KR102245565B1 - 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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- KR102245565B1 KR102245565B1 KR1020150019958A KR20150019958A KR102245565B1 KR 102245565 B1 KR102245565 B1 KR 102245565B1 KR 1020150019958 A KR1020150019958 A KR 1020150019958A KR 20150019958 A KR20150019958 A KR 20150019958A KR 102245565 B1 KR102245565 B1 KR 102245565B1
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- silver
- indium oxide
- oxide film
- film
- indium
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000004332 silver Substances 0.000 title claims abstract description 125
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000000758 substrate Substances 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title abstract description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 101
- 229910003437 indium oxide Inorganic materials 0.000 claims description 61
- 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 61
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000002356 single layer Substances 0.000 claims description 9
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims 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 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 19
- 150000002739 metals Chemical class 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- LXFUCSMCVAEMCD-UHFFFAOYSA-N acetic acid;nitric acid;phosphoric acid Chemical compound CC(O)=O.O[N+]([O-])=O.OP(O)(O)=O LXFUCSMCVAEMCD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 인산, 질산, 아세트산, 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제 및 물을 포함하는 은 식각액 조성물 및 이를 이용한 표시 기판에 관한 것으로, 상기 은 식각액 조성물은 은을 포함하는 금속막 식각시 발생하는 은 재흡착 현상을 방지할 수 있다.The present invention relates to a silver etchant composition comprising phosphoric acid, nitric acid, acetic acid, a nitrogen atom (N) and a carboxyl group (-COOH), and water, and a display substrate using the same, wherein the silver etchant composition comprises silver. Silver re-adsorption phenomenon that occurs when etching the metal layer can be prevented.
Description
본 발명은 은 식각액 조성물 및 이를 이용한 표시 기판에 관한 것으로, 보다 자세하게는 인산, 질산, 아세트산, 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제 및 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 in more detail, a silver etchant composition including water and an additive including phosphoric acid, nitric acid, acetic acid, nitrogen atom (N) and carboxyl group (-COOH), and using the same It relates to a display substrate.
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 the information age enters into the full-scale information age, the field of display processing and displaying a large amount of information has rapidly developed, and in response to this, various flat panel displays have been developed and are in the spotlight.
이러한 평판디스플레이 장치의 예로는 액정디스플레이장치(Liquid Crystal Display device: LCD), 플라즈마 디스플레이장치(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 flat panel display devices include a liquid crystal display device (LCD), a plasma display panel device (PDP), a field emission display device (FED), and an electroluminescence display device. Display device: ELD), organic light emitting display (OrgaNic Light Emitting Diodes: OLED), and the like, and such flat panel display devices are used not only in home appliances such as televisions and videos, but also in computers and mobile phones such as laptops. These flat panel display devices are rapidly replacing the existing cathode ray tube (NIT) due to their excellent performance such as thinner, lighter, 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, since OLEDs emit light by themselves and can be driven even at low voltages, they are rapidly being applied to small display markets such as portable devices. In addition, OLED is on the verge of commercializing 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. It is widely used as. However, these metals also have high resistance, which is an obstacle to the large-sized and high-resolution flat panel display devices through improvement in 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, materials with higher reflectivity are being sought. To this end, silver (Ag: resistivity about 1.59 μΩcm) film, silver alloy, or multilayer film including the same, which has lower specific resistance and higher luminance than metals applied to flat panel display devices, is used as a color filter electrode, LCD or OLED wiring, and For application to reflectors, to realize a large-sized flat panel display device, high resolution, and low power consumption, the development of an etching solution for the application of this material was required.
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, making it difficult to deposit and lift the wiring. (lifting) or peeling is easily induced. In addition, even when a silver (Ag) conductive layer is deposited on the substrate, an etchant is used to pattern it. When a conventional etchant is used as such an etchant, silver (Ag) is excessively etched or etched in a non-uniform manner, resulting in a phenomenon of lifting or peeling of the wiring, and a side profile of the wiring is deteriorated.
대한민국 등록특허 제10-0579421호에 제시된 은 식각액은 인산, 질산, 초산에 첨가제로서 보조 산화물 용해제와 함불소형 탄소계 계면활성제를 사용하였다. 그러나 보조 산화물 용해제로 사용된 SO4 2 - 화합물은 은(Ag)과 반응을 하여 황화은(Ag2S)의 형태로 기판 내에 잔사로 남게 되는 단점이 있고, ClO4 - 화합물은 현재 환경 규제 물질로 규정되어 사용함에 어려움이 있다. 또한 함불소형 탄소계 계면활성제의 경우 은의 하부막이 유기절연막인 경우 기판의 테두리 부분에 있는 유기절연막이 식각액에 의해 쉽게 손상을 받아 벗겨짐(Peeling) 현상이 유발되는 문제점이 있다.The silver etching solution presented in Korean Patent Registration No. 10-0579421 used an auxiliary oxide solubilizer and a fluorinated carbon-based surfactant as additives to phosphoric acid, nitric acid, and acetic acid. However, the SO 4 2 - compound used as an auxiliary oxide solvent reacts with silver (Ag) and remains as a residue in the substrate in the form of silver sulfide (Ag 2 S), and the ClO 4 - compound is currently an environmentally regulated substance. It is prescribed and is difficult to use. In addition, in the case of a fluorinated carbon-based surfactant, when the lower layer of silver is an organic insulating layer, there is a problem in that the organic insulating layer on the edge of the substrate is easily damaged by the etching solution, causing peeling.
본 발명은 은을 포함하는 금속막의 식각시 발생하는 은 재흡착 현상을 억제하는 은 식각액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a silver etchant composition that suppresses a silver re-adsorption phenomenon that occurs during etching of a metal film containing silver.
또한, 본 발명은 은을 포함하는 금속막의 하부막을 손상시키지 않으며, 균일한 식각 특성을 나타내는 은 식각액 조성물을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a silver etchant composition that does not damage a lower layer of a metal film containing silver and exhibits uniform etching characteristics.
또한, 본 발명은 상기 은 식각액 조성물을 사용하여 제조된 표시 기판 및 배선을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a display substrate and a wiring manufactured using the silver etchant composition.
상기 목적을 달성하기 위하여,To achieve the above object,
본 발명은 은 식각액 조성물 총 중량에 대하여, 인산 40 내지 60 중량%, 질산 3 내지 8 중량%, 아세트산 5 내지 20 중량%, 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제 0.1 내지 3 중량% 및 은 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 은 식각액 조성물을 제공한다.The present invention is based on the total weight of the silver etchant composition, phosphoric acid 40 to 60% by weight, nitric acid 3 to 8% by weight, acetic acid 5 to 20% by weight, additives containing a nitrogen atom (N) and a carboxyl group (-COOH) 0.1 to 3 It provides a silver etchant composition including the remaining amount of water so that the weight% and the total weight of the silver etchant composition is 100% by weight.
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 film 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 조성물은 은을 포함하는 금속막의 식각시 발생하는 은 재흡착 현상을 억제하는 효과를 지니고 있다.The silver etchant composition of the present invention has an effect of suppressing re-adsorption of silver that occurs when etching a metal film containing silver.
또한, 본 발명의 은 식각액 조성물로 식각된 금속막을 포함하는 표시 기판은 우수한 구동 특성을 갖는다.In addition, a display substrate including a metal film etched with the silver etchant composition of the present invention has excellent driving characteristics.
도 1은 본 발명의 은 식각액 조성물로 식각시, 은 잔사가 발생하지 않은 것을 관찰한 SEM 사진이다.
도 2는 종래의 은 식각액 조성물로 식각시, 은 잔사가 발생한 것을 관찰한 SEM 사진이다.
도 3은 본 발명의 은 식각액 조성물로 식각시, 은 재흡착이 발생하지 않은 것을 관찰한 SEM 사진이다.
도 4는 종래의 은 식각액 조성물로 식각시, 은 재흡착이 발생한 것을 관찰한 SEM 사진이다.1 is a SEM photograph of observation that no silver residues were generated when etching with the silver etchant composition of the present invention.
FIG. 2 is a SEM photograph observing that silver residues are generated when etching with a conventional silver etchant composition.
3 is a SEM photograph of observation that silver re-adsorption did not occur when etching with the silver etchant composition of the present invention.
FIG. 4 is a SEM photograph observing that silver re-adsorption occurs when etching with a conventional silver etchant composition.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 은 식각액 조성물 총 중량에 대하여, 인산 40 내지 60 중량%, 질산 3 내지 8 중량%, 아세트산 5 내지 20 중량%, 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제 0.1 내지 3 중량% 및 은 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하는 은 식각액 조성물에 관한 것이다.
The present invention is based on the total weight of the silver etchant composition, phosphoric acid 40 to 60% by weight, nitric acid 3 to 8% by weight, acetic acid 5 to 20% by weight, additives containing a nitrogen atom (N) and a carboxyl group (-COOH) 0.1 to 3 It relates to a silver etchant composition comprising the balance of water so that the weight% and the total weight of the silver etchant composition is 100% by weight.
본 발명의 은 식각액 조성물은 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막을 식각할 수 있는 것이 특징이며, 상기 다층막은 동시에 일괄 식각할 수 있다.The silver etchant composition of the present invention is characterized in that it can etch 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, and the multilayer film can be etched at the same time.
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 is composed of silver as a main component, and alloy forms including 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 shape, 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 gallium 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, an indium oxide film/silver alloy, an indium oxide film/silver/indium oxide film, or an indium oxide film/silver alloy/indium oxide film.
본 발명의 은 식각액 조성물에 포함되는 인산(H3PO4)은 주산화제로서, 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막 식각시, 은(Ag) 또는 은 합금과 산화인듐막을 산화시켜 습식 식각하는 역할을 수행한다. Phosphoric acid (H 3 PO 4 ) contained in the silver etchant composition of the present invention is the main oxidizing agent, and when etching a single layer made of silver (Ag) or a silver alloy, or a multilayer film composed of the single layer and an indium oxide layer, silver ( Ag) or a silver alloy and an indium oxide film are oxidized to perform wet etching.
상기 인산은 은 식각액 조성물 총 중량에 대해 40 내지 60 중량%로 포함되며, 바람직하게는 50 내지 60 중량%로 포함된다. The phosphoric acid is included in an amount of 40 to 60% by weight, preferably 50 to 60% by weight, based on the total weight of the silver etchant composition.
상기 인산이 40 중량% 미만으로 포함되면, 식각능력이 부족하여 상기 단일막 또는 다층막의 식각 속도 저하 및 은 잔사 발생이 일어날 수 있다. 또한, 공정이 진행되어 일정량 이상의 은(Ag)이 은 식각액 조성물에 용해되어 들어가게 되면 은(Ag) 재흡착 또는 은(Ag) 석출물이 발생하여 후속 공정에서 전기적 쇼트가 발생할 수 있어 불량 발생의 원인이 될 수 있다. When the phosphoric acid is contained in an amount of less than 40% by weight, the etching capability may be insufficient, and thus the etching rate of the single layer or the multilayer layer may decrease and silver residue may occur. In addition, if a certain amount of silver (Ag) is dissolved in the silver etchant composition as the process proceeds, silver (Ag) re-adsorption or silver (Ag) precipitates may occur, which may cause an electrical short circuit in the subsequent process, causing defects. Can be.
상기 인산이 60 중량%를 초과하여 포함되면, 상기 다층막 식각시, 산화인듐막의 식각 속도는 저하되고, 은 또는 은 합금의 식각 속도는 너무 빨라져 과식각이 발생할 수 있으며, 이로 인하여 배선의 역할을 수행할 수 없을 만큼의 과식각이 발생할 수 있다. 또한, 이러한 은 또는 은 합금과 산화인듐막의 식각 속도 차에 의하여 산화인듐막의 팁(Tip)이 발생하게 되어 후속공정에 문제가 발생할 수 있다.
If the phosphoric acid is contained in an amount exceeding 60% by weight, the etching rate of the indium oxide layer is lowered when the multilayer layer is etched, and the etching rate of silver or silver alloy is too high to cause over-etching, thereby performing the role of wiring. Overetching can occur that is not possible. In addition, a tip of the indium oxide film may be generated due to the difference in etching rate between the silver or silver alloy and the indium oxide film, which may cause a problem in a subsequent process.
본 발명의 은 식각액 조성물에 포함되는 질산(HNO3)은 보조 산화제의 역할을 하는 성분으로, 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막 식각시 은(Ag) 또는 은 합금과 산화인듐막을 산화시켜 습식 식각하는 역할을 수행한다. Nitric acid (HNO 3 ) contained in the silver etchant composition of the present invention is a component that serves as a secondary oxidizing agent, and when etching a single layer made of silver (Ag) or a silver alloy, or a multilayered film composed of the single layer and the indium oxide layer It performs wet etching by oxidizing silver (Ag) or a silver alloy and indium oxide film.
상기 질산은 은 식각액 조성물 총 중량에 대하여 3 내지 8 중량%로 포함되며, 바람직하게는 4 내지 7 중량%로 포함된다. The silver nitrate is included in an amount of 3 to 8% by weight, and preferably 4 to 7% by weight, based on the total weight of the silver etchant composition.
상기 질산의 함량이 3 중량% 미만으로 포함되면, 식각 속도가 저하되어 그로 인하여 식각 균일성이 감소하여 얼룩이 발생할 수 있다. 또한, 상기 얼룩은 후속 공정 진행에 따라 전기적 쇼트 및 잔사가 남아 있는 영역이 어둡게 보이는 현상인 암점을 발생시킬 수 있다. When the nitric acid content is contained in an amount of less than 3% by weight, the etching rate is lowered, thereby reducing the etching uniformity and staining may occur. In addition, the spot may generate a dark spot, which is a phenomenon in which an electric short and an area where the residue remains darkened as a subsequent process proceeds.
또한, 질산의 함량이 8 중량%를 초과하여 포함되면, 다층막 식각시 산화인듐막의 식각 속도가 가속화되어 공정상 식각 조절이 어렵고, 과식각이 발생하여 후속 공정을 원활하게 수행할 수 없게 된다.
In addition, if the content of nitric acid exceeds 8% by weight, the etching rate of the indium oxide layer is accelerated when etching the multilayer layer, making it difficult to control etching during the process, and overetching occurs, making it impossible to smoothly perform the subsequent process.
본 발명의 은 식각액 조성물에 포함되는 아세트산(CH3COOH)은 보조 산화제이며, 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막 식각시 은 또는 은 합금을 산화시켜 습식 식각하는 역할을 수행한다. Acetic acid (CH 3 COOH) contained in the silver etchant composition of the present invention is a secondary oxidizing agent, and when etching a single layer made of silver (Ag) or a silver alloy, or a multilayer film composed of the single layer and an indium oxide film, silver or silver alloy It performs a role of wet etching by oxidizing.
상기 아세트산은 은 식각액 조성물 총 중량에 대하여 5 내지 20 중량%로 포함되며, 바람직하게는 7 내지 15 중량%로 포함된다. The acetic acid is included in an amount of 5 to 20% by weight, preferably 7 to 15% by weight, based on the total weight of the silver etchant composition.
상기 아세트산의 함량이 5 중량% 미만으로 포함되면, 식각 속도가 불균일해져 얼룩이 발생하는 문제점이 발생한다. If the amount of acetic acid is contained in an amount of less than 5% by weight, the etching rate becomes non-uniform, resulting in a problem that stains are generated.
또한, 상기 아세트산의 함량이 20 중량%를 초과하게 되면, 거품이 발생하며, 상기 거품으로 인하여 완전한 식각이 이루어지지 않아 후속 공정을 진행하기 어려운 문제점이 발생한다.
In addition, when the acetic acid content exceeds 20% by weight, bubbles are generated, and due to the bubbles, complete etching is not performed, making it difficult to proceed with a subsequent process.
본 발명의 은 식각액 조성물에 포함되는 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제는 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막 식각시 발생하는 은 재흡착 발생을 억제시키는 역할을 수행한다. 은 재흡착 발생을 억제시킴으로써, 은 재흡착으로 인한 불량 발생 및 후속 공정 진행의 어려움 등을 해결할 수 있다.The additive containing a nitrogen atom (N) and a carboxyl group (-COOH) included in the silver etchant composition of the present invention is 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. It plays a role in suppressing the occurrence of resorption. By suppressing the occurrence of silver re-adsorption, it is possible to solve the occurrence of defects due to re-adsorption of silver and the difficulty of proceeding with subsequent processes.
상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제는 그 종류를 특별히 한정하는 것은 아니나, 바람직하게는 이미노디아세트산(iminodiacetic acid, IDA), EDTA 및 DTPA로 이루어진 군으로부터 선택되는 1종 이상을 포함하며, 보다 바람직하게는 이미노디아세트산을 포함한다.The additive containing the nitrogen atom (N) and carboxyl group (-COOH) is not particularly limited in its kind, but is preferably one selected from the group consisting of iminodiacetic acid (IDA), EDTA, and DTPA. The above is included, more preferably iminodiacetic acid is included.
상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제는 은 식각액 조성물 총 중량에 대하여 0.1 내지 3 중량%로 포함되며, 바람직하게는 0.5 내지 2 중량%로 포함된다.The additive containing a nitrogen atom (N) and a carboxyl group (-COOH) is contained in an amount of 0.1 to 3% by weight, preferably 0.5 to 2% by weight, based on the total weight of the silver etchant composition.
상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제가 0.1 중량% 미만으로 포함되면, 은 또는 은합금의 과 식각이 발생하게 되고, 상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제가 3 중량%를 초과하여 포함되면, 식각 속도가 저하 되어 잔사 발생 및 식각 불량이 발생하게 된다.
When the additive including the nitrogen atom (N) and carboxyl group (-COOH) is contained in an amount of less than 0.1% by weight, over-etching of silver or silver alloy occurs, and the nitrogen atom (N) and carboxyl group (-COOH) If the included additive is included in an amount exceeding 3% by weight, the etching rate is lowered, resulting in occurrence of residues and poor etching.
본 발명의 은 식각액 조성물에 포함되는 물은 조성물 총 중량이 100 중량%가 되도록 잔량으로 포함된다. 상기 물은 특별히 한정되지 않으나, 탈이온수를 이용하는 것이 바람직하다. 또한, 상기 물은 물 속에 이온이 제거된 정도를 보여주는 물의 비저항 값이 18MΩ·cm 이상인 탈이온수를 이용하는 것이 보다 바람직하다.
The water contained in the silver etchant composition of the present invention is included in the balance so that the total weight of the composition is 100% by weight. The water is not particularly limited, but it is preferable to use deionized water. In addition, it is more preferable to use deionized water having a specific resistance value of 18 MΩ·cm or more, which shows the degree to which ions have been removed from the water.
본 발명의 은 식각액 조성물은 상기에 언급된 성분들 외에 이 분야에서 통상적으로 사용되는 식각 조절제 및 pH 조절제 중 하나 이상을 더 포함할 수 있다.In addition to the above-mentioned components, the silver etchant composition of the present invention may further include at least one of an etch control agent and a pH control agent commonly used in this field.
상기 추가로 포함될 수 있는 식각 조절제로는 초산칼륨 또는 초산나트륨 중 1개의 초산염을 포함하는 화합물이며, 추가로 포함될 수 있는 pH 조절제로는 글리콜산, 글루탐산 또는 글리신 중 1개의 유기산을 포함하는 화합물이다.
The etch control agent that may be additionally included is a compound containing one acetate of potassium acetate or sodium acetate, and the pH adjusting agent that may be additionally included is a compound containing one organic acid of glycolic acid, glutamic acid, or glycine.
또한, 본 발명은 본 발명의 은 식각액 조성물로 식각된 금속막을 포함하는 표시 기판을 제공할 수 있다.In addition, the present invention can provide a display substrate including a metal film 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 liquid crystal display (LCD) or a thin film transistor (TFT) substrate of 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 layer may be stacked on top and bottom, and the metal layer may be etched with the silver etchant composition of the present invention. In addition, by controlling the thickness of the metal film on the upper and lower portions of the metal film to be stacked, the metal film can 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 layer should have a thickness through which light is hardly transmitted, and the semi-transmissive layer should have a thickness through which light is almost transmitted. Therefore, it is preferable that the thickness of the metal layer is 50 to 5000 Å.
상기 금속막은 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 이루어진 다층막이다.The metal film is 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 is composed of silver as a main component, and alloy forms including 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 shape, 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 gallium 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, 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 can provide a 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 or a flexible silver nanowire wiring that reads signals mainly sensed in X and Y coordinates in a touch screen panel (TSP).
또한, 상기 배선은 은(Ag) 또는 은 합금으로 이루어진 단일막, 또는 상기 단일막과 산화인듐막으로 구성되는 다층막으로 이루어져 있다.Further, the wiring is made of 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 is composed of silver as a main component, and alloy forms including 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 shape, 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 gallium 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, 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 for explaining the present invention more specifically, 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 4 및 1 to 4 and 비교예Comparative example 1 내지 5. 1 to 5.
하기의 표 1에 나타낸 조성에 따라 실시예 1 내지 4 및 비교예 1 내지 5의 은 식각액 조성물을 제조하였으며, 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하였다.Silver etchant compositions of Examples 1 to 4 and Comparative Examples 1 to 5 were prepared according to the composition shown in Table 1 below, and the remaining amount of water was included so that the total weight of the etchant composition was 100% by weight.
IDA : iminodiacetic acid
IDA: iminodiacetic acid
실험예Experimental example 1. 은 1. silver 식각액Etchant 조성물의 성능 테스트 Composition Test
기판 상에 유기 절연막을 증착하고, 그 위에 ITO/APC(Ag, Pd 및 Cu 합금)/ITO 삼중막을 증착한 것을 다이아몬드 칼을 이용하여 500X600mm로 절단하여 시편을 준비하였다. An organic insulating film was deposited on the substrate, and the ITO/APC (Ag, Pd and Cu alloy)/ITO triple film was deposited on the substrate and cut into 500×600 mm using a diamond knife to prepare a specimen.
상기 삼중막 상에 소정의 패턴을 가진 포토레지스트가 형성되도록 한 후, 분사식 식각 방식의 실험장비(모델명: ETCHER(TFT), K.C.Tech사) 내에 상기 실시예 1 내지 4 및 비교예 1 내지 5의 은 식각액 조성물을 각각 넣고, 온도를 40℃로 설정하여 가온한 후, 온도가 40±0.1℃에 도달하였을 때 상기 시편의 식각 공정을 수행하였다. 총 식각 시간은 60초로 실시하였다.After forming a photoresist having a predetermined pattern on the triple layer, in the experimental equipment (model name: ETCHER (TFT), KCTech) of the spray type etching method, the examples 1 to 4 and Comparative Examples 1 to 5 Each silver etchant composition was added, heated by setting the temperature to 40° C., and then, when the temperature reached 40±0.1° C., the etching process of the specimen was performed. The total etching time was 60 seconds.
기판을 넣고 분사를 시작하여 60초의 식각 시간이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍건조장치를 이용하여 건조하고, 포토레지스트 박리기(PR stripper)를 이용하여 포토레지스트를 제거하였다. 세정 및 건조 후 기판을 절단하고 단면을 전자주사현미경(SEM; 모델명:SU-8010, HITACHI사 제조)을 이용하여 측정하였다.
The substrate was put in, sprayed, and when the etching time of 60 seconds was over, it was taken out, washed with deionized water, dried using a hot air dryer, and the photoresist was removed using a photoresist stripper (PR stripper). After cleaning and drying, the substrate was cut and the cross section was measured using an electron scanning microscope (SEM; model name: SU-8010, manufactured by HITACHI).
1. One. 양 쪽의Both 편측Unilateral 식각Etching 거리(Side bias) 측정 Side bias measurement
편측 식각 거리 측정 기준으로는 포토레지스트 끝 부분부터 금속이 식각 되어 안쪽까지 들어간 양 쪽의 너비를 측정하였으며, 하기의 기준으로 평가하였으며, 결과를 하기 표 2에 나타내었다.
As a standard for measuring the one-sided etching distance, the widths of both sides of the photoresist, which were etched from the end of the photoresist to the inside, were measured, and evaluated according to the following criteria, and the results are shown in Table 2 below.
<양 쪽의 편측 식각 거리 측정 평가 기준><Evaluation criteria for measuring the etching distance on both sides>
○ : (우수) 0.25 μm 이하○: (Excellent) 0.25 μm or less
△ : (양호) 0.25 μm 초과 0.40 μm 이하△: (Good) more than 0.25 μm and less than 0.40 μm
X : (불량) 0.40 μm 초과
X: (defective) exceeding 0.40 μm
2. 2. 잔사Residue 측정 Measure
포토레지스트가 덮여 있지 않은 부분에 은(Ag)이 식각 되지 않고 남아 있는 현상인 잔사를 측정하였다. The residue, which is a phenomenon in which silver (Ag) was not etched, was measured in the part not covered with photoresist.
잔사가 발생하지 않은 표면은 도 1과 같이 관찰되었고, 잔사가 발생한 표면은 도 2와 같이 기판 전면에 무정형으로 존재한 것이 관찰되었다. The surface where the residue did not occur was observed as shown in FIG. 1, and the surface where the residue was generated was observed to exist in an amorphous form on the entire surface of the substrate as shown in FIG. 2.
상기 실시에 1 내지 4 및 비교예 1 내지 5의 결과를 하기 표 2에 나타내었다.
The results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 2 below.
3. 재흡착 측정3. Measurement of resorption
주로 데이터 배선 등 이종 금속이 노출된 부분이나 굴곡 현상에 의해 마찰이 발생할 수 있는 특정 부위에 식각된 은(Ag)이 흡착되어 있는 현상을 전면 관찰을 통한 분석을 진행하였다. The analysis was conducted through full observation of the phenomenon that the etched silver (Ag) is adsorbed on the part where the dissimilar metals are exposed, such as the data wiring, or the specific part where friction may occur due to the bending phenomenon.
재흡착이 발생하지 않은 표면은 도 3과 같이 관찰되었고, 은 환원에 의하여 재흡착이 발생한 표면은 도 4와 같이 관찰되었으며, 은의 재흡착은 구형으로 관찰되었다. The surface in which re-adsorption did not occur was observed as shown in FIG. 3, the surface in which re-adsorption occurred due to silver reduction was observed as in FIG. 4, and the re-adsorption of silver was observed in a spherical shape.
상기 실시에 1 내지 4 및 비교예 1 내지 5의 결과를 하기 표 2에 나타내었다.
The results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table 2 below.
상기 표 2의 결과에서, 본 발명의 은 식각액 조성물인 실시예 1 내지 4는 식각시, 은 잔사 및 은 재흡착이 모두 발생하지 않았으며, 양 편측 식각거리 모두 양호 및 우수한 결과를 얻었다.In the results of Table 2, Examples 1 to 4, which are silver etchant compositions of the present invention, did not generate silver residue and silver re-adsorption at the time of etching, and both etch distances were good and excellent results were obtained.
또한, 비교예 1 내지 5의 은 식각액 조성물 모두 양 편측 식각거리 모두 우수한 결과를 보였다.In addition, both of the silver etchant compositions of Comparative Examples 1 to 5 showed excellent results in both etching distances.
그러나, 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제를 포함하지 않은 비교예 1의 은 식각액 조성물은 은 재흡착이 발생하였으며, 상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제를 은 식각액 조성물 총 중량에 대하여 0.1 중량% 미만으로 포함한 비교예 2의 은 식각액 조성물 및 3 중량%를 초과하여 포함한 비교예 3 내지 5의 은 식각액 조성물은 모두 은 잔사 및 은 재흡착이 발생하는 결과를 보였다.
However, the silver etchant composition of Comparative Example 1 that did not contain an additive containing a nitrogen atom (N) and a carboxyl group (-COOH) had re-adsorption of silver, and contained the nitrogen atom (N) and a carboxyl group (-COOH). The silver etchant composition of Comparative Example 2 and the silver etchant composition of Comparative Examples 3 to 5 containing more than 3% by weight of the silver etchant composition containing less than 0.1% by weight of the total weight of the silver etchant composition are all silver residues and silver re-adsorption occurs. Showed the result.
따라서, 본 발명의 은 식각액 조성물은 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제를 은 식각액 조성물 총 중량에 대하여 0.1 내지 3 중량%로 포함함으로써, 은을 포함하는 금속막 식각시 발생하는 은 재흡착 현상을 방지할 수 있다는 것을 실험을 통하여 확인할 수 있었다.Therefore, the silver etchant composition of the present invention contains an additive containing a nitrogen atom (N) and a carboxyl group (-COOH) in an amount of 0.1 to 3% by weight based on the total weight of the silver etchant composition. It was confirmed through an experiment that it can prevent re-adsorption.
Claims (18)
인산 40 내지 60 중량%;
질산 3 내지 8 중량%;
아세트산 5 내지 20 중량%;
질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제 0.1 내지 3 중량% 및 은 식각액 조성물 총 중량이 100 중량%가 되도록 잔량의 물을 포함하고,
상기 질소원자(N) 및 카르복실기(-COOH)를 포함하는 첨가제는 이미노디아세트산, EDTA 및 DTPA로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는, 은 식각액 조성물.Based on the total weight of the silver etchant composition,
40 to 60% by weight of phosphoric acid;
3 to 8% by weight of nitric acid;
5 to 20% by weight of acetic acid;
0.1 to 3% by weight of an additive containing a nitrogen atom (N) and a carboxyl group (-COOH), and the remaining amount of water so that the total weight of the silver etchant composition is 100% by weight,
The additive containing a nitrogen atom (N) and a carboxyl group (-COOH) is characterized in that it contains at least one selected from the group consisting of iminodiacetic acid, EDTA and DTPA, silver etchant composition.
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