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WO2011028037A2 - Agent de gravure pour un affichage à cristaux liquides à transistors à couches minces - Google Patents

Agent de gravure pour un affichage à cristaux liquides à transistors à couches minces Download PDF

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Publication number
WO2011028037A2
WO2011028037A2 PCT/KR2010/005960 KR2010005960W WO2011028037A2 WO 2011028037 A2 WO2011028037 A2 WO 2011028037A2 KR 2010005960 W KR2010005960 W KR 2010005960W WO 2011028037 A2 WO2011028037 A2 WO 2011028037A2
Authority
WO
WIPO (PCT)
Prior art keywords
etchant
group
film
total weight
content
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/KR2010/005960
Other languages
English (en)
Other versions
WO2011028037A3 (fr
Inventor
Yong Sung Song
Tai Hyung Rhee
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.)
Techno Semichem Co Ltd
Original Assignee
Techno Semichem 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 Techno Semichem Co Ltd filed Critical Techno Semichem Co Ltd
Publication of WO2011028037A2 publication Critical patent/WO2011028037A2/fr
Publication of WO2011028037A3 publication Critical patent/WO2011028037A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H10P50/667—
    • 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
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/6729—Thin-film transistors [TFT] characterised by the electrodes
    • H10D30/6737—Thin-film transistors [TFT] characterised by the electrodes characterised by the electrode materials
    • H10D30/6739—Conductor-insulator-semiconductor electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H10D30/60—Insulated-gate field-effect transistors [IGFET]
    • H10D30/67—Thin-film transistors [TFT]
    • H10D30/674—Thin-film transistors [TFT] characterised by the active materials
    • H10D30/6741—Group IV materials, e.g. germanium or silicon carbide
    • H10D30/6743—Silicon

Definitions

  • the following disclosure relates to an etchant of a metal film and in particular, to a single layer selected from a copper film, a titanium film, a molybdenum film and an alloy film thereof or a multi-layer that the single layers are independently multi layered as many as more than two layers.
  • An embodiment of the present invention is directed to providing an etchant that performs bulk etching of a single layer selected from a copper film, a titanium film and a molybdenumfilm and an alloy film for forming a metal wiring; or a multi-layer that the single layers are independently multilayered as many as more than two layers, and that effectively adjust its etch rate, etching amount and taper angle.
  • an etchant of a metal film includes an organic chelating agent with an amino group and a carboxyl group; peroxides; oxidants fluorine compounds glycols; additives and deionized water.
  • the metal film is a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof; or a multilayer that the single layers are independently multilayered as many as more than two layers.
  • the present invention has advantages that bulk etching of a multi-layer that two or more layers are multilayered as well as a single layeris possible and another etching is also possible. Its process can be performed even in low temperature compared to other etching compositions.
  • the present invention relates to an etchant of metal films including 0.1 ⁇ 5wt of an organic chelating agent with an amino group and a carboxyl group; 5 - 25 wt%of peroxides; 0.5 ⁇ 5wt% of oxidants 0.1 ⁇ lwt% of fluorine compounds 1 ⁇ 10 wt% of glycols; and 0.1 ⁇ 5wt% of additives and deionized water contained to make the total weight of 100 wt .
  • the etchant according to the present invention has advantages that non-uniform etching occurring by high viscosity of the phosphorous etchant can be prevented and the safety problem can be solved when they are respectively mixed in the above-mentioned range, compared to the peroxide etchant.
  • the organic chelating agent may be one or more selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid and diethylene trinitrilo pentaacetic acid (DTPA), and the organic chelating agent may be 0.1 to 5wt% based on the total amount of the etchant.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylene trinitrilo pentaacetic acid
  • the organic chelating agent has a function thatprevents degradation of etching ability due to increased metal ions when the number of processed sheets of a metal film to be etched is increased.
  • the organic chelating agent exceeds 5 wt%, its effect is not increased as much as the amount of the increased chelating agents, which means inefficient. Also, there is a possibility to be precipitated since its solubility drops. And when the organic chelating agent is contained below 0.1 wt , it is not possible to prevent degradation of etching ability according to increase of the number of processed sheets of the metal film to be etched.
  • the peroxides are one or more selected from ammonium persulfate, sodium persulfate and patassium persulfate and its content may be 5 to 25wt% based on the total amount of the etchant.
  • the peroxides play a role of oxidizing the metal of the metal film. Specifically, the peroxides play a role of forming a copper oxide by oxidizing copper.
  • the peroxides are containedbelow 5wt%, the etching of the metal may be non-uniform, and when the peroxides are contained over 25wt%, there is a disadvantage that it maybe precipitated.
  • the oxidants according to the present invention are one or more selected from
  • the oxidant according to the present invention makes metal oxides generated by peroxides have solubility in water through substitution so that it can be dissolved in the etchant. More specifically, when the metal is copper, the copper oxide generated by peroxides is substituted by copper nitrate (Cu(N0 3 ) 2 )or copper sulfate, and the generated compound is dissolved in the etchant.
  • the content of the oxidant may be 0.5 ⁇ 5wt% of the entire compositions, and when it is below 0.5wt%, the etching of the metal film is not properly achieved. When the content of the oxidant exceeds 5wt%, it causesdamage of a substrate by enhancing activity of fluorine ions of fluorine compounds contained in the etchant.
  • the fluorine compound may be one or more selected from ammonium hydrogen fluoride (NH 4 F2), hexafluorosilicic acid (H 2 SiF 6 ) and potassium bifluoride (KHF 2 ), and its content may be 0.1 to lwt% based on the total amount of the etchant.
  • the fluorine compound is used for etching a metal film. When the fluorine compound exceeds 1 wt%, the substrate or silicone film maybe excessively etched. When the fluorine compound is contained below 0.1 wt , it remarkably degrades the etch rate of the metal film to cause generation of residues and tails and difficulty in a post-process. It is desirable that the fluorine compounds are included in a range that the substrate or silicone film is not etched.
  • a general substrate may be used without limitation, and more specifically, a glass substrate may be used.
  • the glycols may be one or more selected from ethylene glycol, polyethylene glycol and glycolic acid, and its content is 1 to 10wt% based on the total amount of the etchant.
  • the present invention can overcome a weak point in time change by using glycols, and it plays a role of a boiling point adjuster of the etchant. It is possible to overcome the weak point in time change when it is included in the range.
  • Examples of the additives may include azole compounds, and more preferably, one or more selected from 5-aminotetrazole, 1,2,3-benzotrazole, methylbenzotriazole and imidazole, and its content may be 0.1 to 5wt%based on the total amount of the etchant.
  • Critical Dimension CD which is a loss by etching, may become large.
  • the additives are contained more than5 wt%, the etch rate of the metal film may be retarded and a taper angle may be non-uniform. Accordingly, the preferred content according to the composition of the present invention should be included.
  • the residual amount of the entire compositions may be mixed with deionied water, and plays a role of diluting the etchant.
  • the loss due to etching is less than l.O/ffli, and the taper angle is 20°or more. Accordingly, the effective etching can be executed.
  • the metal film may be a single layer selected from a copper film, a titanium film, a molybdenum film and alloy films thereof: or a multi-layer thatthe single layers are independently multilayered as many as more than two layers.
  • the etchant according to the present invention is used for patterning of the metal film, which is a wiring material of a gate electrode and source/drain forming a Thin Film Transistor-Liquid Crystal Display (TFT-LCD).
  • TFT-LCD Thin Film Transistor-Liquid Crystal Display
  • the etchant according to the present invention forms uniform etching and has
  • the etchant has a uniform etching property by solving a spot problem due to high viscosity of a high composition of the phosphorous etchant.
  • the etchant has an advantage that bulk etching of the single layer as well as multi-layers is possible.
  • FIG. 1 is a picture showing a profile of a titanium film/copper film observed by
  • SEM Scanning Electron Microscope
  • FIG. 2 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Example 1 and performing strip of a photo resist of the titanium film/copper film.
  • FIG. 3 is a picture showing a profile of the titanium film/copper film oserved by the SEM after performing an etching process with the etchant of Comparative Example 1 according to the method suggested in Test Example 1.
  • FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example lwith the etchant of Comparative Example 1 and performing strip of the photo resist of the titanium film/copper film.
  • Table 2 showed a result obtained by measuring an etching loss and an i angle after performing an etching process with the etchant of Examples 1 Comparative Examples 1 to 4 according to the method described above.
  • 1 etching loss was 0.5pm 0.2pm or less and the inclination angle was 30 or 1 result of the properties evaluation was "excellent”.
  • the etching loss 0.3 m or less and the inclination angle was 20 or higher, the result of the evaluation was "good”.
  • the etching loss was obtained by observii the etched titanium film/copper film through Scanning Electron Microsa 4700 by Hitach Company) and measuring a distance between an end of tl and an end of the copper film.
  • the inclination angle was obtained b profile of the etched titanium film/copper film through Scanning Electroi (SEM, S-4700 by Hitach Company) and measuring a value of an inclinat an etched side.
  • FIG. 1 is a picture showing a profile of the titanium film/copper film ot SEM after performing an etching process with the etchant of Example la according to the method suggested in Test Example 1.
  • FIG. 4 is a picture showing a glass substrate observed by the SEM after performing the method suggested in Test Example 1 with the etchant of Comparative Example land performing strip of the photo resist of the titanium film/copper film. In FIG. 4, there are no tail and residues.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)
  • Thin Film Transistor (AREA)
  • Liquid Crystal (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)

Abstract

La présente invention se rapporte à un agent de gravure d'un film métallique comprenant un agent chélatant organique avec un groupe amino et un groupe carboxyle ; des peroxydes ; des composés de fluor oxydants ; des glycols ; des additifs et de l'eau déminéralisée. La présente invention se rapporte également à une composition d'un agent de gravure permettant la formation d'un motif d'un film de cuivre qui est un matériau de câblage d'une électrode grille ou d'une source/d'un drain formant un affichage à cristaux liquides à transistors à couches minces (TFT-LCD). L'agent de gravure génère une gravure uniforme et présente une excellente stabilité de sorte qu'il améliore l'effet de gravure non uniforme générée par une viscosité élevée, ce qui est un inconvénient de l'agent de gravure au phosphore, ainsi qu'une stabilité de l'agent de gravure au peroxyde. L'agent de gravure présente une propriété de gravure uniforme en résolvant le problème de tache dû à une viscosité élevée d'une composition importante de l'agent de gravure au phosphore. Une gravure en volume d'une seule couche ainsi que de multiples couches est possible.
PCT/KR2010/005960 2009-09-07 2010-09-02 Agent de gravure pour un affichage à cristaux liquides à transistors à couches minces Ceased WO2011028037A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090083770A KR101146099B1 (ko) 2009-09-07 2009-09-07 박막 트랜지스터 액정표시장치용 식각조성물
KR10-2009-0083770 2009-09-07

Publications (2)

Publication Number Publication Date
WO2011028037A2 true WO2011028037A2 (fr) 2011-03-10
WO2011028037A3 WO2011028037A3 (fr) 2011-07-07

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PCT/KR2010/005960 Ceased WO2011028037A2 (fr) 2009-09-07 2010-09-02 Agent de gravure pour un affichage à cristaux liquides à transistors à couches minces

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KR (1) KR101146099B1 (fr)
TW (1) TWI473910B (fr)
WO (1) WO2011028037A2 (fr)

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KR101922625B1 (ko) 2012-07-03 2018-11-28 삼성디스플레이 주식회사 금속 배선 식각액 및 이를 이용한 금속 배선 형성 방법
KR20140013310A (ko) 2012-07-23 2014-02-05 삼성디스플레이 주식회사 식각액 조성물, 및 이를 이용한 금속 배선과 박막 트랜지스터 표시판 제조 방법
KR102331036B1 (ko) 2014-10-10 2021-11-26 삼영순화(주) 에칭액 조성물 및 이를 이용하는 다층막의 에칭 방법
KR102487940B1 (ko) 2018-03-19 2023-01-16 삼성디스플레이 주식회사 식각액 조성물 및 이를 이용한 금속 패턴과 어레이 기판의 제조 방법
KR102648664B1 (ko) 2018-12-04 2024-03-19 삼성디스플레이 주식회사 식각액 조성물 및 이를 이용한 금속 패턴과 어레이 기판의 제조 방법
US12312695B2 (en) 2020-12-30 2025-05-27 Samsung Display Co., Ltd. Etchant composition, and method for manufacturing metal pattern and thin film transistor substrate using the same

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JP4668533B2 (ja) * 2001-07-06 2011-04-13 サムスン エレクトロニクス カンパニー リミテッド 配線用エッチング液とこれを利用した配線の製造方法及びこれを含む薄膜トランジスタ基板の製造方法
KR101174767B1 (ko) * 2005-03-10 2012-08-17 솔브레인 주식회사 금속배선 식각용액을 이용한 액정표시장치의 제조방법
KR20080015027A (ko) * 2005-06-13 2008-02-15 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 금속 규화물 형성 후 금속 또는 금속 합금의 선택적인제거를 위한 조성물 및 방법
KR101310310B1 (ko) * 2007-03-15 2013-09-23 주식회사 동진쎄미켐 박막트랜지스터 액정표시장치의 식각액 조성물
KR100883960B1 (ko) * 2007-10-01 2009-02-17 (주)이그잭스 구리 또는 구리 합금 막의 에칭제
KR101346976B1 (ko) * 2008-02-12 2014-01-03 동우 화인켐 주식회사 박막트랜지스터의 제조방법, 및 상기 방법에 이용되는식각액 조성물

Also Published As

Publication number Publication date
KR20110026050A (ko) 2011-03-15
TW201113395A (en) 2011-04-16
TWI473910B (zh) 2015-02-21
KR101146099B1 (ko) 2012-05-16
WO2011028037A3 (fr) 2011-07-07

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