KR101805187B1 - An etching solution composition - Google Patents

An etching solution composition Download PDF

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KR101805187B1
KR101805187B1 KR1020100104831A KR20100104831A KR101805187B1 KR 101805187 B1 KR101805187 B1 KR 101805187B1 KR 1020100104831 A KR1020100104831 A KR 1020100104831A KR 20100104831 A KR20100104831 A KR 20100104831A KR 101805187 B1 KR101805187 B1 KR 101805187B1
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film
metal film
weight
array substrate
composition
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KR1020100104831A
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Korean (ko)
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KR20110047983A (en
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양승재
이석준
권오병
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동우 화인켐 주식회사
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Priority to KR1020100104831A priority Critical patent/KR101805187B1/en
Priority to JP2012536673A priority patent/JP5753180B2/en
Priority to CN201080049609.8A priority patent/CN102597162B/en
Priority to PCT/KR2010/007417 priority patent/WO2011052989A2/en
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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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
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  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Weting (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mathematical Physics (AREA)
  • ing And Chemical Polishing (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

The present invention relates to a composition comprising 45 to 70% by weight phosphoric acid based on the total weight of the composition; 2 to 10% by weight of nitric acid; 5 to 25% by weight of acetic acid; 0.01 to 3% by weight of a fluorine compound; 0.1 to 5% by weight of phosphate; And an amount of water remaining. The present invention also relates to an etchant composition for a triple film comprising In, Al and Mo.

Description

AN ETCHING SOLUTION COMPOSITION [0001]

The present invention relates to a flat panel display device comprising a pixel electrode including indium, a source / drain electrode including aluminum, and a triple film including In, Al and Mo capable of collectively etching a buffer film containing molybdenum A method of manufacturing an array substrate for a flat panel display device using the etchant composition, and an array substrate for a flat panel display manufactured thereby.

The process of forming a metal wiring on a substrate in a flat panel display typically includes a process of forming a metal film by sputtering, a process of applying a photoresist on a metal film, exposing and developing it to form a photoresist in a selective region, And etching the film. It also includes cleaning processes before and after individual unit processes. This etch process refers to a process that uses a photoresist as a mask to leave a metal film in a selective region. As the etching process, dry etching using plasma or wet etching using an etching solution is usually used.

On the other hand, a transparent conductive film containing indium as a main component is mainly used as a pixel electrode in a flat panel display. In addition, an aluminum film or an aluminum alloy film, particularly Al-La-X (X = Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, , Sn, Fe, Si, Mo, Pt, and C) is mainly used. In addition, a molybdenum film or an alloy film containing molybdenum as a main component is mainly used as a buffer film which acts as a buffer on the top / bottom of the source / drain electrode.

Conventionally, in order to etch the pixel electrode, the source / drain electrode, and the buffer film of the flat panel display device, it is necessary to use etchant compositions different for each electrode. For example, Korean Patent No. 10-0502796 discloses an etchant for indium tin oxide which is a pixel electrode. Korean Patent Laid-Open No. 10-2006-0066349 discloses an etchant composition for a single metal alloy film composed of aluminum, nickel, and an additive metal which are source / drain electrodes.

However, if different etchant compositions are used to etch the pixel electrode, the source / drain electrode, and the buffer layer, the etch process becomes complicated and uneconomical.

It is an object of the present invention to provide an etchant composition for a triple film comprising In, Al, and Mo capable of batch wet etching a triple film including a pixel electrode, a source / drain electrode, and a buffer film.

It is also an object of the present invention to provide an etchant composition for a triple film comprising In, Al and Mo having uniform etching properties.

It is also an object of the present invention to provide a method of manufacturing an array substrate for a flat panel display device using the etchant composition and an array substrate for a flat panel display manufactured thereby.

The present invention relates to a composition comprising 45 to 70% by weight phosphoric acid based on the total weight of the composition; 2 to 10% by weight of nitric acid; 5 to 25% by weight of acetic acid; 0.01 to 3% by weight of a fluorine compound; 0.1 to 5% by weight of phosphate; And an amount of residual water. The present invention also provides an etchant composition for a trilayer film comprising ITO, Al and Mo.

In addition, the present invention provides a method for manufacturing an array substrate for a flat panel display, which comprises etching a triple film including ITO, Al and Mo using the etching liquid composition.

Further, the present invention provides an array substrate for a flat panel display, comprising a pixel electrode, a source / drain electrode, and a buffer film formed using the etchant composition.

The flat panel display array substrate may be a thin film transistor (TFT) array substrate.

The etchant composition of the present invention is characterized in that the transparent conductive film containing indium as a main component and the aluminum or aluminum alloy film used as the source / drain electrode, particularly Al-La-X (X = Mg, Zn, In, Ca, Te, An aluminum alloy film in the form of one or more elements selected from the group consisting of Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Mo, The molybdenum film or the alloy film containing molybdenum as a main component can be collectively etched. In addition, the etching solution composition of the present invention essentially solves the curling phenomenon on the metal film and exhibits uniform etching characteristics.

FIG. 1 is a photograph showing the etch profile of an ITO / Al-La-Ni / Mo triple layer etched with the etchant composition of Example 2. FIG.
FIG. 2 is a photograph showing the residue of an ITO / Al-La-Ni / Mo triple film etched with the etchant composition of Example 2. FIG.
FIG. 3 is a photograph showing the etching profile of the lower Mo of the ITO / Al-La-Ni / Mo triple layer etched with the etching composition of Comparative Example 1. FIG.
Figure 4 is a photograph after the strip of Figure 3;
5 is a photograph showing the etch profile of the upper ITO of the ITO / Al-La-Ni / Mo triple layer etched with the etchant composition of Comparative Example 2. FIG.
6 is a photograph showing the etching profile of lower Mo of an ITO / Al-La-Ni / Mo triple layer etched with the etching composition of Comparative Example 2. FIG.

Hereinafter, the present invention will be described in detail.

The etching composition for a triple film containing ITO, Al and Mo of the present invention includes phosphoric acid, nitric acid, acetic acid, fluorine compound, phosphate and water balance.

The phosphoric acid contained in the etchant composition of the present invention may be included as a main oxidizing agent in an amount of 45 to 70% by weight based on the total weight of the composition, more preferably 50 to 60% by weight. When the above-described range is satisfied, it is possible to etch the metal film including molybdenum and the metal film including aluminum, to easily adjust the etching rate, and to realize uniform etching characteristics.

The nitric acid silver-containing oxidizing agent contained in the etchant composition of the present invention may be contained in an amount of 2 to 10 wt%, more preferably 3 to 9 wt%, based on the total weight of the composition. When the above range is satisfied, it is possible to etch the metal film including molybdenum and the aluminum film together with the phosphoric acid, and it is easy to control the etching speed, the side etch, and the taper angle.

The nitric acid contained in the etchant composition of the present invention is a buffer for controlling the reaction rate, and is contained in an amount of 5 to 25% by weight based on the total weight of the composition, more preferably 10 to 20% by weight. When the above range is satisfied, the etching rate can be improved by appropriately adjusting the reaction rate.

The fluorine-containing compound contained in the etchant composition of the present invention may be contained in an amount of 0.01 to 3% by weight based on the total weight of the composition, more preferably 0.05 to 1% by weight. When it is included in the above-mentioned range, it is possible to etch a metal film containing oxidized aluminum, a metal film containing molybdenum, and a metal film containing In.

The fluorinated compound is a compound capable of dissociating into fluorine ion or polyatomic fluorine ion. The fluorinated compound is preferably one or more selected from the group consisting of ammonium fluoride, sodium fluoride, phosphoric acid, ammonium fluoride, sodium fluoride, and phosphoric acid.

The phosphate contained in the etchant composition of the present invention may be contained in an amount of 0.1 to 5% by weight based on the total weight of the composition, and may be 0.5 to 3% by weight based on the total weight of the composition, More preferably, When included in the above range, the etching rate of the metal film including molybdenum and the metal film including aluminum can be easily controlled, and uniform etching characteristics can be realized.

The phosphate may be prepared by reacting 1 to 3 hydrogen atoms contained in phosphoric acid with a monovalent or divalent cation Lt; / RTI > Examples of the monovalent or divalent cation include ammonium, alkali metal ions, and alkaline earth metal ions. Specific examples of the phosphate include ammonium hydrogen phosphate, potassium dihydrogen phosphate, etc. These may be used alone or in combination of two or more.

The water contained in the etchant composition of the present invention means deionized water and is used for semiconductor processing, and preferably water of 18 M / cm or more is used. The water is contained in the balance such that the total weight of the etchant composition of the present invention is 100% by weight.

The etchant composition of the present invention may further contain one or more selected from the group consisting of an etching control agent, a surfactant, a sequestering agent, and a corrosion inhibitor in addition to the above-mentioned components.

In the present invention, the triple films including ITO, Al and Mo include triple films consisting of an ITO film, a metal film containing aluminum, and a metal film containing molybdenum. The metal film containing aluminum is preferably an aluminum film or an aluminum alloy film. The aluminum alloy film is represented by Al-La-X wherein X is at least one element selected from the group consisting of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, , Pt, and C, or a mixture of two or more thereof.

The present invention relates to a transparent conductive film mainly composed of indium as a pixel electrode, that is, an aluminum or aluminum alloy film, particularly Al-La-X (X = Mg, Zn, In, Ca, Te, An aluminum alloy film in the form of one or more elements selected from the group consisting of Sr, Cr, Co, Mo, Nb, Ta, W, Ni, Nd, Sn, Fe, Si, Mo, , Or an alloy film containing molybdenum as a main component.

Hereinafter, the present invention will be described in more detail by way of Examples and Test Examples. However, the scope of the present invention is not limited by the following examples and test examples.

Examples 1 to 5, Comparative Examples 1 to 3: Preparation of an etching liquid composition

The composition of the etchant was prepared to be 180 kg according to the ingredients and composition ratio shown in Table 1 below.

Phosphoric acid
(weight%) nitric acid
(weight%) Acetic acid
(weight%) Ammonium bisulfite
(weight%) Ammonium phosphate
(weight%) water Example 1 55 5 12 0.2 2 Balance Example 2 55 7 15 0.3 3 Balance Example 3 60 7 12 0.1 One Balance Example 4 60 5 17 0.3 One Balance Example 5 55 9 15 0.1 2 Balance Comparative Example 1 50 12 10 0 One Balance Comparative Example 2 60 9 12 0.05 0 Balance Comparative Example 3 60 10 15 4 3 Balance

Test Example: Characteristic Evaluation of Etchant Composition

<Evaluation of etching characteristics>

A substrate on which ITO / Al-La-Ni / Mo triplet deposited on the glass and patterned with a photoresist in a certain shape was used. The etchant compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were placed in an experimental apparatus (SEMES, model name: ETCHER (TFT)) of a spray-type etching system, and the temperature was set to 40 ° C. Then, after reaching a temperature of 40 +/- 0.1 DEG C, an etching process was performed. The total etching time was 60% based on the EPD. When the etching was completed, the test piece was injected. After the etching was completed, the substrate was washed with deionized water, dried using a hot air drying apparatus, and photoresist was removed using a photoresist (PR) stripper. After cleaning and drying, the inclination angle, side etch (CD (criMocal dimension) loss, etch residue and underlying film damage were evaluated using an electron microscope (SEM; model name: S-4700, The results are shown in Table 2 and Figs.

Types of Thin Films Etching profile Underlying membrane damage Residue Example 1 ITO / Al-La-Ni / Mo ◎ none none Example 2 ◎ none none Example 3 ◎ none none Example 4 ◎ none none Example 5 ○ none none Comparative Example 1 Lower Mo unetch Comparative Example 2 × none none Comparative Example 3 × has exist none

[Evaluation Criteria of Etching Profile]

⊚: very good (CD Skew: ≤1 μm, Taper Angle: 45 ° to 80 °)

?: Excellent (CD Skew:? 1.5 m, Taper Angle: 45 to 80)

?: Good (CD Skew:? 2 mu m, Taper Angle: 45 to 80)

X: Bad (metal film disappearance and residue)

Referring to Table 2, the metal films etched with the etchant compositions of Examples 1 to 6 exhibited excellent etch profile, lower film damage, and no residue. However, when etching with the etchant compositions of Comparative Examples 1 to 3, the etch profile was not good and bad results were obtained with molybdenum films having free etch, residue and underlying film damage.

1 is a photograph showing an etching profile of a metal film etched with the etching solution composition of Example 2. Fig. FIG. 2 is a photograph showing the residue of a metal film etched with the etching solution composition of Example 2. FIG. 3 is a photograph showing the etching profile of the lower Mo of the metal film etched with the etching solution composition of Comparative Example 1. Fig. 4 is a photograph showing a strip after a metal film etched with the etchant composition of Comparative Example 1. Fig. 5 is a photograph showing the etching profile of the upper ITO of the metal film etched with the etchant composition of Comparative Example 2. Fig. 6 is a photograph showing the lower Mo of the metal film etched by the etchant composition of Comparative Example 2. Fig.

Referring to FIGS. 1 to 6, when the metal film is etched with the etchant composition of Example 2, it is found that the etch profile is excellent and there is no residue. On the other hand, when the metal film is etched with the etchant composition of Comparative Example 1, the underlying molybdenum film is not etched. Further, when the metal film is etched with the etchant composition of Comparative Example 2, a tip is generated in ITO which is an upper film, and an undercut occurs in molybdenum in a lower film.

Claims (10)

45 to 70% by weight, based on the total weight of the composition, of phosphoric acid; 2 to 10% by weight of nitric acid; 5 to 25% by weight of acetic acid; 0.01 to 3% by weight of a fluorine compound; 0.1 to 5% by weight of phosphate; And a water balance, wherein the metal film comprises an ITO film, a metal film containing aluminum, and a metal film containing molybdenum. [4] The method according to claim 1, wherein the fluorine compound is at least one selected from the group consisting of ammonium fluoride, sodium fluoride, fluorophosphoric acid, ammonium fluoride, sodium bisulfite, , A metal film containing aluminum, and a metal film containing molybdenum. [3] The method according to claim 1, wherein the phosphate is at least one selected from the group consisting of ammonium phosphate and potassium dihydrogenphosphate. The ITO film, the metal film containing aluminum, and the metal containing molybdenum Film etching solution composition for a three-layer film. delete The batch etchant composition of a ternary film comprising an ITO film, a metal film comprising aluminum, and a metal film comprising molybdenum, characterized in that the metal film comprising aluminum is an aluminum film or an aluminum alloy film . The method of claim 5, wherein the aluminum alloy film is represented by Al-La-X, wherein X is at least one element selected from the group consisting of Mg, Zn, In, Ca, Te, Sr, Cr, Co, Mo, Nb, Ta, W, Ni, And a metal film including molybdenum, and at least one selected from the group consisting of Fe, Si, Mo, Pt, and C, Etchant composition. A process for producing an array substrate for a flat panel display, comprising the step of collectively etching a triple film comprising an ITO film, a metal film containing aluminum, and a metal film containing molybdenum, using the etching liquid composition of claim 1 Way. The method of manufacturing an array substrate for a flat panel display according to claim 7, wherein the array substrate for a flat panel display is a thin film transistor array substrate. An array substrate for a flat panel display, comprising a pixel electrode, a source / drain electrode, and a buffer film formed using the etching liquid composition of claim 1. The flat panel display array substrate according to claim 9, wherein the flat panel display array substrate is a thin film transistor array substrate.
KR1020100104831A 2009-10-30 2010-10-26 An etching solution composition KR101805187B1 (en)

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KR1020100104831A KR101805187B1 (en) 2009-10-30 2010-10-26 An etching solution composition
JP2012536673A JP5753180B2 (en) 2009-10-30 2010-10-27 Etching solution composition
CN201080049609.8A CN102597162B (en) 2009-10-30 2010-10-27 Etching solution composition
PCT/KR2010/007417 WO2011052989A2 (en) 2009-10-30 2010-10-27 Etching solution composition

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KR101361839B1 (en) * 2011-10-27 2014-02-11 한국항공대학교산학협력단 Etchant composition, and method for etching a multi-layered metal film
KR101394469B1 (en) * 2012-07-20 2014-05-13 한국항공대학교산학협력단 Etchant composition, and method for etching a multi-layered metal film
KR101404511B1 (en) * 2012-07-24 2014-06-09 플란제 에스이 Etchant composition, and method for etching a multi-layered metal film
KR102091541B1 (en) * 2014-02-25 2020-03-20 동우 화인켐 주식회사 Preparing method for organic light emitting display device
JP2016025321A (en) * 2014-07-24 2016-02-08 関東化學株式会社 Etchant composition and etching method
KR102254561B1 (en) * 2014-09-30 2021-05-21 동우 화인켐 주식회사 Etchant composition for silver nanowires
CN105463463B (en) * 2015-11-25 2018-04-24 江阴江化微电子材料股份有限公司 A kind of AMOLED ITO-Ag-ITO etching solutions
KR102384563B1 (en) * 2016-03-24 2022-04-08 동우 화인켐 주식회사 Composition for Etching Indium Oxide Layer
CN107620066A (en) * 2017-09-14 2018-01-23 合肥惠科金扬科技有限公司 A kind of display screen acidic etching liquid
CN109439329A (en) * 2018-10-29 2019-03-08 苏州博洋化学股份有限公司 FPD array process novel I GZO etching solution
CN110195229B (en) * 2019-06-21 2021-05-14 湖北兴福电子材料有限公司 Etching solution for tungsten and titanium nitride metal film and use method thereof

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KR100444345B1 (en) * 2002-03-28 2004-08-16 테크노세미켐 주식회사 Etchant for making metal electrodes of TFT in FPD
JP2005163070A (en) * 2003-11-28 2005-06-23 Sharp Corp Etching solution, and etching method
KR101216651B1 (en) * 2005-05-30 2012-12-28 주식회사 동진쎄미켐 etching composition
JP4864434B2 (en) * 2005-11-29 2012-02-01 エルジー ディスプレイ カンパニー リミテッド Etching composition for thin film transistor liquid crystal display device
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KR20110047983A (en) 2011-05-09
CN102597162B (en) 2014-10-01
WO2011052989A2 (en) 2011-05-05
JP2013509703A (en) 2013-03-14
CN102597162A (en) 2012-07-18
WO2011052989A3 (en) 2011-09-15

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