KR20130070517A - Manufacturing method of an array substrate for liquid crystal display - Google Patents

Manufacturing method of an array substrate for liquid crystal display Download PDF

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KR20130070517A
KR20130070517A KR1020120133091A KR20120133091A KR20130070517A KR 20130070517 A KR20130070517 A KR 20130070517A KR 1020120133091 A KR1020120133091 A KR 1020120133091A KR 20120133091 A KR20120133091 A KR 20120133091A KR 20130070517 A KR20130070517 A KR 20130070517A
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copper
etching
acid
weight
film
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KR1020120133091A
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Korean (ko)
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윤영진
유인호
조성배
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동우 화인켐 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • 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
    • G02F1/136286—Wiring, e.g. gate line, drain line
    • 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
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/45—Ohmic electrodes
    • H01L29/456—Ohmic electrodes on silicon
    • H01L29/458—Ohmic electrodes on silicon for thin film silicon, e.g. source or drain electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/4908—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET for thin film semiconductor, e.g. gate of TFT

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  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

PURPOSE: A method for manufacturing an array substrate for a liquid crystal display device is provided to improve the etching efficiency of a copper metal layer by maintaining an etch property using an etchant composition instead of hydrogen peroxide. CONSTITUTION: After a gate electrode is formed on a substrate, a gate insulating layer is formed on the substrate. After a semiconductor layer is formed on the gate insulating layer, a source/drain electrode is formed on the semiconductor layer. A pixel electrode is formed. The gate electrode and the source/drain electrode are formed by etching a copper metal layer. The etchant composition includes peracetic acid 1 to10 weight %, fluorine compound 0.01 to 2 weight %, water-soluble cyclic amine compound 0.01 to 5.0 weight %, organic acid/inorganic acid 0.1 to 5 weight %, and water.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an array substrate for a liquid crystal display

The present invention relates to a method of manufacturing an array substrate for a liquid crystal display device; An etchant composition of a copper-based metal film; And a method of etching a copper-based metal film using the etchant composition.

The process of forming a metal wiring on a substrate in a semiconductor device is generally composed of a metal film forming process by sputtering or the like, a photoresist coating process, a photoresist forming process in an optional region by exposure and development, and an etching process , A cleaning process before and after the individual unit process, and the like. This etching process refers to a process of leaving a metal film in a selective region using a photoresist as a mask. Typically, dry etching using plasma or wet etching using an etching composition is used.

In such a semiconductor device, resistance of metal wiring has recently become a major concern. This is because resolving the RC signal delay problem in TFT-LCD (thin film transistor-liquid crystal display) is a key factor in increasing the panel size and achieving a high resolution, because the resistance is a major factor causing the RC signal delay. Therefore, it is essential to develop a low-resistance material in order to realize reduction of the RC signal delay, which is indispensably required for enlarging the TFT-LCD.

Chromium which was mainly used conventionally (Cr, specific resistance: 12.7 × 10 -8 Ωm), molybdenum (Mo, specific resistance: 5 × 10 -8 Ωm), aluminum (Al, specific resistance: 2.65 × 10 -8 Ωm), and alloys thereof Is difficult to be used for gate and data wiring used in a large-sized TFT LCD. Therefore, a copper-based metal film such as a copper film and a copper molybdenum film and an etchant composition therefor are attracting attention as a low resistance metal film.

By the way, the development of the copper-based metal film is separate, and the etching liquid compositions for the copper-based metal film known to date do not sufficiently satisfy the needs of the user.

 For example, Korean Patent Laid-Open No. 10-2003-0082375 discloses an etching solution of a copper monolayer or a copper molybdenum film containing hydrogen peroxide water, an organic acid, a phosphate, a nitrogen, a fluorine compound and deionized water. Although the etching composition of the hydrogen peroxide etching composition is excellent in the etching property against the copper-based metal film, there is a danger in the process due to the overheating due to the chain decomposition reaction of hydrogen peroxide as the concentration of copper ions eluted into the etching solution increases. There is a problem that etching does not proceed.

Korean Patent Laid-Open No. 10-2009-0042173 discloses an etchant composition comprising ammonium perphosphate ((NH4) 2S2O8, ammonium persulfate), inorganic acid, acetate salt, fluorine-containing compound, sulfonic acid compound, azole- . Although the etchant composition solves the overheat stability, there is a problem that addition of a chelating agent is required for etching.

Korean Patent Publication No. 10-2003-0082375 Korean Patent Publication No. 10-2009-0042173

The present invention eliminates the hydrogen peroxide used as an oxidizing agent in the etching of a copper-based metal film and controls the concentration of copper ions present in the etchant at the time of etching to prevent the risk of overheating due to a chain decomposition reaction of hydrogen peroxide And an etchant composition for a copper-based metal film that maintains an etching property equal to or greater than that at the same time when a large amount of hydrogen peroxide is used.

In addition, an object of the present invention is to provide an etching liquid composition of a copper-based metal film which is excellent in linearity during etching and provides a low angle taper profile and does not generate residue of the metal film.

Another object of the present invention is to provide a copper-based metal film etchant composition capable of collectively etching gate electrodes, gate wirings, source / drain electrodes, and data wirings.

Another object of the present invention is to provide a method for manufacturing an array substrate for a liquid crystal display device using the etching solution composition of the copper-based metal film.

According to the present invention,

a) forming a gate electrode on a substrate;

b) forming a gate insulating layer on the substrate including the gate electrode;

c) forming a semiconductor layer on the gate insulating layer;

d) forming a source / drain electrode on the semiconductor layer; And

e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:

Step a) or step d) includes etching each copper-based metal film to form respective electrodes, wherein the etchant composition used for etching includes: A) peracetic acid 1 based on the total weight of the composition; To 10% by weight, B) 0.01 to 2% by weight of the fluorine-containing compound, C) 0.01 to 5% by weight of the water-soluble cyclic amine compound, D) 0.1 to 5% by weight of at least one selected from the group consisting of organic and inorganic acids, and F) It provides a manufacturing method of an array substrate for a liquid crystal display device, characterized in that it comprises a residual amount of water.

The step a) includes forming a copper-based metal film on the substrate, and etching the copper-based metal film with the etchant composition to form a gate electrode, and step d) includes forming a copper-based metal film on the semiconductor layer. And etching the copper-based metal layer with the etchant composition to form a source / drain electrode.

In addition, the present invention is based on the total weight of the composition, A) 1 to 10% by weight peracetic acid, B) 0.01 to 2% by weight fluorine-containing compound, C) 0.01 to 5% by weight water-soluble cyclic amine compound, D (1) 0.1 to 5% by weight selected from the group consisting of an organic acid and an inorganic acid, and F) a residual amount of an etching liquid composition comprising a residual amount of water.

In addition,

I) forming a copper-based metal film on a substrate;

II) selectively leaving a photoreactive material on the copper-based metal film formed in the step I); And

III) etching the copper-based metal film treated in the step (II) using the etchant composition of the present invention.

In the etching method, a conventional photoresist material may be used as the photoreactive material, and may be selectively left by a conventional exposure and development process.

In addition, the present invention provides an array substrate for a liquid crystal display device including any one or more of a gate electrode and a source / drain electrode etched using the etchant composition of the present invention.

The etchant composition of the present invention minimizes the content of peracetic acid and blocks the risk of overheating due to the chain decomposition reaction by eliminating hydrogen peroxide, while maintaining the etching characteristics equivalent to or higher than when using a large amount of hydrogen peroxide. The etching efficiency of the metal film is greatly improved.

In addition, the etchant composition of the present invention has the effect that the composition is easy to control the composition.

In addition, the etching solution composition of the present invention realizes a taper profile having excellent linearity when etching a copper-based metal film, and does not generate residues, and thus does not cause problems such as electrical shorts, poor wiring, and reduced luminance.

In addition, the etchant composition of the present invention enables batch etching of the gate electrode, the gate wiring, the source / drain electrode, and the data wiring, thereby simplifying the etching process and maximizing the process yield.

In addition, since the etchant composition of the present invention provides the above-mentioned effects, it can be very usefully used in manufacturing an array substrate for a liquid crystal display device in which a large-sized circuit and a high-brightness circuit are realized.

FIG. 1 is an SEM photograph of the surface of a copper / titanium double layer etched with the etchant composition of Example 1 of the present invention (Cu 0 ppm).
FIG. 2 is a SEM photograph (Cu 300 ppm) of the surface of a copper / titanium double layer etched with the etchant composition of Example 1 of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention is based on the total weight of the composition, A) 1 to 10% by weight peracetic acid, B) 0.01 to 2% by weight fluorine-containing compound, C) 0.01 to 5% by weight water-soluble cyclic amine compound, D) organic acid And at least one selected from the group consisting of inorganic acids 0.1 to 5% by weight, and F) a residual amount of the etching liquid composition comprising a metal film.

In the present invention, the copper-based metal film includes copper as a constituent of the film, and includes a single film of copper or a copper alloy (including a copper nitride film, a copper oxide film, etc.); And a multilayer film including at least one film selected from a copper film and a copper alloy film, and at least one film selected from the group consisting of molybdenum film, molybdenum alloy film, titanium film, and titanium alloy film.

Examples of the multilayer film include a double film such as a copper / molybdenum film, a copper / molybdenum alloy film, a copper alloy / molybdenum alloy film, a copper / titanium film, or a triple film. The copper / molybdenum film is meant to include a molybdenum layer and a copper layer formed on the molybdenum layer, and the copper / molybdenum alloy film means a copper layer formed on the molybdenum alloy layer and the molybdenum alloy layer, copper The alloy / molybdenum alloy film is meant to include a molybdenum alloy layer and a copper alloy layer formed on the molybdenum alloy layer, and the copper / titanium film means a titanium layer and a copper layer formed on the titanium layer.

In addition, the molybdenum alloy layer is, for example, at least one selected from the group consisting of titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), indium (In) and the like. A layer made of an alloy of metal and molybdenum.

In particular, the etchant composition of the present invention can be preferably applied to a copper alloy film or a copper / titanium film.

Acetate ions separated from A) and acetic acid (per acetic acid) included in the etchant composition of the present invention serves to control the etching rate of Cu through the interlocking with the copper surface.

The peracetic acid is preferably included in 1 to 10% by weight, more preferably 2 to 5% by weight based on the total weight of the composition. When the peracetic acid is contained in less than 1% by weight, the Cu etching power is significantly lowered, so it is difficult to maintain proper etching time, and the etching uniformity is lowered. When it exceeds 10% by weight, the Cu etching rate is significantly increased to control the Cu etching amount. Difficult and process control is also difficult.

B) fluorine compound included in the etchant composition of the present invention is a main component for etching the titanium metal film and at the same time remove the lower film residue.

The B) fluorine-containing compound is not particularly limited as long as it can be dissociated into fluorine ions or polyatomic fluoride ions in solution as a material commonly used in the art. For example, ammonium fluoride (NH 4 F), sodium fluoride (NaF), potassium fluoride (KF), ammonium bifluoride (NH 4 FHF), sodium bifluoride (sodium bifluoride: NaFHF), potassium bifluoride (KFHF), and the like, and these may be used alone or in combination of two or more thereof.

The fluorine-containing compound is preferably included in an amount of 0.01 to 2% by weight, more preferably 0.1 to 1% by weight based on the total weight of the composition. If the fluorine-containing compound is contained in less than 0.01% by weight may cause metal etching residue, when contained in more than 2% by weight may cause a problem that the glass damage of the glass substrate increases.

C) water-soluble cyclic amine compound included in the etchant composition of the present invention controls the etching rate of the copper-based metal and serves to increase the process margin by reducing the CD loss of the pattern. The C) water-soluble cyclic amine compound is preferably included in 0.01 to 5% by weight, more preferably in 0.01 to 3% by weight based on the total weight of the composition. When the content of the C) water-soluble cyclic amine compound is less than 0.01% by weight, cisidose may be generated too large, and when it exceeds 5% by weight, the etching speed of copper is increased and the etching rate of molybdenum or molybdenum alloy is slow. The loss of CDiros increases and the possibility of molybdenum or molybdenum alloy residues increases.

The C) water-soluble cyclic amine compound is aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, Pyrrole (pyrrole), pyrrolidine (pyrrolidine), pyrroline (pyrroline) and the like, these may be used alone or in combination of two or more.

At least one selected from the group consisting of D) organic acid and inorganic acid included in the etchant composition of the present invention serves to adjust the pH to create an environment in which the copper-based metal film can be etched, and to lower the pH to inhibit peracetic acid decomposition do.

The at least one content selected from the group consisting of organic acids and inorganic acids is preferably 0.1 to 5% by weight, and less than 0.1% by weight based on the total weight of the composition, and at least one selected from the group consisting of organic and inorganic acids. In this case, there is a problem of accelerating peracetic acid decomposition due to lack of influence of pH adjustment, and at the same time, the rate of deterioration of copper's etching performance may increase rapidly. If the content exceeds 5% by weight, the copper's etching rate is increased and barrier ( Barrie) Because the etching speed of titanium, which is a film quality, is slowed down, CD Loss is increased compared to titanium film and residue of titanium film may be caused.

Examples of the organic acid include compounds having an amino group and a carboxyl group, such as acetic acid, glycolic acid, citric acid, oxalic acid, and iminodiacetic acid. Examples of the inorganic acid include nitric acid compounds such as nitric acid and nitrous acid, sulfuric acid, phosphoric acid, and perchloric acid. have. In particular, at least one selected from the group consisting of organic and inorganic acids may be preferably used with acetic acid, nitric acid-based compounds and compounds having amino and carboxyl groups.

The etchant composition of the present invention may further comprise E) a water-soluble compound having a nitrogen atom and a sulfonic acid.

E) The water-soluble compound having the nitrogen atom and sulfonic acid included in the etchant composition of the present invention has the effect of increasing the shelf life of the product by inhibiting the decomposition rate of peracetic acid, which has a relatively high self-decomposition rate, than the permeable system. .

E) The water-soluble compound having a nitrogen atom and sulfonic acid is preferably included in 0.1 to 5% by weight based on the total weight of the composition. When the water-soluble compound having a nitrogen atom and a sulfonic acid is contained in an amount of less than 0.1% by weight, the decomposition ability of peracetic acid is remarkably decreased and it is difficult to secure the stability of the peracetic acid etchant over time. When the amount exceeds 5% by weight, It is difficult to control the etching amount and also it is difficult to control the process.

E) The water-soluble compound having a nitrogen atom and a sulfonic acid in one molecule is preferably one or two or more selected from the group consisting of sulfamic acid, sulfonamide and derivatives thereof.

F) water contained in the etching liquid composition of this invention is not specifically limited, 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 kW / cm or more is used.

In addition to the above-mentioned components, conventional additives may be further added to the etchant composition of the present invention. Typical examples of the additive include metal ion sequestrants and corrosion inhibitors.

At least one selected from the group consisting of A) per acetic acid, B) fluorine-containing compound, C) water-soluble cyclic amine compound, D) organic acid and inorganic acid used in the etchant composition of the present invention, and E) The remaining amount of water preferably has a purity for the semiconductor process.

The etchant composition of the present invention can collectively etch the gate electrode, the gate wiring, the source / drain electrode, and the data wiring of the liquid crystal display device made of a copper-based metal film, and can also etch the indium oxide film.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example  1 and Comparative example  1 to 2: Etchant  Preparation of the composition

According to the composition shown in Table 1, each component was mixed to prepare each of the etching solution composition of Example 1 and Comparative Examples 1 to 2 by 6 kg.

Peracetic acid NH 4 HF 2 Water soluble cyclic amine compound nitric acid Deionized water Example 1 4.0 0.5 0.5 2.0 93.0 Comparative Example 1 4.0 0.5 0.5 0.01 94.9 Comparative Example 2 4.0 0.5 0.5 7.0 88.0

                                                         (Unit: wt%)

Test Example  One: Etchant  Of the composition Evaluation of etching characteristics

The Cu / Ti metal film deposited on the glass substrate by the sputtering method was etched using the etchant compositions of Example 1, Comparative Example 1 and Comparative Example 2 prepared above. The etching solution was injected into an experimental apparatus (model name: ETCHER (TFT), SEMES) of a spray-type etching system, the temperature was raised to 28 ° C, and the etching process was performed when the temperature reached 28 ± 0.1 ° C. The total etching time of the Cu / Ti metal film was performed by giving 100% of the over etching based on the endpoint detection (EPD). The substrate was sprayed, and when the etching was completed, the substrate was ejected, removed, washed with deionized water, dried using a hot air dryer, and removed using a photoresist stripper. After washing and drying, the etching characteristics were evaluated using an electron scanning microscope (SEM; model name: S-4700, manufactured by HITACHI Co., Ltd.), and the results are shown in Table 2, FIGS. 1 and 2.

Membrane Side Etch (μm)
(Cu 0 ppm) Taper Angle (°)
(Cu 0 ppm) Side Etch (μm)
(Cu 3000ppm) Taper Angle (°)
(Cu 3000ppm) Example 1 Cu / Ti 1.45 26.2 1.35 27.6 Comparative Example 1 Cu / Ti          - - Cu EPD 6 sec Delay Cu EPD 6 sec Delay Comparative Example 2 Cu / Ti Pattern out Pattern out Pattern out Pattern out

As can be seen in Table 3, Figure 1 (Cu 0 ppm) and Figure 2 (Cu 3000ppm), the etchant composition of Example 1 exhibited good etching characteristics. However, in the etching solution of Comparative Example 2, excessive amount of nitric acid was included so that Pattern Out occurred due to over etching of Cu. In the case of the etching solution of Example 1, when the Cu was 0 ppm and the Cu was eluted at 3000 ppm, the S / E change rate after Cu / Ti etching was less than 10%. However, in the etching liquid composition of Comparative Example 1 containing a very small amount of nitric acid, when the 3000 ppm of Cu eluted, it can be seen that the EPD after the Cu / Ti etching was greatly reduced.

Test Example  2: Etchant  Evaluation of shelf life characteristics of composition

Using the etching solution compositions of Examples 2 to 4, each of which added Sulfamic Acid to each of Example 1 prepared above, the etching solution composition was set to an expiration date immediately before the etching rate of the metal to be etched after storage at room temperature.

And acetic acid NH 4 HF 2 Water soluble cyclic
Amine compound nitric acid Sulfamic acid Deionized water Validity
(Room temperature, day) Example 2 4 0.5 0.5 2.0 2.0 93 3 day Example 1 4 0.5 0.5 2.0 - 95 1 day Example 3 4 0.5 0.5 2.0 1.0 94 2 day Example 4 4 0.5 0.5 2.0 3.0 92 3 day

Referring to Example 2 in Table 3, when the sulfamic acid 2.0% is added, the change in Etchant's own aging is not significant, and thus the usable shelf life is extended to 200 days compared to Example 1 as the available shelf life is 3 days. In Example 3, the shelf life was extended by 1 day compared with Example 1, and in Example 4, 3% of sulfamic acid was added, but the shelf life was not longer.

Claims (12)

a) forming a gate electrode on a substrate;
b) forming a gate insulating layer on the substrate including the gate electrode;
c) forming a semiconductor layer on the gate insulating layer;
d) forming a source / drain electrode on the semiconductor layer; And
e) forming a pixel electrode connected to the drain electrode, the method comprising the steps of:
Step a) or step d) includes etching each copper-based metal film to form respective electrodes, wherein the etchant composition used for etching includes: A) peracetic acid 1 based on the total weight of the composition; To 10% by weight, B) 0.01 to 2% by weight of the fluorine-containing compound, C) 0.01 to 5% by weight of the water-soluble cyclic amine compound, D) 0.1 to 5% by weight of at least one selected from the group consisting of organic and inorganic acids, and E) A method of manufacturing an array substrate for a liquid crystal display device, characterized in that it contains residual amount of water. The method of manufacturing an array substrate for a liquid crystal display device according to claim 1, wherein the array substrate for liquid crystal display device is a thin film transistor (TFT) array substrate. The method according to claim 1,
The etching liquid composition used for the etching, E) 0.1 to 5% by weight of the water-soluble compound having a nitrogen atom and sulfonic acid with respect to the total weight of the composition, the manufacturing method of an array substrate for a liquid crystal display device. A) 1 to 10% by weight peracetic acid, B) 0.01 to 2% by weight fluorine-containing compound, C) 0.01 to 5% by weight of water-soluble cyclic amine compound, D) organic and inorganic acids 0.1 to 5% by weight of at least one selected from the group consisting of, and E) the etching liquid composition of the copper-based metal film comprising a residual amount of water. The method of claim 4,
The etchant composition of the copper-based metal film is E) 0.1 to 5% by weight of the water-soluble compound having a nitrogen atom and sulfonic acid. The copper-based compound according to claim 4, wherein the B) fluorine-containing compound is one or two or more selected from the group consisting of ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride and potassium bifluoride. Etch solution composition of the metal film. The method according to claim 4, wherein the C) water-soluble cyclic amine compound is one selected from the group consisting of aminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine and pyrroline Etching liquid composition of a copper-based metal film, characterized in that two or more kinds. The method according to claim 4, wherein at least one selected from the group consisting of D) an organic acid and an inorganic acid is acetic acid, glycolic acid, citric acid, oxalic acid, a compound having an amino group and a carboxyl group, a nitric acid compound, sulfuric acid, phosphoric acid, and perchloric acid Etching liquid composition of the copper-based metal film, characterized in that it is selected from. The method of claim 5, wherein the water-soluble compound having a nitrogen atom and sulfonic acid is one or two or more selected from the group consisting of sulfamic acid, sulfaamide, and derivatives thereof. Etch solution composition of the metal film. The method of claim 4, wherein the copper-based metal film is a single film of copper or copper alloy; And a multilayer film including at least one film selected from a copper film and a copper alloy film, and at least one film selected from the group consisting of molybdenum film, molybdenum alloy film, titanium film, and titanium alloy film. Composition. I) forming a copper-based metal film on a substrate;
II) selectively leaving a photoreactive material on the copper-based metal film formed in the step I); And
III) Etching the copper-based metal film comprising the step of etching the copper-based metal film treated in step II) using the etching solution composition of claim 4. An array substrate for a liquid crystal display device comprising at least one of a gate electrode and a source / drain electrode etched using the etchant composition of claim 4.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170035225A (en) * 2015-09-22 2017-03-30 동우 화인켐 주식회사 Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170035225A (en) * 2015-09-22 2017-03-30 동우 화인켐 주식회사 Etchant composition for metal layer and preparing method of an array substrate for liquid crystal display using same

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