching solution composition according to Example 1, no etching residues remained.
  • the etchant composition of the present invention provides excellent tapered profile of the copper-based metal film, the linearity of the pattern, and an appropriate etching rate, in particular, it can be seen that it has a characteristic that no residue remains after etching.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention concerne un procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides, selon lequel une composition de solution de gravure est utilisée qui comporte, par rapport au poids total de la composition, a) entre 5 et 25% en poids de peroxyde d'hydrogène (H2O2); b) entre 0,1 et 5% en poids d'acide sulfurique ; c) entre 0,01 et 1% en poids d'un composé fluoré ; d) entre 0,1 et 5% en poids d'un composé azole ; e) entre 0,1 et 5% en poids d'un composé imidazole ; et f) le reste étant de l'eau.
PCT/KR2010/005019 2010-07-30 2010-07-30 Procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides Ceased WO2012015088A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/KR2010/005019 WO2012015088A1 (fr) 2010-07-30 2010-07-30 Procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides
CN201080068296.0A CN103026293B (zh) 2010-07-30 2010-07-30 用于制造液晶显示装置用阵列基板的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2010/005019 WO2012015088A1 (fr) 2010-07-30 2010-07-30 Procédé pour la production d'un substrat de réseau pour un dispositif d'affichage à cristaux liquides

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WO2012015088A1 true WO2012015088A1 (fr) 2012-02-02

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WO (1) WO2012015088A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN103627400A (zh) * 2012-08-22 2014-03-12 易安爱富科技有限公司 钼合金膜与氧化铟膜液体腐蚀剂组成物质

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KR20170056279A (ko) * 2015-11-13 2017-05-23 동우 화인켐 주식회사 은 식각액 조성물
CN114164003A (zh) * 2021-12-06 2022-03-11 Tcl华星光电技术有限公司 用于显示面板的蚀刻剂组合物及显示面板的蚀刻方法

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CN101382712B (zh) * 2007-09-07 2010-12-08 北京京东方光电科技有限公司 液晶显示装置阵列基板的制造方法
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KR20050000682A (ko) * 2003-06-24 2005-01-06 엘지.필립스 엘시디 주식회사 구리(또는 구리합금층)를 포함하는 이중금속층을 일괄식각하기위한 식각액
KR20050067934A (ko) * 2003-12-29 2005-07-05 엘지.필립스 엘시디 주식회사 금속 배선의 형성방법 및 이를 이용한 액정표시장치의제조방법
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103627400A (zh) * 2012-08-22 2014-03-12 易安爱富科技有限公司 钼合金膜与氧化铟膜液体腐蚀剂组成物质
CN103627400B (zh) * 2012-08-22 2016-02-17 易安爱富科技有限公司 钼合金膜与氧化铟膜液体腐蚀剂组成物质

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CN103026293A (zh) 2013-04-03
CN103026293B (zh) 2016-01-13

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