KR102400311B1 - Etching solution composition for silver layer and an display substrate using the same - Google Patents
Etching solution composition for silver layer and an display substrate using the same Download PDFInfo
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- KR102400311B1 KR102400311B1 KR1020150123044A KR20150123044A KR102400311B1 KR 102400311 B1 KR102400311 B1 KR 102400311B1 KR 1020150123044 A KR1020150123044 A KR 1020150123044A KR 20150123044 A KR20150123044 A KR 20150123044A KR 102400311 B1 KR102400311 B1 KR 102400311B1
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- Prior art keywords
- silver
- indium oxide
- etchant composition
- oxide film
- film
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004332 silver Substances 0.000 title claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000005530 etching Methods 0.000 title claims description 37
- 239000000758 substrate Substances 0.000 title claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- -1 phosphate compound Chemical class 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 111
- 229910003437 indium oxide Inorganic materials 0.000 claims description 65
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 65
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910001923 silver oxide Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims 1
- 235000019801 trisodium phosphate Nutrition 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 23
- 229910052719 titanium Inorganic materials 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000001039 wet etching Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002042 Silver nanowire Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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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
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- C23F1/10—Etching compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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- C23F1/00—Etching metallic material by chemical means
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- C23F1/00—Etching metallic material by chemical means
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- 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
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Abstract
본 발명은 (a) 인산(H3PO44), (b) 질산(HNO3), (c) 아세트산(CH3COOH), (d) 인산염 화합물 (e) 나트륨계 화합물, 및 (f) 물을 포함하는 은 식각액 조성물에 대한 것이다.The present invention relates to (a) phosphoric acid (H 3 PO4 4 ), (b) nitric acid (HNO 3 ), (c) acetic acid (CH 3 COOH), (d) phosphate compound (e) sodium-based compound, and (f) water It relates to a silver etchant composition comprising a.
Description
본 발명은 은 식각액 조성물 및 이를 이용한 표시 기판에 관한 것으로, 보다 자세하게는 (a) 인산(H3PO44), (b) 질산(HNO3), (c) 아세트산(CH3COOH), (d) 인산염 화합물, (e) 나트륨계 화합물 및 (f) 물을 포함하는 은 식각액 조성물 및 이를 이용한 표시 기판에 관한 것이다.The present invention relates to a silver etchant composition and a display substrate using the same, and more particularly, (a) phosphoric acid (H 3 PO4 4 ), (b) nitric acid (HNO 3 ), (c) acetic acid (CH 3 COOH), (d) ) A silver etchant composition comprising a phosphate compound, (e) a sodium-based compound, and (f) water, and a display substrate using the same.
본격적인 정보화 시대로 접어들게 됨에 따라 대량의 정보를 처리 및 표시하는 디스플레이 분야가 급속도로 발전해 왔으며, 이에 부응하여 다양한 평판 디스플레이가 개발되어 각광받고 있다.As we enter the information age in earnest, the field of display that processes and displays a large amount of information has developed rapidly, and various flat panel displays have been developed and are in the spotlight in response to this.
이러한 평판디스플레이 장치의 예로는 액정디스플레이장치(Liquid Crystal Display device: LCD), 플라즈마디스플레이장치(Plasma Display Panel device : PDP), 전계방출디스플레이장치(Field Emission Display device : FED), 전기발광디스플레이장치(Electroluminescence Display device : ELD), 유기발광디스플레이(OrgaNic Light Emitting Diodes : OLED) 등을 들 수 있으며, 이러한 평판디스플레이 장치는 텔레비전이나 비디오 등의 가전분야 뿐만 아니라 노트북과 같은 컴퓨터 및 핸드폰 등에 다양한 용도로 사용되고 있다. 이들 평판디스플레이 장치는 박형화, 경량화, 및 저소비전력화 등의 우수한 성능으로 인하여 기존에 사용되었던 브라운관(Cathode Ray Tube : NIT)을 빠르게 대체하고 있는 실정이다. Examples of such a flat panel display device include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescence display device (Electroluminescence). Display device: ELD), organic light emitting display (OrgaNic Light Emitting Diodes: OLED), etc. are mentioned, and these flat panel display devices are used for various purposes such as computers and mobile phones such as laptops as well as home appliances such as televisions and videos. These flat panel display devices are rapidly replacing conventional cathode ray tubes (NITs) due to their excellent performance such as thinness, weight reduction, and low power consumption.
특히 OLED는 소자 자체적으로 빛을 발광하며 저전압에서도 구동될 수 있기 때문에 최근 휴대기기 등의 소형 디스플레이 시장에 빠르게 적용되고 있다. 또한 OLED는 소형 디스플레이를 넘어서 대형 TV의 상용화를 목전에 둔 상태이다.In particular, OLEDs emit light by themselves and can be driven at low voltages, so they are rapidly being applied to small display markets such as portable devices. In addition, OLED is on the verge of commercialization of large TVs beyond small displays.
한편, 산화주석인듐(Indium Tin Oxide, ITO)과 산화아연인듐(Indium Zinc Oxide, IZO)과 같은 도전성 금속은 빛에 대한 투과율이 비교적 뛰어나고, 도전성을 가지므로 평판디스플레이장치에 사용되는 칼라필터의 전극으로 널리 쓰이고 있다. 그러나 이들 금속들 또한 높은 저항을 가져 응답속도의 개선을 통한 평판표시장치의 대형화 및 고해상도 실현에 장애가 되고 있다.On the other hand, conductive metals such as indium tin oxide (ITO) and indium zinc oxide (IZO) have relatively excellent light transmittance and conductivity, so the electrode of a color filter used in a flat panel display device. is widely used as However, these metals also have high resistance, which is an obstacle to enlargement of the flat panel display and realization of high resolution through improvement of response speed.
또한, 반사판의 경우 과거 알루미늄(Al) 반사판을 주로 제품에 이용해왔으나, 휘도 향상을 통한 저전력 소비실현을 위해서는 반사율이 더 높은 금속으로의 재료변경을 모색하고 있는 상태이다. 이를 위해 평판디스플레이장치에 적용되고 있는 금속들에 비해 낮은 비저항과 높은 휘도를 가지고 있는 은(Ag: 비저항 약 1.59μΩ㎝)막, 은합금 또는 이를 포함한 다층막을 칼라필터의 전극, LCD 또는 OLED 배선 및 반사판에 적용, 평판표시장치의 대형화와 고 해상도 및 저전력 소비 등을 실현하고자 하여, 이 재료의 적용을 위한 식각액의 개발이 요구되었다.In the case of reflectors, aluminum (Al) reflectors have been mainly used in products in the past, but in order to realize low power consumption through improved luminance, they are seeking to change materials to metals with higher reflectance. For this purpose, a silver (Ag: resistivity about 1.59 μΩcm) film, a silver alloy, or a multilayer film containing the same, which has a lower resistivity and higher luminance than metals applied to flat panel display devices, is used for color filter electrodes, LCD or OLED wiring and The development of an etchant for the application of this material was required in order to realize the application to the reflector, enlargement of the flat panel display, high resolution, and low power consumption.
그러나, 은(Ag)은 유리 등의 절연 기판 또는 진성 비정질 규소나 도핑된 비정질 규소 등으로 이루어진 반도체 기판 등의 하부 기판에 대해 접착성(adhesion)이 극히 불량하여 증착이 용이하지 않고, 배선의 들뜸(lifting) 또는 벗겨짐(Peeling)이 쉽게 유발된다. 또한, 은(Ag)도전층이 기판에 증착된 경우에도 이를 패터닝하기 위해 식각액을 사용하게 된다. 이러한 식각액으로서 종래의 식각액을 사용하는 경우 은(Ag)이 과도하게 식각되거나, 불균질하게 식각되어 배선의 들뜸 또는 벗겨짐 현상이 발생하고, 배선의 측면 프로파일이 불량하게 된다.However, silver (Ag) has extremely poor adhesion to an insulating substrate such as glass or a lower substrate such as a semiconductor substrate made of intrinsic amorphous silicon or doped amorphous silicon. Lifting or peeling is easily induced. In addition, even when the silver (Ag) conductive layer is deposited on the substrate, an etchant is used to pattern the silver (Ag) conductive layer. When a conventional etchant is used as such an etchant, silver (Ag) is excessively etched or etched non-uniformly, causing lifting or peeling of the wiring, and the side profile of the wiring is poor.
대한민국 공개공보 제 10-2008-0110259호에는 인산, 질산, 아세트산, 제1인산나트륨(NaH2PO4) 등을 포함하는 은 식각액 조성물이 기재되어 있으나, Pad부에 노출된 S/D 배선 (Ti/Al/Ti 삼중막)에 손상(Damage)을 억제할 수 없는 문제점이 있다. Korean Publication No. 10-2008-0110259 discloses a silver etchant composition containing phosphoric acid, nitric acid, acetic acid, monosodium phosphate (NaH2PO4), etc., but S/D wiring (Ti/Al/Ti/Al/ There is a problem in that the damage to the Ti triple film cannot be suppressed.
이에, Pad부에 노출된 S/D 배선 (Ti/Al/Ti 삼중막)에 손상(Damage)을 억제할 수 있는 은 식각액 조성물의 개발이 필요한 실정이다.Accordingly, there is a need to develop a silver etchant composition capable of suppressing damage to the S/D wiring (Ti/Al/Ti triple film) exposed to the pad portion.
본 발명의 목적은 은(Ag) 또는 은합금으로 이루어진 단일막 및 상기 단일막과 산화인듐막으로 구성된 다층막, 바람직하게는 산화인듐막/은 또는 산화인듐막/은/산화인듐막으로 형성된 다층막에 대해 사용할 수 있으며, Pad 부에 노출된 데이터(Data) 배선을 손상시키지 않고 은(Ag)의 재흡착 현상을 억제하며 식각 균일성을 나타내는 습식 식각에 유용한 식각액을 제공하는 것이다.An object of the present invention is to provide a single film made of silver (Ag) or a silver alloy and a multilayer film composed of the single film and an indium oxide film, preferably a multilayer film formed of an indium oxide film/silver or indium oxide film/silver/indium oxide film. It is to provide an etchant useful for wet etching that exhibits etch uniformity while suppressing the re-adsorption of silver (Ag) without damaging the data wiring exposed on the pad part.
또한, 본 발명은 상기 은 식각액 조성물을 사용하여 제조된 표시 기판 및 배선을 제공하는 것을 목적으로 한다.Another object of the present invention is to provide a display substrate and wiring manufactured by using the silver etchant composition.
상기 목적의 달성을 위하여, 본 발명은 인산(H3PO4), 질산(HNO3), 아세트산(CH3COOH), 인산염 화합물, 알루미늄 (Al) 식각억제제 및 탈이온수를 함유하는 은(Ag) 식각액 조성물을 제공한다.In order to achieve the above object, the present invention provides phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ), acetic acid (CH 3 COOH), phosphate compound, aluminum (Al) etch inhibitor and silver (Ag) containing deionized water An etchant composition is provided.
또한, 본 발명은 상기 은 식각액 조성물로 식각된 금속막을 포함하는 표시 기판을 제공한다.In addition, the present invention provides a display substrate including a metal layer etched with the silver etchant composition.
또한, 본 발명은 상기 은 식각액 조성물로 식각된 배선을 제공한다.In addition, the present invention provides a wiring etched with the silver etchant composition.
본 발명의 은 식각액 Pad 부에 노출된 데이터(Data) 배선을 손상시키지 않고 은(Ag)의 재흡착 현상을 억제하며 식각 균일성을 나타내는 습식 식각에 유용하다. It is useful for wet etching that suppresses re-adsorption of silver (Ag) without damaging the data wiring exposed on the silver etchant pad part of the present invention and exhibits etch uniformity.
또한, 본 발명의 은 식각액 조성물로 식각된 금속막을 포함하는 표시 기판은 우수한 구동 특성을 갖는다.In addition, the display substrate including the metal layer etched with the silver etchant composition of the present invention has excellent driving characteristics.
도 1은 실시예 4의 식각액 조성물로 티타늄/알루미늄/티타늄을 식각한 알루미늄 Damage 평가 그림(Side Etch 0.1㎛ 이하 - 매우 우수)이다.
도 2는 비교예 8의 식각액 조성물로 티타늄/알루미늄/티타늄을 식각한 알루미늄 Damage 평가 그림(Side Etch 0.4㎛ 이상 - 불량)이다.
도 3은 실시예 4의 식각액 조성물로 산화인듐막/은/산화인듐막을 식각한 APC 식각 프로파일 평가 그림(Side Etch 0.3㎛ 이하 - 매우 우수)이다.
도 4는 실시예 4의 식각액 조성물로 산화인듐막/은/산화인듐막을 식각한 APC 식각 프로파일 평가 그림(Side Etch 1.0㎛ 이상 - 불량)이다.1 is a diagram of aluminum damage evaluation (side etch of 0.1 μm or less - very good) obtained by etching titanium/aluminum/titanium with the etchant composition of Example 4;
2 is a diagram of aluminum damage evaluation (side etch of 0.4 µm or more - bad) obtained by etching titanium/aluminum/titanium with the etchant composition of Comparative Example 8. FIG.
FIG. 3 is an APC etching profile evaluation diagram (side etch 0.3 μm or less - very good) obtained by etching an indium oxide film/silver/indium oxide film with the etchant composition of Example 4;
4 is an APC etching profile evaluation diagram (Side Etch of 1.0 µm or more - bad) in which an indium oxide film/silver/indium oxide film is etched with the etchant composition of Example 4;
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
상기 목적의 달성을 위하여, 본 발명은 (a) 인산(H3PO44), (b) 질산(HNO3), (c) 아세트산(CH3COOH), (d) 인산염 화합물, (e) 나트륨계 화합물 및 (f) 물을 포함하는 은 식각액 조성물을 제공한다. 본 발명은 알루미늄 식각 억제제로서 (e) 나트륨계 화합물이 조성물에 포함되는 경우, 액정 표시 장치의 제조에서 배선 및 반사막으로 사용되는 은(Ag) 또는 은합금으로 이루어진 단일막 또는 이의 다층막에 대해 적용시, Pad부에 노출된 데이터(Data) 배선인 티타늄/알루미늄/티타늄에서 알루미늄을 손상시키지 않고 패턴(Pattern) 부의 배선 및 반사막에 대한 식각 균일성을 나타내고 Pad부 데이터(Data)의 손상으로부터 발생하는 은(Ag) 재흡착 문제도 개선할 수 있음을 실험적으로 확인하여 환성하였다. In order to achieve the above object, the present invention provides (a) phosphoric acid (H 3 PO4 4 ), (b) nitric acid (HNO 3 ), (c) acetic acid (CH 3 COOH), (d) phosphate compound, (e) sodium It provides a silver etchant composition comprising a compound and (f) water. When the present invention is applied to a single film or a multilayer film made of silver (Ag) or a silver alloy used as wiring and a reflective film in the manufacture of a liquid crystal display device when (e) a sodium-based compound is included in the composition as an aluminum etch inhibitor , In titanium/aluminum/titanium, which is the data wiring exposed in the pad part, it does not damage the aluminum and shows the uniformity of etching for the wiring and the reflective film in the pattern part, and the silver generated from damage to the data (data) in the pad part (Ag) It was confirmed experimentally that the re-adsorption problem could also be improved.
이하, 본 발명을 구성별로 상세히 설명한다. Hereinafter, the present invention will be described in detail for each configuration.
(a) 인산((a) phosphoric acid ( HH 33 PO4PO4 44 ))
본 발명의 식각액에 포함되는 인산(H3PO4)은 주 산화제로 사용되는 성분으로서, 산화인듐막/은(Ag)/산화인듐막에서 은(Ag)과 산화인듐막을 산화시켜 습식식각하는 역할을 수행한다. Phosphoric acid (H 3 PO 4 ) contained in the etchant of the present invention is a component used as the main oxidizing agent, and serves to oxidize the silver (Ag) and indium oxide films in the indium oxide film/silver (Ag)/indium oxide film to perform wet etching. carry out
본 발명의 식각액에 포함되는 인산(H3PO4)의 함량은 식각액 조성물 총중량에 대하여 40~60 중량%이다. 인산의 함량이 40 중량% 미만인 경우에는 은의 식각 속도 저하와 식각 프로파일의 불량을 야기시킬 수 있으며, 60 중량%를 초과하는 경우에는 산화인듐막의 식각 속도는 저하되고, 은의 식각 속도는 너무 빨라져 상하부 산화인듐막의 팁(Tip)이 발생하게 되어 후속공정에 문제가 되는 불리한 점이 있다. The content of phosphoric acid (H 3 PO 4 ) contained in the etchant of the present invention is 40 to 60% by weight based on the total weight of the etchant composition. If the phosphoric acid content is less than 40 wt%, it may cause a decrease in the etching rate of silver and a poor etching profile. There is a disadvantage in that a tip of the indium film is generated, which causes a problem in the subsequent process.
(b) 질산((b) nitric acid ( HNOHNO 33 ))
본 발명의 식각액에 포함되는 질산(HNO3)은 보조 산화제로 사용되는 성분으로서, 산화인듐막/은(Ag)/산화인듐막에서 은(Ag)과 산화인듐막을 산화시켜 습식식각하는 역할을 수행한다. Nitric acid (HNO 3 ) contained in the etchant of the present invention is a component used as an auxiliary oxidizing agent, and serves to oxidize the silver (Ag) and indium oxide films in the indium oxide film/silver (Ag)/indium oxide film to perform a wet etching role. do.
본 발명의 식각액에 포함되는 질산(HNO3)의 함량은 식각액 조성물 총중량에 대하여 3~8 중량%이다. 질산의 함량이 3 중량% 미만인 경우에는 은(Ag)과 ITO의 식각 속도 저하가 발생하여 이로써 기판내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 8 중량%를 초과하는 경우에는 상하부 산화인듐막의 식각 속도가 가속화 되어 상하부 산화인듐막의 언더컷 발생으로 후속 공정에 문제가 발생되는 불리한 점이 있다.The content of nitric acid (HNO 3 ) contained in the etchant of the present invention is 3 to 8% by weight based on the total weight of the etchant composition. When the content of nitric acid is less than 3% by weight, the etching rate of silver (Ag) and ITO is lowered, thereby making the etching uniformity in the substrate poor, so staining occurs. There is a disadvantage in that the etching rate of the indium film is accelerated, and a problem occurs in a subsequent process due to the occurrence of undercuts in the upper and lower indium oxide films.
(c) 아세트산(CH(c) acetic acid (CH 33 COOH)COOH)
본 발명의 식각액에 포함되는 아세트산(CH3COOH)은 보조 산화제로 사용되는 성분으로서, 산화인듐막/은(Ag)/산화인듐막에서 은(Ag)을 산화시켜 습식식각하는 역할을 수행한다. Acetic acid (CH 3 COOH) contained in the etchant of the present invention is a component used as an auxiliary oxidizing agent, and performs a wet etching role by oxidizing silver (Ag) in the indium oxide layer/silver (Ag)/indium oxide layer.
본 발명의 식각액에 포함되는 아세트산(CH3COOH)의 함량은 식각액 조성물 총중량에 대하여 5~20 중량%이다. 아세트산의 함량이 5 중량% 미만인 경우에는 기판 내의 식각 속도 불균일로 얼룩이 발생하는 문제점이 있고, 20 중량%를 초과하는 경우에는 거품발생이 야기되며 이러한 거품이 기판내에 존재하게 되면 완전한 식각이 이루어지지 않아 후속공정에 문제를 야기할 수 있다.The content of acetic acid (CH 3 COOH) contained in the etchant of the present invention is 5 to 20% by weight based on the total weight of the etchant composition. If the content of acetic acid is less than 5% by weight, there is a problem in that staining occurs due to uneven etching rate in the substrate, and if it exceeds 20% by weight, foaming is caused. It may cause problems in the subsequent process.
(d) 인산염 화합물 (d) phosphate compounds
상기 인산염 화합물은 본 발명의 식각액 중의 인산염 화합물 첨가제로 사용되는 성분으로서, 습식 식각 시 박막에 대한 CD 스큐(CD Skew)를 감소시키고 또한 균일하게 식각되도록 식각 속도를 조절한다. The phosphate compound is a component used as a phosphate compound additive in the etchant of the present invention, and the etching rate is controlled to reduce CD skew of the thin film during wet etching and to etch uniformly.
상기 인산염 화합물은 제1인산나트륨, 제2인산나트륨 및 제3인산나트륨에서 선택되는 하나 이상일 수 있으며, 제1인산나트륨인 것이 가장 바람직하다. The phosphate compound may be at least one selected from sodium phosphate monobasic, sodium phosphate dibasic, and sodium triphosphate, and most preferably sodium phosphate monobasic.
상기 인산염 화합물의 함량은 식각액 조성물 총중량에 대하여 0.1~3 중량%이다. 제1인산나트륨의 함량이 0.1중량% 미만인 경우에는 기판 내의 식각 균일성(Uniformity)이 저하되고 또한 기판 내에 부분적으로 은 잔사가 생길 수 있으며, 3 중량%를 초과하는 경우에는 식각 속도가 저하되어 원하는 식각 속도를 구현할 수 없으므로 공정상에 문제가 될 수 있다.The content of the phosphate compound is 0.1 to 3% by weight based on the total weight of the etchant composition. If the content of monobasic sodium phosphate is less than 0.1% by weight, the etching uniformity in the substrate may be lowered and silver residue may be partially generated in the substrate, and if it exceeds 3% by weight, the etching rate is lowered and desired Since the etching rate cannot be realized, it may be a problem in the process.
(e) 나트륨계 화합물(e) sodium-based compounds
본 발명의 식각액 중의 나트륨계 화합물은 알루미늄 식각억제제로서, 습식 식각 시 Pad 부에 노출된 데이터(Data) 배선인 티타늄/알루미늄/티타늄 금속 다층막에서 알루미늄의 식각을 억제하여 손상(Damage)을 방지하고, 후속 공정에서 발생할 수 있는 문제들을 개선할 수 있다. The sodium-based compound in the etchant of the present invention is an aluminum etch inhibitor, and prevents damage by inhibiting the etching of aluminum in the titanium/aluminum/titanium metal multilayer film, which is the data wiring exposed to the pad during wet etching, Problems that may occur in subsequent processes can be improved.
상기 나트륨계 화합물은 바람직하게는 질산나트륨, 황산나트륨, 아세트산나트륨, 아질산나트륨, 및 아황산나트륨 중에서 선택되는 하나 이상일 수 있다. The sodium-based compound may be preferably at least one selected from sodium nitrate, sodium sulfate, sodium acetate, sodium nitrite, and sodium sulfite.
상기 나트륨계 화합물의 함량은 식각액 조성물 총중량에 대하여 0.1~3 중량%이다. Al 식각억제제 함량이 0.1중량% 미만인 경우에는 Data배선의 손상(Damage)을 억제하지 못하며, 3 중량%를 초과하는 경우에는 Ag의 식각 속도가 저하되어 원하는 식각 속도를 구현할 수 없으므로 공정상에 문제가 될 수 있다.The content of the sodium-based compound is 0.1 to 3% by weight based on the total weight of the etchant composition. If the Al etch inhibitor content is less than 0.1 wt%, damage to the data wiring cannot be suppressed. can be
(f) 물(f) water
본 발명의 물은 식각액 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함될 수 있다. Water of the present invention may be included in the remaining amount so that the total weight of the etchant composition is 100% by weight.
본 발명의 은 식각액 조성물은 은 식각액 조성물은 은 또는 은합금으로 이루어진 단일막과, 상기 단일막과 산화인듐막으로 이루어진 다층막을 식각할 수 있다. 구체적으로, 상기 산화인듐은 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상일 수 있으며, 상기 단일막과 산화인듐막으로 이루어진 다층막은 산화인듐막/은, 산화인듐막/은 합금, 산화인듐막/은/산화인듐막 또는 산화인듐막/은 합금/산화인듐막일 수 있다. The silver etchant composition of the present invention may etch a single layer made of silver or a silver alloy, and a multilayer layer made of the single layer and the indium oxide layer. Specifically, the indium oxide may be at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), and indium gallium zinc oxide (IGZO), and the single The multilayer film composed of the film and the indium oxide film may be an indium oxide film/silver film, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film.
액정 표시 장치의 제조 시, 배선 및 반사막으로 사용되는 은(Ag) 또는 은합금으로 이루어진 단일막 및 상기 단일막과 산화인듐막으로 구성된 다층막, 바람직하게는 산화인듐막/은 또는 산화인듐막/은/산화인듐막으로 구성된 다층막에 대해 본 발명의 식각액 조성물을 사용하는 경우, Pad부에 노출된 데이타(Data) 배선인 티타늄/알루미늄/티타늄에서 알루미늄을 손상시키지 않고 패턴(Pattern) 부의 배선 및 반사막에 대한 식각 균일성을 나타내고 Pad부 데이타(Data) 배선의 손상으로부터 발생하는 은(Ag) 재흡착 문제도 개선할 수 있다. A single film made of silver (Ag) or a silver alloy used as a wiring and a reflective film in manufacturing a liquid crystal display device, and a multilayer film composed of the single film and an indium oxide film, preferably an indium oxide film/silver or indium oxide film/silver / When the etchant composition of the present invention is used for a multilayer film composed of an indium oxide film, it does not damage aluminum in titanium/aluminum/titanium, which is the data wiring exposed in the pad part, and is applied to the wiring and the reflective film of the pattern part. It is possible to improve the etch uniformity of the substrate and also improve the silver (Ag) re-adsorption problem caused by damage to the data wiring in the pad part.
본 발명의 은 식각액 조성물은 상기에 언급된 성분들 외에 이 분야에서통상적으로 사용되는 첨가제를 더 포함할 수 있다.The silver etchant composition of the present invention may further include additives commonly used in this field in addition to the above-mentioned components.
또한, 본 발명은 본 발명의 은 식각액 조성물로 식각된 금속막을 포함하는 표시 기판을 제공할 수 있다.In addition, the present invention may provide a display substrate including a metal layer etched with the silver etchant composition of the present invention.
보다 자세하게는 상기 표시 장치는 액정표시장치(LCD) 또는 유기발광소자(OLED)의 박막트랜지스터(TFT) 기판일 수 있다.In more detail, the display device may be a thin film transistor (TFT) substrate of a liquid crystal display (LCD) or an organic light emitting device (OLED).
또한, 상기 OLED는 금속막을 상부 및 하부에 적층할 수 있으며, 본 발명의 은 식각액 조성물로 금속막을 식각할 수 있다. 또한, 상부 및 하부에 금속막의 두께를 조절하여 적층함으로써, OLED에서 상기 금속막은 반사막 및 반투과막의 역할을 수행할 수 있다.In addition, in the OLED, a metal film may be laminated on the upper and lower portions, and the metal film may be etched with the silver etchant composition of the present invention. In addition, by stacking the metal film on the upper and lower portions by controlling the thickness, the metal film may serve as a reflective film and a semi-transmissive film in the OLED.
상기 반사막은 빛이 거의 투과되지 않는 두께이어야 하며, 상기 반투과막은 빛이 거의 투과되는 두께이어야 한다. 따라서, 상기 금속막의 두께는 50 내지 5000Å인 것이 바람직하다.The reflective film should have a thickness that hardly transmits light, and the semi-transmissive film should have a thickness that almost transmits light. Therefore, the thickness of the metal film is preferably 50 to 5000 Å.
상기 금속막은 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 이루어진 다층막이다.The metal film may be a single film made of silver (Ag) or a silver alloy, or a multilayer film made of the single film and an indium oxide film.
상기 은 합금은 은을 주성분으로 하며, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 등의 다른 금속을 포함하는 합금 형태와, 은의 질화물, 규화물, 탄화물 및 산화물 형태 등으로 다양할 수 있으나, 이에 한정되는 것은 아니다.The silver alloy contains silver as a main component, and includes an alloy form containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti, and nitrides, silicides, carbides and oxides of silver. It may be various in the form, etc., but is not limited thereto.
또한, 상기 산화인듐은 산화주석인듐(ITO), 산화아연인듐(IZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상이다.In addition, the indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), and indium zinc oxide (IGZO).
또한, 상기 다층막은 산화인듐막/은, 산화인듐막/은 합금, 산화인듐막/은/산화인듐막 또는 산화인듐막/은 합금/산화인듐막으로 형성된 다층막일 수 있다.In addition, the multilayer film may be a multilayer film formed of an indium oxide film/silver film, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film.
또한, 본 발명은 본 발명의 은 식각액 조성물로 식각된 배선을 제공할 수 있다.In addition, the present invention may provide wiring etched with the silver etchant composition of the present invention.
보다 자세하게, 상기 배선은 터치스크린패널(Touch screen panel, TSP)에서 주로 X, Y좌표에 센싱된 신호를 읽어들이는 트레이스(Trace)배선 또는 플렉서블용 은 나노와이어 배선일 수 있다. In more detail, the wiring may be a trace wiring that reads signals mainly sensed at X and Y coordinates in a touch screen panel (TSP) or a flexible silver nanowire wiring.
또한, 상기 배선은 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막으로 이루어져 있다.In addition, the wiring consists of a single film made of silver (Ag) or a silver alloy, or a multilayer film composed of the single film and an indium oxide film.
상기 은 합금은 은을 주성분으로 하며, Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 등의 다른 금속을 포함하는 합금 형태와, 은의 질화물, 규화물, 탄화물 및 산화물 형태 등으로 다양할 수 있으나, 이에 한정되는 것은 아니다.The silver alloy contains silver as a main component, and includes an alloy form containing other metals such as Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti, and nitrides, silicides, carbides and oxides of silver. It may be various in the form, etc., but is not limited thereto.
또한, 상기 산화인듐은 산화주석인듐(ITO), 산화아연인듐(IZO) 및 산화갈륨아연인듐(IGZO)으로 이루어진 군으로부터 선택되는 1종 이상이다.In addition, the indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), and indium zinc oxide (IGZO).
또한, 상기 다층막은 산화인듐막/은, 산화인듐막/은 합금, 산화인듐막/은/산화인듐막 또는 산화인듐막/은 합금/산화인듐막으로 형성된 다층막일 수 있다.In addition, the multilayer film may be a multilayer film formed of an indium oxide film/silver film, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<은 < silver 식각액etchant 조성물 제조> Composition Preparation>
실시예Example 1 내지 7 및 1 to 7 and 비교예comparative example 1 내지 10 1 to 10
하기의 표 1 및 표 2에 나타낸 조성에 따라 실시예 1 내지 7 및 비교예 1 내지 10의 은 식각액 조성물을 제조하였으며, 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하였다.The silver etchant compositions of Examples 1 to 7 and Comparative Examples 1 to 10 were prepared according to the compositions shown in Tables 1 and 2 below, and the remaining amount of water was included so that the total weight of the etchant composition was 100% by weight.
실험예 1. 은 식각액 조성물의 알루미늄 손상(Damage) 평가Experimental Example 1. Evaluation of aluminum damage of silver etchant composition
상기 실시예 및 비교예의 식각액 조성물로 티타늄/알루미늄/티타늄을 식각하였다. 구체적으로, 분사식 식각 방식의 실험장비 (모델명: Mini ETCHER(TFT), AST社) 내에 제조된 식각액을 넣고 온도를 40로 설정하여 가온한 후, 온도가 40±0.1에 도달하였을 때 식각 공정을 수행하였다. 총 식각 시간은 엔드포인트 검출(End Point Detection, EPD)을 기준으로 하여 오버 에치(Over Etch) 50%를 주어 실시하였다. Titanium/aluminum/titanium was etched with the etchant compositions of Examples and Comparative Examples. Specifically, the etchant prepared in the experimental equipment of the spray-type etching method (model name: Mini ETCHER (TFT), AST Company) was put in, the temperature was set to 40 and heated, and the etching process was performed when the temperature reached 40±0.1. did The total etching time was performed by giving 50% of the over etch (Over Etch) based on the endpoint detection (End Point Detection, EPD).
기판을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 에어블로잉을 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경 (SEM; 모델명: S-4700, HITACHI사 제조)을 이용하여) 알루미늄 손상을 평가하였다. 평가 기준은 다음과 같으며, 결과를 도 1, 도 2 및 표 1에 나타내었다. The substrate was put in, sprayed, and when the etching was completed, it was taken out, washed with deionized water, dried using air blowing, and the photoresist was removed using a photoresist stripper (PR stripper). After washing and drying, damage to aluminum was evaluated using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI). The evaluation criteria are as follows, and the results are shown in FIGS. 1, 2 and Table 1.
[알루미늄 Damage 평가 기준][Aluminum Damage Evaluation Criteria]
◎ : 매우 우수 (Side Etch : < 0.1㎛)◎: Very good (Side Etch: < 0.1㎛)
○ : 우수 (Side Etch : < 0.2㎛, > 0.1㎛)○: Excellent (Side Etch: < 0.2㎛, > 0.1㎛)
△ : 양호 (Side Etch : < 0.3㎛, > 0.2㎛)△: Good (Side Etch: < 0.3㎛, > 0.2㎛)
Ⅹ : 불량 (Side Etch : > 0.3㎛)Ⅹ : Bad (Side Etch : > 0.3㎛)
도 1은 실시예 4의 식각액 조성물로 티타늄/알루미늄/티타늄을 식각한 알루미늄 손상(Damage) 평가 그림으로 Side Etch 0.1㎛ 이하는 매우 우수함을 나타낸다. 1 is an aluminum damage evaluation diagram obtained by etching titanium/aluminum/titanium with the etchant composition of Example 4, and a side etch of 0.1 μm or less is very good.
도 2는 비교예 8의 식각액 조성물로 티타늄/알루미늄/티타늄을 식각한 알루미늄 손상(Damage) 평가 그림으로 Side Etch 0.4㎛ 이상은 불량함을 나타낸다. 2 is an aluminum damage evaluation diagram obtained by etching titanium/aluminum/titanium with the etchant composition of Comparative Example 8, and a side etch of 0.4 μm or more indicates poor quality.
실험예 2. 은 식각액 조성물의 APC 식각 프로파일 평가Experimental Example 2. APC etch profile evaluation of silver etchant composition
상기 실시예 및 비교예의 식각액 조성물로 산화인듐막/은/산화인듐막을 식각한 APC 식각 프로파일을 (분사식 식각 방식의 실험장비 (모델명: Mini ETCHER(TFT), AST社) 내에 제조된 식각액을 넣고 온도를 40로 설정하여 가온한 후, 온도가 40±0.1에 도달하였을 때 식각 공정을 수행하였다. 총 식각 시간은 엔드포인트 검출(End Point Detection, EPD)을 기준으로 하여 오버 에치(Over Etch) 50%를 주어 실시하였다. The APC etching profile obtained by etching the indium oxide film/silver/indium oxide film with the etchant composition of Examples and Comparative Examples (experimental equipment for injection etching method (model name: Mini ETCHER(TFT), AST Company)) After heating by setting the temperature to 40, the etching process was performed when the temperature reached 40±0.1. The total etching time was 50% over etch based on the end point detection (EPD). was given and carried out.
기판을 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, d에어블로잉을 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 전자주사현미경 (SEM; 모델명: S-4700, HITACHI사 제조)을 이용하여 CD skew 및 식각 잔류물 발생 정도의 식각 프로파일을 평가하였다. 평가 기준은 다음과 같으며, 결과를 도 3, 도 4 및 표 1에 나타내었다. After inserting the substrate and starting spraying, when the etching was completed, it was taken out, washed with deionized water, dried using d air-blowing, and the photoresist was removed using a photoresist stripper (PR stripper). After washing and drying, the etch profile of CD skew and etch residue generation was evaluated using a scanning electron microscope (SEM; model name: S-4700, manufactured by HITACHI). The evaluation criteria are as follows, and the results are shown in FIGS. 3, 4 and Table 1.
[APC 식각프로파일 평가 기준][APC etch profile evaluation criteria]
◎ : 매우 우수 (Side Etch : < 0.3㎛)◎: Excellent (Side Etch: < 0.3㎛)
○ : 우수 (Side Etch : < 0.5㎛, > 0.3㎛)○: Excellent (Side Etch: < 0.5㎛, > 0.3㎛)
△ : 양호 (Side Etch : < 0.5㎛, > 1.0㎛)△: Good (Side Etch: < 0.5㎛, > 1.0㎛)
Ⅹ : 불량 (Side Etch : > 1.0㎛)Ⅹ : Bad (Side Etch : > 1.0㎛)
도 3은 실시예 4의 식각액 조성물로 산화인듐막/은/산화인듐막을 식각한 APC 식각 프로파일 평가 그림으로 Side Etch 0.3㎛ 이하는 매우 우수함을 나타낸다. 3 is an APC etch profile evaluation diagram obtained by etching an indium oxide film/silver/indium oxide film with the etchant composition of Example 4, and a side etch of 0.3 μm or less is very good.
도 4는 실시예 4의 식각액 조성물로 산화인듐막/은/산화인듐막을 식각한 APC 식각 프로파일 평가 그림으로 Side Etch 1.0㎛ 이상은 불량함을 나타낸다. 4 is an APC etching profile evaluation diagram obtained by etching an indium oxide film/silver/indium oxide film with the etchant composition of Example 4, and a side etch of 1.0 µm or more is poor.
상기 실험 결과를 통해, 본 발명의 은 식각액 조성물은 알루미늄 손상(Damage) 및 APC 식각 프로파일의 측면에서 매우 우수한 효과를 가짐을 확인하였다. Through the above experimental results, it was confirmed that the silver etchant composition of the present invention had a very good effect in terms of aluminum damage and APC etch profile.
이에 반해, 비교예의 조성물의 경우, 알루미늄 손상(Damage) 및/또는 APC 식각 프로파일의 측면의 효과가 좋지 않았으며, 특히, 식각 억제제로 나트륨계 화합물 대신 EDTA (ethylenediaminetetraacetic acid)를 사용한 비교예 10의 경우, 알루미늄 손상 문제가 해결되지 않음을 확인하였다. 이를 통해, 식각 억제제로 나트륨계 화합물을 사용하는 본 발명의 조성물이 알루미늄 손상 문제를 해결하는 우수한 효과를 가짐을 확인할 수 있었다. On the other hand, in the case of the composition of Comparative Example, the effect of aluminum damage and/or APC etching profile was not good. In particular, in Comparative Example 10 using ethylenediaminetetraacetic acid (EDTA) instead of sodium-based compound as an etching inhibitor , it was confirmed that the aluminum damage problem was not solved. Through this, it was confirmed that the composition of the present invention using a sodium-based compound as an etching inhibitor has an excellent effect in solving the aluminum damage problem.
따라서, 액정 표시 장치의 제조 시, 배선 및 반사막으로 사용되는 은(Ag) 또는 은합금으로 이루어진 단일막 및 기 단일막과 산화인듐막으로 구성된 다층막, 바람직하게는 산화인듐막/은 또는 산화인듐막/은/산화인듐막으로 구성된 다층막에 대해 본 발명의 식각액 조성물을 사용하는 경우, Pad부에 노출된 데이터(Data) 배선인 티타늄/알루미늄/티타늄에서 알루미늄을 손상시키지 않고 패턴(Pattern) 부의 배선 및 반사막에 대한 식각 균일성을 나타내고 Pad부 데이터(Data) 배선의 손상으로부터 발생하는 은(Ag) 재흡착 문제도 개선할 수 있다.Therefore, when manufacturing a liquid crystal display device, a single film made of silver (Ag) or a silver alloy used as a wiring and a reflective film, and a multilayer film composed of a single film and an indium oxide film, preferably an indium oxide film/silver or indium oxide film / When using the etchant composition of the present invention for a multilayer film composed of / silver / indium oxide film, the pattern portion wiring and It is possible to show the etch uniformity of the reflective film and to improve the problem of silver (Ag) re-adsorption caused by damage to the data (Data) wiring of the pad part.
Claims (11)
(a) 인산(H3PO44) 40~60 중량%;
(b) 질산(HNO3) 3~8 중량%;
(c) 아세트산(CH3COOH) 5~20 중량%;
(d) 인산염 화합물 0.1~3 중량%;
(e) 나트륨계 화합물 0.1~3 중량%; 및
(f) 잔량의 물을 포함하며,
상기 (e) 나트륨계 화합물은 황산나트륨, 아질산나트륨, 및 아황산나트륨 중 에서 선택되는 하나 이상인, 은 식각액 조성물.
with respect to the total weight of the composition,
(a) 40-60 wt% of phosphoric acid (H 3 PO4 4 );
(b) 3-8% by weight of nitric acid (HNO 3 );
(c) 5-20% by weight of acetic acid (CH 3 COOH);
(d) 0.1 to 3% by weight of a phosphate compound;
(e) 0.1 to 3% by weight of a sodium-based compound; and
(f) including the balance of water;
The (e) sodium-based compound is at least one selected from sodium sulfate, sodium nitrite, and sodium sulfite, silver etchant composition.
The silver etchant composition of claim 1, wherein the (d) phosphate compound is at least one selected from monosodium phosphate, disodium phosphate, and trisodium phosphate.
The silver etchant composition of claim 1, wherein the (e) sodium-based compound is an aluminum etch inhibitor.
은 식각액 조성물은 은 또는 은합금으로 이루어진 단일막과, 상기 단일막과 산화인듐막으로 이루어진 다층막을 식각하는 것을 특징으로 하는 은 식각액 조성물.
The method according to claim 1,
The silver etchant composition comprises etching a single layer made of silver or a silver alloy, and a multilayer layer comprising the single layer and the indium oxide layer.
The method according to claim 6, wherein the indium oxide is at least one selected from the group consisting of indium tin oxide (ITO), indium zinc oxide (IZO), indium tin oxide (ITZO), and indium gallium zinc oxide (IGZO). A silver etchant composition.
The method according to claim 6, wherein the multilayer film consisting of the single film and the indium oxide film is an indium oxide film/silver, indium oxide film/silver alloy, indium oxide film/silver/indium oxide film, or indium oxide film/silver alloy/indium oxide film. A silver etchant composition, characterized in that
A display substrate comprising a metal layer etched with the silver etchant composition of any one of claims 1, 3, 4, and 6 to 8.
The display substrate of claim 9 , wherein the display substrate is a thin film transistor (TFT) substrate of a liquid crystal display (LCD) or an organic light emitting diode (OLED).
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