KR102603630B1 - Manufacturing method of an array substrate for a display divice - Google Patents

Manufacturing method of an array substrate for a display divice Download PDF

Info

Publication number
KR102603630B1
KR102603630B1 KR1020160049998A KR20160049998A KR102603630B1 KR 102603630 B1 KR102603630 B1 KR 102603630B1 KR 1020160049998 A KR1020160049998 A KR 1020160049998A KR 20160049998 A KR20160049998 A KR 20160049998A KR 102603630 B1 KR102603630 B1 KR 102603630B1
Authority
KR
South Korea
Prior art keywords
weight
copper
film
composition
array substrate
Prior art date
Application number
KR1020160049998A
Other languages
Korean (ko)
Other versions
KR20170121505A (en
Inventor
유인호
김보형
남기용
Original Assignee
동우 화인켐 주식회사
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 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to KR1020160049998A priority Critical patent/KR102603630B1/en
Priority to CN201710271534.1A priority patent/CN107316836B/en
Publication of KR20170121505A publication Critical patent/KR20170121505A/en
Application granted granted Critical
Publication of KR102603630B1 publication Critical patent/KR102603630B1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • 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
    • 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
    • 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
    • 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
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • 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
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
    • 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
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film

Landscapes

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

Abstract

본 발명은 조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.01~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.1~5 중량%의 글리신, 0.5~6 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 구리계 금속막용 식각액 조성물, 및 그를 사용하는 표시장치용 어레이 기판의 제조 방법, 및 그에 의해 제조된 표시장치용 어레이 기판에 관한 것이다.The present invention is a composition comprising 15 to 25% by weight of hydrogen peroxide, 0.01 to 5% by weight of a fluorinated compound, 0.1 to 5% by weight of an azole compound, 0.1 to 5% by weight of glycine, and 0.5 to 6% by weight of alcohol, based on the total weight of the composition. An etchant composition for a copper-based metal film containing sulfamic acid, 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a residual amount of water, and a method for manufacturing an array substrate for a display device using the same, and a product manufactured thereby It relates to an array substrate for a display device.

Description

표시장치용 어레이 기판의 제조방법{MANUFACTURING METHOD OF AN ARRAY SUBSTRATE FOR A DISPLAY DIVICE}{MANUFACTURING METHOD OF AN ARRAY SUBSTRATE FOR A DISPLAY DIVICE}

본 발명은 표시장치용 어레이 기판의 제조방법, 구리계 금속막용 식각액 조성물, 및 표시장치용 어레이 기판에 관한 것이다. The present invention relates to a method of manufacturing an array substrate for a display device, an etchant composition for a copper-based metal film, and an array substrate for a display device.

반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링 등에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정 및 식각공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식식각 또는 식각액 조성물을 이용하는 습식식각이 사용된다.The process of forming metal wiring on a substrate in a semiconductor device typically consists of a metal film formation process by sputtering, photoresist application, a photoresist formation process in a selective area by exposure and development, and an etching process, Includes cleaning processes before and after individual unit processes. This etching process refers to a process of leaving a metal film in a selective area using a photoresist as a mask, and typically dry etching using plasma or the like or wet etching using an etchant composition is used.

종래에는 게이트와 소스/드레인 전극용 배선 재료로 알루미늄 또는 이의 합금과 다른 금속이 적층된 금속막이 사용되었다. 알루미늄은 가격이 저렴하고 저항이 낮은 반면, 내화학성이 좋지 못하고 후 공정에서 힐락(hillock)과 같은 불량에 의해 다른 전도층과 쇼트(short) 현상을 일으킬 수 있다. 또한, 산화물층과의 접촉에 의한 절연층을 형성시키는 등 액정패널의 동작 불량을 유발시킨다.Conventionally, a metal film in which aluminum or an alloy thereof and another metal is laminated has been used as a wiring material for gate and source/drain electrodes. While aluminum is inexpensive and has low resistance, it has poor chemical resistance and can cause short circuits with other conductive layers due to defects such as hillock in post-processing. In addition, it causes malfunction of the liquid crystal panel, such as formation of an insulating layer due to contact with the oxide layer.

이러한 점을 고려하여, 게이트와 소스/드레인 전극용 배선 재료로 구리막과 몰리브덴막, 구리막과 몰리브덴 합금막, 구리합금막과 몰리브덴 합금막 등의 구리계 금속막의 다층막이 제안되었다 (대한민국 공개특허 10-2007-0055259호).In consideration of this, multilayer films of copper-based metal films such as copper film and molybdenum film, copper film and molybdenum alloy film, and copper alloy film and molybdenum alloy film have been proposed as wiring materials for gate and source/drain electrodes (Korean published patent) No. 10-2007-0055259).

그러나, 이러한 구리계 금속막의 다층막을 식각하기 위해서는 각 금속막을 식각하기 위한 서로 다른 2종의 식각액을 이용해야 하며, 그렇지 않을 경우 식각 프로파일 불량이 발생하고, 잔사 등이 발생하는 문제가 있었다. However, in order to etch such a multilayer of copper-based metal films, two different types of etchants must be used to etch each metal film. Otherwise, there was a problem of defective etch profiles and residues.

또한, 식각 경시에 따라 테이퍼앵글 및 싸이드에치의 변화량이 너무 커서 기판의 처리매수가 충분하지 못한 단점이 있었다. In addition, there was a disadvantage in that the amount of change in the taper angle and side etch as the etching progressed was so large that the number of substrates to be processed was not sufficient.

대한민국 공개특허 2012-0055449Republic of Korea Open Patent 2012-0055449

본 발명은, 상기 종래 기술의 문제를 해결하기 위하여 안출된 것으로서,The present invention was devised to solve the problems of the prior art,

식각 경시에 따르는 테이퍼앵글 및 싸이드에치의 변화량을 최소화시킴으로써 기판의 처리매수를 크게 향상시키는 구리계 금속막용 식각액 조성물을 제공하는 것을 목적으로 한다.The purpose of the present invention is to provide an etchant composition for a copper-based metal film that significantly improves the number of substrates processed by minimizing the amount of change in taper angle and side etch with etching time.

또한, 본 발명은 상기 식각액을 사용함으로써 생산효율이 크게 향상되는 표시장치용 어레이 기판의 제조방법을 제공하는 것을 목적으로 한다.Additionally, the purpose of the present invention is to provide a method of manufacturing an array substrate for a display device in which production efficiency is greatly improved by using the etchant.

또한, 본 발명은 상기 방법으로 제조되어 구동성능 및 수명특성이 우수한 표시장치용 어레이 기판을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an array substrate for a display device manufactured by the above method and having excellent driving performance and lifespan characteristics.

본 발명은This invention

a) 기판 상에 게이트 배선을 형성하는 단계;a) forming gate wiring on the substrate;

b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;

c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;

d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; and

e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계;를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; in a method of manufacturing an array substrate for a display device, including:

상기 a) 단계 및 d) 단계 중 하나 이상의 단계는 구리계 금속막을 형성하고, 상기 구리계 금속막을 식각액 조성물로 식각하는 공정을 포함하며,At least one of steps a) and d) includes forming a copper-based metal film and etching the copper-based metal film with an etchant composition,

상기 식각액 조성물은 조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.01~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.1~5 중량%의 글리신, 0.5~6 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법을 제공한다.The etchant composition contains 15 to 25% by weight of hydrogen peroxide, 0.01 to 5% by weight of a fluorinated compound, 0.1 to 5% by weight of an azole compound, 0.1 to 5% by weight of glycine, and 0.5 to 6% by weight based on the total weight of the composition. A method for manufacturing an array substrate for a display device is provided, comprising sulfamic acid, 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a residual amount of water.

또한, 본 발명은 In addition, the present invention

조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.01~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.1~5 중량%의 글리신, 0.5~6 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 구리계 금속막용 식각액 조성물을 제공한다.Based on the total weight of the composition, 15 to 25% by weight of hydrogen peroxide, 0.01 to 5% by weight of fluorinated compound, 0.1 to 5% by weight of azole compound, 0.1 to 5% by weight of glycine, and 0.5 to 6% by weight of sulfamic acid. Provides an etchant composition for a copper-based metal film containing acid), 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a remaining amount of water.

또한, 본 발명은 In addition, the present invention

본 발명의 구리계 금속막용 식각액 조성물로 식각된 게이트 배선, 소스 전극, 및 드레인 전극 중 어느 하나 이상을 포함하는 표시장치용 어레이 기판을 제공한다.Provided is an array substrate for a display device including at least one of a gate wire, a source electrode, and a drain electrode etched with the etchant composition for a copper-based metal film of the present invention.

본 발명의 구리계 금속막용 식각액 조성물은 식각 경시에 따르는 테이퍼앵글 및 싸이드에치의 변화량을 최소화시킴으로써 기판의 처리매수를 크게 향상시키는 구리계 금속막용 식각액 조성물을 제공한다. The etchant composition for copper-based metal films of the present invention provides an etchant composition for copper-based metal films that significantly improves the number of substrates to be processed by minimizing the amount of change in taper angle and side etch with etching time.

또한, 본 발명의 표시장치용 어레이 기판의 제조방법은 상기 구리계 금속막용 식각액 조성물을 사용함으로써 생산효율이 크게 향상시키는 효과를 제공한다. In addition, the method of manufacturing an array substrate for a display device of the present invention provides the effect of greatly improving production efficiency by using the etchant composition for a copper-based metal film.

또한, 상기와 같은 식각액을 사용하여 제조된 본 발명의 표시장치용 어레이 기판은 구동성능 및 수명특성이 우수한 특징을 갖는다. In addition, the array substrate for a display device of the present invention manufactured using the above-described etchant has excellent driving performance and lifespan characteristics.

도 1은 본 발명의 시험예 1에 따르는 실시예와 비교예 식각액 조성물의 사이드에치의 변화량을 나타낸 그래프이다.Figure 1 is a graph showing the amount of change in side etch of the etchant compositions of Examples and Comparative Examples according to Test Example 1 of the present invention.

본 발명은 조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.01~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.1~5 중량%의 글리신, 0.5~6 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 구리계 금속막용 식각액 조성물에 관한 것이다.The present invention is a composition comprising 15 to 25% by weight of hydrogen peroxide, 0.01 to 5% by weight of a fluorinated compound, 0.1 to 5% by weight of an azole compound, 0.1 to 5% by weight of glycine, and 0.5 to 6% by weight of alcohol, based on the total weight of the composition. It relates to an etchant composition for a copper-based metal film containing sulfamic acid, 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a residual amount of water.

상기 구리계 금속막은 막의 구성 성분 중에 구리(Cu)를 포함하는 것으로, 단일막 및 이중막 이상의 다층막을 포함하는 개념이다. 보다 상세하게 상기 구리계 금속막은 구리 또는 구리 합금(Cu alloy)의 단일막; 또는 상기 구리막 및 구리 합금막으로부터 선택되는 하나 이상의 막과 몰리브덴막, 몰리브덴 합금막, 티타늄막 및 티타늄 합금막으로부터 선택되는 하나 이상의 막을 포함하는 다층막을 포함하는 개념이다. 여기서, 합금막이라 함은 질화막 또는 산화막도 포함한다.The copper-based metal film contains copper (Cu) as a component of the film, and is a concept that includes a single film and a multilayer film of a double film or more. More specifically, the copper-based metal film is a single film of copper or copper alloy (Cu alloy); Alternatively, the concept includes a multilayer film including one or more films selected from the copper film and copper alloy film and one or more films selected from the molybdenum film, molybdenum alloy film, titanium film, and titanium alloy film. Here, the alloy film also includes a nitride film or an oxide film.

상기 단일막으로서 구리계 금속막은 구리 단일막, 구리(Cu)막 또는 구리를 주성분으로 하며 알루미늄(Al), 마그네슘(Mg), 칼슘(Ca), 티타늄(Ti), 은(Ag), 크롬(Cr), 망간(Mn), 철(Fe), 지르코늄(Zr), 니오븀(Nb), 몰리브덴(Mo), 팔라듐(Pd), 하프늄(Hf), 탄탈륨(Ta) 및 텅스텐(W) 등으로부터 선택되는 1종 이상의 금속을 포함하는 구리 합금막 등을 들 수 있다. 본 발명의 식각액 조성물은 이들 중에서 특히 구리 단일막, 구리와 몰리브덴의 합금막에 바람직하게 사용될 수 있다. As the single film, the copper-based metal film is a copper single film, a copper (Cu) film, or a copper (Cu) film, or a copper-based metal film, and is composed of aluminum (Al), magnesium (Mg), calcium (Ca), titanium (Ti), silver (Ag), and chromium ( Choose from Cr), manganese (Mn), iron (Fe), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), hafnium (Hf), tantalum (Ta), and tungsten (W). and a copper alloy film containing one or more types of metal. Among these, the etchant composition of the present invention can be preferably used for copper single films and alloy films of copper and molybdenum.

또한, 다층막의 예로는 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴막, 구리 합금/몰리브덴 합금막 등의 2중막, 또는 구리/몰리브덴/구리막 3중막을 들 수 있다. 특히, 본 발명의 식각액 조성물은 상기 예시된 다층막에 바람직하게 사용될 수 있다. Additionally, examples of multilayer films include double films such as copper/molybdenum films, copper/molybdenum alloy films, copper alloy/molybdenum films, and copper alloy/molybdenum alloy films, or triple films of copper/molybdenum/copper films. In particular, the etchant composition of the present invention can be preferably used for the multilayer films exemplified above.

또한, 상기 몰리브덴 합금막은 예컨대, 티타늄(Ti), 탄탈륨(Ta), 크롬(Cr), 니켈(Ni), 네오디늄(Nd), 및 인듐(In)으로부터 선택되는 1종 이상의 금속과 몰리브덴의 합금으로 이루어진 층을 의미한다.In addition, the molybdenum alloy film is, for example, an alloy of molybdenum and one or more metals selected from titanium (Ti), tantalum (Ta), chromium (Cr), nickel (Ni), neodymium (Nd), and indium (In). It means a layer made up of.

본 발명의 식각액 조성물은 특히, 두께가 5,000Å 이상인 후막의 구리 또는 구리 합금막을 포함하는 구리계 금속막의 식각에 바람직하게 사용될 수 있다. In particular, the etchant composition of the present invention can be preferably used for etching copper-based metal films including thick copper or copper alloy films with a thickness of 5,000 Å or more.

상기 두께가 5000Å 이상인 후막은 박막 대비 GLS 한 매 당 식각액에 녹아 나오는 구리이온의 양이 많고, 이에 따라 처리매수를 향상시키기 위해서는 구리이온으로 인해 발생하는 과산화수소의 분해반응을 억제하고 안정성을 보장해야 하는 점에서 박막과 명백히 구별된다. The thick film with a thickness of 5000 Å or more contains a large amount of copper ions dissolved in the etchant per sheet of GLS compared to the thin film. Accordingly, in order to improve the number of treated sheets, it is necessary to suppress the decomposition reaction of hydrogen peroxide caused by copper ions and ensure stability. In this respect, it is clearly distinguished from thin film.

종래의 구리계 금속막 식각액의 경우 식각액 상에 녹아있는 구리이온의 농도가 증가할수록 초기에 의도했던 사이드에치 및 테이퍼앵글이 변형되어 공정상 사용가능한 처리매수가 제한된다.In the case of a conventional copper-based metal film etchant, as the concentration of copper ions dissolved in the etchant increases, the initially intended side etch and taper angle are deformed, limiting the number of processing sheets that can be used in the process.

이하, 본 발명의 식각액 조성물을 구성하는 각 성분을 설명한다.Hereinafter, each component constituting the etchant composition of the present invention will be described.

(A) 과산화수소(A) Hydrogen peroxide

본 발명의 식각액 조성물에 포함되는 과산화수소(H2O2)는 주산화제로 사용되는 성분으로서, 구리계 금속막의 식각 속도에 영향을 준다(구리계 금속막에 포함되는 합금막의 식각 속도에도 영향을 미친다).Hydrogen peroxide (H 2 O 2 ) contained in the etchant composition of the present invention is a component used as the main oxidizing agent, and affects the etching rate of the copper-based metal film (it also affects the etching rate of the alloy film included in the copper-based metal film). ).

상기 과산화수소는 조성물 총 중량에 대하여, 15 내지 25 중량%로 포함되는 것을 특징으로 하며, 18 내지 23 중량%로 포함되는 것이 보다 바람직하다. The hydrogen peroxide is characterized in that it is contained in 15 to 25% by weight, based on the total weight of the composition, and is more preferably contained in 18 to 23% by weight.

상기 과산화수소의 함량이 15 중량% 미만으로 포함될 경우 구리계 금속막의 단일막 또는 다층막에 대한 식각력 저하를 야기하며, 식각 속도가 느려질 수 있다. 반면 25 중량%를 초과할 경우 구리 이온 증가에 따른 발열 안정성이 크게 저하될 수 있고, 식각 속도가 전체적으로 빨라져 공정을 컨트롤하는 것이 어려워질 수 있다.If the content of hydrogen peroxide is less than 15% by weight, the etching power of the single or multilayer copper-based metal film may be reduced and the etching speed may be slowed. On the other hand, if it exceeds 25% by weight, the thermal stability may be greatly reduced due to the increase in copper ions, and the overall etching rate may become faster, making it difficult to control the process.

(B)(B) 함box 불소화합물fluorine compounds

본 발명의 식각액 조성물에 포함되는 함불소화합물은 물에 해리되어 F이온을 낼 수 있는 화합물을 의미한다. 상기 함불소화합물은 몰리브덴 합금막의 식각 속도에 영향을 주는 보조산화제이며, 몰리브덴 합금막의 식각 속도를 조절한다.The fluorine-containing compound included in the etchant composition of the present invention refers to a compound that can dissociate in water and produce F ions. The fluorine-containing compound is an auxiliary oxidizing agent that affects the etching rate of the molybdenum alloy film and controls the etching rate of the molybdenum alloy film.

상기 함불소화합물은 이 분야에서 사용되는 것이라면 특별히 한정되지 않는다. 그러나, HF, NaF, NH4F, NH4BF4, NH4FHF, KF, KHF2, AlF3 및 HBF4로 이루어진 군에서 선택되는 것이 바람직하고, NH4F2가 보다 바람직하다.The fluorine-containing compound is not particularly limited as long as it is used in this field. However, it is preferably selected from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, KF, KHF 2 , AlF 3 and HBF 4 , and NH 4 F 2 is more preferable.

상기 함불소화합물은 조성물 총 중량에 대하여, 0.01 내지 5.0 중량%, 바람직하게는 0.1 내지 3.0 중량%로 포함된다. 상술한 범위 미만으로 포함되면, 몰리브덴 합금막의 식각 속도가 느려지며, 상술한 범위를 초과하여 포함되면, 몰리브덴 합금막의 식각 성능은 향상되지만, 식각 속도가 전체적으로 빨라지기 때문에 언더컷 현상이나 하부층(n+ a-Si:H, a-Si:G)의 식각 Damage가 크게 나타난다.The fluorinated compound is contained in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 3.0% by weight, based on the total weight of the composition. If the content is less than the above-mentioned range, the etching speed of the molybdenum alloy film slows down, and if the content is more than the above-mentioned range, the etching performance of the molybdenum alloy film improves, but the overall etching speed becomes faster, causing undercut phenomenon or lower layer (n+ a- Si:H, a-Si:G) etch damage appears large.

(C) (C) 아졸계Azole series 화합물 compound

본 발명의 식각액 조성물에 포함되는 C) 아졸화합물은 구리계 금속막의 식각 속도를 조절하며 패턴의 시디로스(CD Loss)를 줄여주어 공정상의 마진을 높이는 역할을 한다.C) Azole compound included in the etchant composition of the present invention controls the etching speed of the copper-based metal film and reduces CD Loss of the pattern, thereby increasing process margins.

상기 아졸화합물로는 예컨대, 피롤(pyrrole)계 화합물, 피라졸(pyrazol)계 화합물, 이미다졸(imidazole)계 화합물, 트리아졸(triazole)계 화합물, 테트라졸(tetrazole)계 화합물, 펜타졸(pentazole)계 화합물, 옥사졸(oxazole)계 화합물, 이소옥사졸(isoxazole)계 화합물, 디아졸(thiazole)계 화합물, 이소디아졸(isothiazole)계 화합물 등을 들 수 있으며, 이들은 1종 단독으로 또는 2종 이상이 함께 사용될 수 있다. 이들 중 테트라졸(tetrazole)계 화합물이 바람직하며, 5-메틸테트라졸 및 5-아미노테트라졸이 가장 바람직하다. The azole compounds include, for example, pyrrole-based compounds, pyrazol-based compounds, imidazole-based compounds, triazole-based compounds, tetrazole-based compounds, and pentazole. )-based compounds, oxazole-based compounds, isoxazole-based compounds, thiazole-based compounds, isothiazole-based compounds, etc., which can be used alone or in combination of two. More than one species may be used together. Among these, tetrazole-based compounds are preferred, and 5-methyltetrazole and 5-aminotetrazole are most preferred.

상기 아졸화합물은 식각속도 조절 능력 및 처리매수에 따른 Etch Profile 변동 감소 능력이 화합물마다 다르므로, 공정 조건에 맞는 배합비를 산출하여 사용할 수 있다.Since the azole compounds have different etch rate control capabilities and ability to reduce etch profile fluctuations depending on the number of treated sheets, each compound can be used by calculating a mixing ratio that suits the process conditions.

상기 아졸화합물은 조성물 총 중량에 대하여, 0.1 내지 5.0중량%로 포함될 수 있으며, 바람직하게는 0.5 내지 1.5중량%로 포함될 수 있다. 상술한 범위 미만으로 포함되면, 식각 속도가 빠르게 되어 시디로스가 너무 크게 발생될 수 있으며, 상술한 범위를 초과하여 포함되는 경우에는 구리계 금속막의 식각 속도가 너무 느려지게 되어 상대적으로 금속산화물막의 식각 속도가 빨라지게 되므로 언더컷이 발생될 수 있다.The azole compound may be included in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 1.5% by weight, based on the total weight of the composition. If the content is less than the above-mentioned range, the etching rate may become fast and excessively large CD loss may be generated. If the content is more than the above-mentioned range, the etching rate of the copper-based metal film may become too slow, resulting in relatively high etching of the metal oxide film. As the speed increases, undercut may occur.

(D) 글라이신((D) Glycine ( GlycineGlycine ))

본 발명의 식각액 조성물에 포함되는 글라이신(Glycine)은 식각액 조성물의 보관 시 발생할 수 있는 과산화수소수의 자체 분해 반응을 막아주고 많은 수의 기판을 식각할 때, 식각 특성이 변하는 것을 방지한다. 일반적으로 과산화수소수를 사용하는 식각액 조성물의 경우 보관시 과산화수소수가 자체 분해하여 그 보관기간이 길지가 못하고 용기가 폭발할 수 있는 위험요소까지 갖추고 있다. Glycine included in the etchant composition of the present invention prevents the self-decomposition reaction of hydrogen peroxide that may occur during storage of the etchant composition and prevents changes in etching characteristics when etching a large number of substrates. In general, in the case of etching solution compositions using hydrogen peroxide, the hydrogen peroxide self-decomposes when stored, so the storage period is not long, and there is a risk that the container may explode.

그러나 상기 글라이신(Glycine)이 포함될 경우 과산화수소수의 분해 속도가 10배 가까이 줄어들어 보관기간 및 안정성 확보에 유리하다. 특히 구리층의 경우 식각액 조성물 내에 구리 이온이 다량 잔존할 경우에 패시베이션(passivation) 막을 형성하여 까맣게 산화된 후 더 이상 식각되지 않는 경우가 많이 발생할 수 있으나 이 화합물을 첨가하였을 경우 이런 현상을 막을 수 있다. However, when glycine is included, the decomposition rate of hydrogen peroxide is reduced by nearly 10 times, which is advantageous in ensuring storage period and stability. In particular, in the case of the copper layer, when a large amount of copper ions remain in the etchant composition, a passivation film is formed, which can cause it to oxidize to black and no longer be etched. However, this phenomenon can be prevented by adding this compound. .

상기 글라이신(Glycine)의 함량은 0.1 내지 5.0 중량%로 포함되고, 특히 바람직하게는 0.5 내지 3.0 중량% 범위로 포함된다. 상기 한 분자 내에 질소원자와 카르복실기를 갖는 수용성 화합물은, 조성물 총 중량에 대하여 0.1 내지 5 중량%로 포함되며, 1 내지 3 중량%로 포함되는 것이 더욱 바람직하다. The content of glycine is contained in the range of 0.1 to 5.0 wt%, and particularly preferably in the range of 0.5 to 3.0 wt%. The water-soluble compound having a nitrogen atom and a carboxyl group in one molecule is included in an amount of 0.1 to 5% by weight, more preferably 1 to 3% by weight, based on the total weight of the composition.

상기 글라이신(Glycine)의 함량이 상술한 범위 미만일 경우, 다량의 기판(약 500매)의 식각 후에는 패시베이션 막이 형성되어 충분한 공정 마진을 얻기가 어려워지며, 상술한 범위를 초과할 경우, 몰리브덴 또는 몰리브덴합금의 식각속도가 느려지므로 구리 몰리브덴막 또는 구리 몰리브덴합금막의 경우 몰리브덴 또는 몰리브덴합금막의 잔사 문제가 발생할수 있다.If the content of glycine is less than the above-mentioned range, a passivation film is formed after etching a large amount of substrates (about 500 sheets), making it difficult to obtain sufficient process margin, and if it exceeds the above-mentioned range, molybdenum or molybdenum Since the etching rate of the alloy is slow, residue problems in the molybdenum or molybdenum alloy film may occur in the case of a copper molybdenum film or copper molybdenum alloy film.

E) E) 술팜산sulfamic acid

본 발명의 식각액 조성물에 포함되는 술팜산은 pH를 조절하여 식각속도를 증가시키고 식각액의 과산화수소 분해반응을 저하시키는 성분이다. 또한 처리매수 진행시 테이퍼앵글을 안정하게 해주어 초기 의도했던 식각 형상을 오랜 시간 동안 유지하게 해준다. Sulfamic acid included in the etchant composition of the present invention is an ingredient that increases the etching rate by adjusting pH and reduces the hydrogen peroxide decomposition reaction of the etchant. Additionally, it stabilizes the taper angle during processing, allowing the initially intended etching shape to be maintained for a long time.

상기 술팜산의 함량은 조성물 총중량에 대하여 0.5 내지 6.0 중량%로 포함되고, 특히 바람직하게는 2.0 내지 5.0 중량% 범위인 조성물로 포함된다. 술팜산이 상술한 범위 미만으로 포함되면 식각속도가 매우 낮아 식각 프로파일이 불량하게 될 수 있으며, 식각액 내 구리이온의 용해도가 현저히 감소하며, 상술한 범위를 초과하여 포함되는 경우에는 식각속도가 너무 빨라져 메탈에 데미지를 입히는 문제가 발생한다. The content of sulfamic acid is included in the composition in the range of 0.5 to 6.0% by weight, especially preferably in the range of 2.0 to 5.0% by weight, based on the total weight of the composition. If sulfamic acid is contained below the above-mentioned range, the etching rate may be very low, resulting in a poor etching profile, and the solubility of copper ions in the etchant will be significantly reduced. If sulfamic acid is contained in excess of the above-mentioned range, the etching speed will be too fast, resulting in a poor etching profile. A problem occurs that causes damage.

(F) (F) 다가알코올형Polyhydric alcohol type 계면활성제 Surfactants

본 발명의 식각액 조성물에 포함되는 다가알코올형 계면활성제는 표면장력을 저하시켜 식각의 균일성을 증가시키는 역할을 한다. 또한, 상기 다가알코올형 계면활성제는 구리막을 식각한 후 식각액에 녹아져 나오는 구리 이온을 둘러 쌈으로서 구리이온의 활동도를 억제하여 과산화수소의 분해 반응을 억제한다. 이렇게 구리 이온의 활동도를 낮추게 되면 식각액을 사용하는 동안 안정적으로 공정을 진행 할 수 있게 된다. The polyhydric alcohol-type surfactant included in the etchant composition of the present invention serves to increase the uniformity of etching by lowering surface tension. In addition, the polyhydric alcohol-type surfactant suppresses the activity of copper ions by surrounding the copper ions dissolved in the etching solution after etching the copper film, thereby suppressing the decomposition reaction of hydrogen peroxide. By lowering the activity of copper ions in this way, the process can proceed stably while using the etchant.

상기 다가알코올형 계면활성제로는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol), 폴리에틸렌 글리콜(polyethylene glycol) 등을 들 수 있다. 이중에서 특히, 트리에틸렌글리콜(triethylene glycol)이 바람직하게 사용될 수 있다.Examples of the polyhydric alcohol-type surfactant include glycerol, triethylene glycol, and polyethylene glycol. Among these, triethylene glycol may be preferably used.

상기 다가알코올형 계면활성제는 0.001 내지 5.0 중량%로 포함되고, 특히 바람직하게는 0.1 내지 3.0 중량% 범위로 포함된다. 상기 다가알코올형 계면활성제의 함량이 상술한 범위 미만으로 포함될 경우, 식각 균일성이 저하되고 과산화수소의 분해가 가속화 되는 문제가 생길 수 있으며, 상술한 범위를 초과하여 포함되면 거품이 많이 발생되는 문제가 야기된다.The polyhydric alcohol-type surfactant is contained in the range of 0.001 to 5.0 wt%, and particularly preferably in the range of 0.1 to 3.0 wt%. If the content of the polyhydric alcohol-type surfactant is contained below the above-mentioned range, the etching uniformity may be reduced and the decomposition of hydrogen peroxide may be accelerated, and if the content of the polyhydric alcohol-type surfactant is contained above the above-mentioned range, the problem of excessive foaming may occur. It is caused.

(G) 물(G) water

본 발명의 식각액 조성물에 포함되는 물은 특별히 한정하지 않으나, 반도체 공정용으로서 탈이온수를 이용하는 것이 바람직하며, 물속에 이온이 제거된 정도를 보여주는 비저항값이 18 ㏁/㎝ 이상인 탈이온수를 이용하는 것이 보다 바람직하다.The water included in the etchant composition of the present invention is not particularly limited, but it is preferable to use deionized water for semiconductor processing, and it is better to use deionized water with a resistivity value of 18 mΩ/cm or more, which shows the degree to which ions have been removed from the water. desirable.

상기 물은 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함된다.The water is included in the remaining amount so that the total weight of the composition is 100% by weight.

본 발명의 구리계 금속막용 식각액 조성물은 상기에 언급한 성분들 외에 첨가제로서 식각 조절제, 금속 이온 봉쇄제, 부식 방지제, pH 조절제 등 이 분야에서 통상적으로 사용하는 첨가제들을 더 포함할 수 있다. In addition to the ingredients mentioned above, the etchant composition for a copper-based metal film of the present invention may further include additives commonly used in this field, such as an etch regulator, a metal ion sequestering agent, a corrosion inhibitor, and a pH regulator.

본 발명의 구리계 금속막용 식각액 조성물에 포함되는 각 구성 성분들은 반도체 공정용의 순도를 가지는 것이 바람직하며, 각 구성 성분들은 통상적으로 공지된 방법에 의해서 제조가 가능하다.Each component included in the etchant composition for a copper-based metal film of the present invention preferably has a purity suitable for semiconductor processing, and each component can be manufactured by a commonly known method.

또한, 본 발명은In addition, the present invention

a) 기판 상에 게이트 배선을 형성하는 단계;a) forming gate wiring on the substrate;

b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;b) forming a gate insulating layer on the substrate including the gate wiring;

c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;c) forming a semiconductor layer on the gate insulating layer;

d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및d) forming source and drain electrodes on the semiconductor layer; and

e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계;를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,e) forming a pixel electrode connected to the drain electrode; in a method of manufacturing an array substrate for a display device, including:

상기 a) 단계 및 d) 단계 중 하나 이상의 단계는 구리계 금속막을 형성하고, 상기 구리계 금속막을 본 발명의 식각액 조성물로 식각하는 공정을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법을 제공한다.At least one of steps a) and d) includes forming a copper-based metal film and etching the copper-based metal film with the etchant composition of the present invention. to provide.

상기 구리계 금속막에 대해서는 상술한 설명을 동일하게 적용할 수 있다. The above description can be equally applied to the copper-based metal film.

상기 표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판일 수 있다. The array substrate for the display device may be a thin film transistor (TFT) array substrate.

또한, 본 발명은 상기 본 발명의 구리계 금속막용 식각액 조성물로 식각된 게이트 배선, 소스 전극, 및 드레인 전극 중 어느 하나 이상을 포함하는 표시장치용 어레이 기판을 제공한다.Additionally, the present invention provides an array substrate for a display device including at least one of a gate wire, a source electrode, and a drain electrode etched with the etchant composition for a copper-based metal film of the present invention.

이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예 및 비교예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않으며, 다양하게 수정 및 변경될 수 있다. Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples and comparative examples are for illustrating the present invention, and the present invention is not limited by the following examples and may be modified and changed in various ways.

실시예Example 및 and 비교예Comparative example : : 식각액etchant 조성물의 제조 Preparation of composition

하기 표 1의 성분 및 함량에 따라 실시예 및 비교예의 식각액 조성물 10kg을 각각 제조하였다.10 kg of the etchant compositions of Examples and Comparative Examples were prepared according to the ingredients and contents in Table 1 below.

구 분division HH 22 OO 22 ABFABF 5-MTZ5-MTZ GlycineGlycine Sulfamic AcidSulfamic Acid TEGTEG IDAIDA DI waterDI water 실시예1Example 1 2323 0.10.1 0.30.3 0.50.5 2.02.0 22 -- 잔량remaining amount 실시예2Example 2 2323 0.10.1 0.30.3 3.03.0 5.05.0 22 -- 잔량remaining amount 비교예1Comparative Example 1 2323 0.10.1 0.30.3 0.50.5 00 22 -- 잔량remaining amount 비교예2Comparative example 2 2323 0.10.1 0.30.3 3.03.0 00 22 -- 잔량remaining amount 비교예3Comparative example 3 2323 0.10.1 0.30.3 00 2.02.0 22 -- 잔량remaining amount 비교예4Comparative Example 4 2323 0.10.1 0.30.3 00 5.05.0 22 -- 잔량remaining amount 비교예5Comparative Example 5 2323 0.10.1 0.30.3 00 5.05.0 22 2.02.0 잔량remaining amount

(단위: 중량%)(Unit: weight%)

(주) (main)

ABF : Ammoniumbifluoride; 5-MTZ: 5-methyltetrazole; IDA: Iminodiacetic aicd; TEG: Triethylene glycolABF: Ammonium bifluoride; 5-MTZ: 5-methyltetrazole; IDA: Iminodiacetic aicd; TEG: Triethylene glycol

시험예Test example 1: 경시에 따른 1: Due to neglect 터이퍼앵글Turper Angle 및 and 사이드에치의side etch 변화 평가 change assessment

실시예 및 비교예의 식각액 조성물을 각각 사용하여 경시에 따르는 터이퍼앵글 및 사이드에치의 변화를 측정하였다. Changes in tipper angle and side etch over time were measured using the etchant compositions of Examples and Comparative Examples, respectively.

100mmX100mm의 유리(SiO2)기판 상에 Cu/MoNb 3,000Å/300Å이 증착된 박막 기판을 시편으로 사용하여, 포토리소그래피(photolithography) 공정을 통하여 기판 상에 소정의 패턴을 가진 포토레지스트가 형성되게 한 후, 실시예 및 비교예 식각액 조성물로 식각을 실시하였다.A thin film substrate with Cu/MoNb 3,000Å/300Å deposited on a 100mm Afterwards, etching was performed using the etchant compositions of Examples and Comparative Examples.

이 때, 시간당 Cu powder 1,000ppm씩 용해시켜 8000ppm까지 식각 테스를 진행하고, SEM 장비를 이용하여 테이퍼앵글과 사이드에치를 측정하고, 그 결과를 하기 표 2 및 3, 및 도 1에 나타내었다.At this time, 1,000ppm of Cu powder was dissolved per hour and an etching test was performed up to 8000ppm. The taper angle and side etch were measured using SEM equipment, and the results are shown in Tables 2 and 3 and Figure 1.

S.A 유/무에 따른 테이퍼앵글 변화Taper angle change depending on presence/absence of S.A 처리매수
Cu ion(ppm)Number of processed sheets
Cu ions (ppm) 실시예1Example 1 실시예2Example 2 비교예1Comparative Example 1 비교예2Comparative example 2 00 45.245.2 41.541.5 46.646.6 39.339.3 10001000 46.646.6 41.641.6 49.949.9 42.642.6 20002000 46.146.1 41.241.2 53.253.2 46.046.0 30003000 47.347.3 41.941.9 57.557.5 51.651.6 40004000 47.147.1 42.642.6 61.861.8 55.155.1 50005000 47.847.8 43.943.9 spec outspec out spec outspec out 60006000 47.647.6 43.143.1 spec outspec out spec out　spec out 70007000 47.947.9 43.043.0 spec outspec out spec out　spec out 80008000 48.748.7 44.844.8 spec outspec out spec out　spec out

(단위: ˚)(unit)

상기 표 2에서 확인되는 바와 같이, 본 발명의 식각액 조성물을 사용하는 경우 구리이온의 농도가 8,000ppm까지 상승하더라도 테이퍼앵글의 변화가 매우 작은 것으로 나타났다. 반면, 비교예의 식각액 조성물을 사용한 경우는 구리이온의 농도가 증가함에 따라 테이퍼앵글의 변화가 매우 크게 나타났다. 상기 spec out　은 0 ppm 대비 테이퍼앵글의 변화가 15도를 초과하는 것을 의미한다.As confirmed in Table 2 above, when using the etchant composition of the present invention, the change in taper angle was found to be very small even if the concentration of copper ions increased to 8,000 ppm. On the other hand, when the etchant composition of the comparative example was used, the change in taper angle was very large as the concentration of copper ions increased. The above spec out means that the change in taper angle exceeds 15 degrees compared to 0 ppm.

Glycine의 유/무 따른 사이드에치 변화Side etch changes with/without glycine 처리매수
Cu ion(ppm)Number of processed sheets
Cu ions (ppm) 실시예1Example 1 실시예2Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 비교예5Comparative Example 5 00 0.920.92 0.800.80 1.211.21 0.980.98 1.071.07 10001000 0.920.92 0.800.80 1.031.03 0.950.95 1.051.05 20002000 0.930.93 0.810.81 0.850.85 0.960.96 1.041.04 30003000 0.920.92 0.800.80 0.670.67 0.950.95 0.990.99 40004000 0.920.92 0.800.80 spec out　spec out 0.910.91 0.950.95 50005000 0.930.93 0.790.79 spec out　spec out 0.860.86 0.870.87 60006000 0.910.91 0.780.78 spec out　spec out 0.730.73 0.800.80 70007000 0.900.90 0.770.77 spec out　spec out spec out　spec out spec out　spec out 80008000 0.870.87 0.730.73 spec out　spec out spec out　spec out spec out　spec out

(단위: ㎛)(Unit: ㎛)

상기 표 3에서 확인되는 바와 같이, 본 발명의 식각액 조성물을 사용하는 경우 구리이온의 농도가 8,000ppm까지 상승하더라도 사이드에치의 변화가 매우 작은 것으로 나타났다. 반면, 비교예의 식각액 조성물을 사용한 경우는 구리이온의 농도가 증가함에 따라 사이드 에치의 변화가 매우 크게 나타났다. As confirmed in Table 3, when using the etchant composition of the present invention, the change in side etch was found to be very small even if the concentration of copper ions increased to 8,000 ppm. On the other hand, when the etchant composition of the comparative example was used, the change in side etch was very large as the concentration of copper ions increased.

상기 spec out은 사이드 에치의 변화가 0ppm대비 0.05um를 초과하는 것을 의미 한다. The above spec out means that the change in side etch exceeds 0.05um compared to 0ppm.

상기 표 2 및 3의 시험결과는 실시예 1 내지 실시예 2와 같이 글라이신과 술팜산이 본 발명의 함량 범위 내로 포함될 경우, 테이퍼앵글 및 사이드에치의 거동이 처리매수에 따라 크게 변화하지 않는 것을 나타낸다. 그리고 이러한 효과는 본 발명의 식각액 조성물의 처리매수특성이 매우 우수한 것을 증명한다.The test results in Tables 2 and 3 show that when glycine and sulfamic acid are included within the content range of the present invention as in Examples 1 and 2, the taper angle and side etch behavior do not change significantly depending on the number of treated sheets. And this effect proves that the treated material water characteristics of the etchant composition of the present invention are very excellent.

Claims (8)

a) 기판 상에 게이트 배선을 형성하는 단계;
b) 상기 게이트 배선을 포함한 기판 상에 게이트 절연층을 형성하는 단계;
c) 상기 게이트 절연층 상에 반도체층을 형성하는 단계;
d) 상기 반도체층 상에 소스 및 드레인 전극을 형성하는 단계; 및
e) 상기 드레인 전극에 연결된 화소전극을 형성하는 단계;를 포함하는 표시장치용 어레이 기판의 제조방법에 있어서,
상기 a) 단계 및 d) 단계 중 하나 이상의 단계는 구리계 금속막을 형성하고, 상기 구리계 금속막을 식각액 조성물로 식각하는 공정을 포함하며,
상기 식각액 조성물은 조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.01~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.5~3.0 중량%의 글리신, 2.0~5.0 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법.a) forming gate wiring on the substrate;
b) forming a gate insulating layer on the substrate including the gate wiring;
c) forming a semiconductor layer on the gate insulating layer;
d) forming source and drain electrodes on the semiconductor layer; and
e) forming a pixel electrode connected to the drain electrode; in a method of manufacturing an array substrate for a display device, including:
At least one of steps a) and d) includes forming a copper-based metal film and etching the copper-based metal film with an etchant composition,
The etchant composition contains 15 to 25% by weight of hydrogen peroxide, 0.01 to 5% by weight of a fluorinated compound, 0.1 to 5% by weight of an azole compound, 0.5 to 3.0% by weight of glycine, and 2.0 to 5.0% by weight based on the total weight of the composition. A method of manufacturing an array substrate for a display device, comprising sulfamic acid, 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a residual amount of water. 청구항 1에 있어서,
상기 표시장치용 어레이 기판은 박막트랜지스터(TFT) 어레이 기판인 것을 특징으로 하는 표시장치용 어레이 기판의 제조 방법. In claim 1,
A method of manufacturing an array substrate for a display device, wherein the array substrate for a display device is a thin film transistor (TFT) array substrate. 조성물 총 중량에 대하여 15~25 중량%의 과산화수소, 0.0~5 중량%의 함불소화합물, 0.1~5 중량%의 아졸화합물, 0.5~3.0 중량%의 글리신, 2.0~5.0 중량%의 술팜산(Sulfamic Acid), 0.001~5 중량%의 다가알코올형 계면활성제, 및 잔량의 물을 포함하는 구리계 금속막용 식각액 조성물. Based on the total weight of the composition, 15 to 25% by weight of hydrogen peroxide, 0.0 to 5% by weight of fluorinated compound, 0.1 to 5% by weight of azole compound, 0.5 to 3.0% by weight of glycine, and 2.0 to 5.0% by weight of sulfamic acid. Acid), 0.001 to 5% by weight of a polyhydric alcohol-type surfactant, and a remaining amount of water. 청구항 3에 있어서,
상기 함불소화합물은 HF, NaF, NH4F, NH4BF4, NH4FHF, KF, KHF2, AlF3 및 HBF4로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리계 금속막용 식각액 조성물.In claim 3,
The fluorinated compound is an etchant for a copper-based metal film, characterized in that at least one selected from the group consisting of HF, NaF, NH 4 F, NH 4 BF 4 , NH 4 FHF, KF, KHF 2 , AlF 3 and HBF 4 Composition. 청구항 3에 있어서,
상기 아졸화합물은 피롤(pyrrole)계 화합물, 피라졸(pyrazol)계 화합물, 이미다졸(imidazole)계 화합물, 트리아졸(triazole)계 화합물, 테트라졸(tetrazole)계 화합물, 펜타졸(pentazole)계 화합물, 옥사졸(oxazole)계 화합물, 이소옥사졸(isoxazole)계 화합물, 디아졸(thiazole)계 화합물, 및 이소디아졸(isothiazole)계 화합물로 이루어진 군에서 선택되는 1종 이상의 것임을 특징으로 하는 구리계 금속막용 식각액 조성물.In claim 3,
The azole compounds include pyrrole-based compounds, pyrazol-based compounds, imidazole-based compounds, triazole-based compounds, tetrazole-based compounds, and pentazole-based compounds. , a copper-based compound characterized in that it is at least one selected from the group consisting of oxazole-based compounds, isoxazole-based compounds, thiazole-based compounds, and isothiazole-based compounds. Etching solution composition for metal films. 청구항 3에 있어서,
상기 다가알코올형 계면활성제는 글리세롤(glycerol), 트리에틸렌글리콜(triethylene glycol), 및 폴리에틸렌 글리콜(polyethylene glycol)로 이루어진 군으로부터 선택되는 1종 이상의 것임을 특징으로 하는 구리계 금속막용 식각액 조성물.In claim 3,
An etchant composition for a copper-based metal film, wherein the polyhydric alcohol-type surfactant is at least one selected from the group consisting of glycerol, triethylene glycol, and polyethylene glycol. 청구항 3에 있어서,
상기 구리계 금속막은 구리/몰리브덴막, 구리/몰리브덴 합금막, 구리 합금/몰리브덴막, 및 구리 합금/몰리브덴 합금막으로 이루어지는 군에서 선택되는 이중막인 것을 특징으로 하는 구리계 금속막용 식각액 조성물.In claim 3,
An etchant composition for a copper-based metal film, wherein the copper-based metal film is a double film selected from the group consisting of a copper/molybdenum film, a copper/molybdenum alloy film, a copper alloy/molybdenum film, and a copper alloy/molybdenum alloy film. 청구항 3의 구리계 금속막용 식각액 조성물로 식각된 게이트 배선, 소스 전극, 및 드레인 전극 중 어느 하나 이상을 포함하는 표시장치용 어레이 기판.
An array substrate for a display device including at least one of a gate wire, a source electrode, and a drain electrode etched with the etchant composition for a copper-based metal film of claim 3.
KR1020160049998A 2016-04-25 2016-04-25 Manufacturing method of an array substrate for a display divice KR102603630B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020160049998A KR102603630B1 (en) 2016-04-25 2016-04-25 Manufacturing method of an array substrate for a display divice
CN201710271534.1A CN107316836B (en) 2016-04-25 2017-04-24 Etching liquid composition, array substrate for display device and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020160049998A KR102603630B1 (en) 2016-04-25 2016-04-25 Manufacturing method of an array substrate for a display divice

Publications (2)

Publication Number Publication Date
KR20170121505A KR20170121505A (en) 2017-11-02
KR102603630B1 true KR102603630B1 (en) 2023-11-17

Family

ID=60185471

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020160049998A KR102603630B1 (en) 2016-04-25 2016-04-25 Manufacturing method of an array substrate for a display divice

Country Status (2)

Country Link
KR (1) KR102603630B1 (en)
CN (1) CN107316836B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102459681B1 (en) * 2018-03-09 2022-10-27 동우 화인켐 주식회사 Etchant for cupper-based metat layer, manufacturing method of an array substrate for liquid crystal display using the same and an array substrate for liquid crystal display
CN110993614B (en) * 2019-11-27 2022-06-10 深圳市华星光电半导体显示技术有限公司 Display panel preparation device and method
CN112080747B (en) * 2020-09-02 2021-10-08 Tcl华星光电技术有限公司 Etching solution composition for etching molybdenum/copper/molybdenum or molybdenum alloy/copper/molybdenum alloy three-layer metal wiring structure and application thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100606187B1 (en) * 2004-07-14 2006-08-01 테크노세미켐 주식회사 Composition for cleaning a semiconductor substrate, method for cleaning a semiconductor substrate and method for manufacturing a semiconductor device using the same
CN102102206A (en) * 2009-12-18 2011-06-22 鑫林科技股份有限公司 Metal etching liquid composition and etching method
KR101292163B1 (en) 2010-11-23 2013-08-12 한양대학교 산학협력단 An Anti―Cancer Composition Containing an Antibody of KRT19
US9365770B2 (en) * 2011-07-26 2016-06-14 Mitsubishi Gas Chemical Company, Inc. Etching solution for copper/molybdenum-based multilayer thin film
KR101951045B1 (en) * 2011-08-04 2019-02-21 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
CN102983101B (en) * 2011-08-04 2015-06-17 东友精细化工有限公司 Manufacturing method of array substrate for liquid crystal display
KR20140028446A (en) * 2012-08-29 2014-03-10 주식회사 동진쎄미켐 Etchant composition for etching metal wire and method for preparing metal wire using the same
KR102048022B1 (en) * 2012-12-18 2019-12-02 주식회사 동진쎄미켐 Composition for etching metal layer and method for etching using the same
KR20140084417A (en) * 2012-12-26 2014-07-07 동우 화인켐 주식회사 Echaing composition for preparing a channel of thin film transistor and method of preparing a channel of thin film transistor
KR101924384B1 (en) * 2012-12-28 2018-12-03 동우 화인켐 주식회사 Etchant composition for copper-containing metal
KR102087791B1 (en) * 2013-03-27 2020-03-12 삼성디스플레이 주식회사 Etchant composition, method of forming a metal pattern and method of manufacturing a display substrate using the same
KR102091847B1 (en) * 2013-08-27 2020-03-20 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display
KR102160286B1 (en) * 2013-11-04 2020-09-28 동우 화인켐 주식회사 Manufacturing method of an array substrate for liquid crystal display

Also Published As

Publication number Publication date
CN107316836A (en) 2017-11-03
CN107316836B (en) 2023-08-01
KR20170121505A (en) 2017-11-02

Similar Documents

Publication Publication Date Title
CN104614907B (en) Method for manufacturing array substrate for liquid crystal display
KR20170120504A (en) Etching composition for mono-layed film or multi-layed film, and etching method using the same
KR102660286B1 (en) Etching solution composition for copper-based metal layer and metal oxide layer and method of etching using the same
KR102293674B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102293675B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102603630B1 (en) Manufacturing method of an array substrate for a display divice
KR102269327B1 (en) Etchant composition and manufacturing method of an array for liquid crystal display
KR102412268B1 (en) Manufacturing method of an array substrate for crystal display
KR102583609B1 (en) Etching solution composition for copper-based metal layer, manufacturing method of an array substrate for crystal display using the same
KR102323941B1 (en) Etching solution composition for copper-based metal layer and method for etching copper-based metal layer using the same
KR102546796B1 (en) Etchant composition
KR102260190B1 (en) Etching solution composition and manufacturing method of an array substrate for Liquid crystal display using the same
KR20150045548A (en) Manufacturing method of an array substrate for liquid crystal display
KR102368365B1 (en) Etchant for cupper-based metat layer and manufacturing method of thin film transistor array substrate using the same and a thin film transistor array substrate
KR102459685B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display
KR20160112471A (en) Etchant composition and manufacturing method of an array for liquid crystal display
KR102310093B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR102642371B1 (en) Etchant composition for etching for copper-based metal layer and method of etching using the same
KR102269325B1 (en) Etching solution composition for molybdenum-containing layer and manufacturing method of an array substrate for liquid crystal display using the same
KR102310097B1 (en) Manufacturing method of an array substrate for liquid crystal display
KR102343735B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display using the same and an array substrate for display
KR102368367B1 (en) Etchant for cupper-based metat layer, manufacturing method of an array substrate for display device using the same and an array substrate for display device
KR20160112473A (en) Etchant composition and manufacturing method of an array for liquid crystal display
KR20160112472A (en) Etchant composition and manufacturing method of an array for liquid crystal display
KR102310094B1 (en) Manufacturing method of an array substrate for liquid crystal display

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant