KR20060043710A - Etching composition - Google Patents
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- KR20060043710A KR20060043710A KR1020050021921A KR20050021921A KR20060043710A KR 20060043710 A KR20060043710 A KR 20060043710A KR 1020050021921 A KR1020050021921 A KR 1020050021921A KR 20050021921 A KR20050021921 A KR 20050021921A KR 20060043710 A KR20060043710 A KR 20060043710A
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- 238000005530 etching Methods 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010408 film Substances 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 12
- 239000012498 ultrapure water Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- UAWBWGUIUMQJIT-UHFFFAOYSA-N azanium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound N.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAWBWGUIUMQJIT-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
-
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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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- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
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- C11D2111/22—
Abstract
본 발명은 박막트랜지스터 액정표시장치의 투명도전막(ITO막)의 선택적인 에칭을 위해 사용되는 에칭 조성물에 관한 것으로, 특히 염산, 초산, 첨가제, 및 초순수를 포함하여 경시변화가 적고 다른 금속배선에 영향을 최소로하여 안정적으로 식각할 수 있으며, 빠른 에칭속도를 갖고 사이드 에칭을 줄일 수 있는 박막트랜지스터 액정표시장치의 에칭 조성물에 관한 것이다.The present invention relates to an etching composition used for the selective etching of the transparent conductive film (ITO film) of the thin film transistor liquid crystal display device, in particular, with little change over time, including hydrochloric acid, acetic acid, additives, and ultrapure water, and affects other metal wiring. The present invention relates to an etching composition of a thin film transistor liquid crystal display device which can be stably etched to a minimum, and has a high etching rate and can reduce side etching.
에칭, 액정표시장치 Etching, Liquid Crystal Display
Description
도 1은 본 발명의 일실시예에 따라 제조한 에칭 조성물의 계면활성제 농도에 따른 표면장력을 나타낸 그래프이다.1 is a graph showing the surface tension according to the surfactant concentration of the etching composition prepared according to an embodiment of the present invention.
도 2는 본 발명의 일실시예에 따라 제조한 에칭 조성물로 처리한 투명도전막(ITO막)의 단면을 나타낸 사진이다.2 is a photograph showing a cross section of a transparent conductive film (ITO film) treated with an etching composition prepared according to an embodiment of the present invention.
도 3은 첨가제를 사용하지 않은 종래의 에칭 조성물로 처리한 투명도전막(ITO막)의 단면을 나타낸 사진이다.3 is a photograph showing a cross section of a transparent conductive film (ITO film) treated with a conventional etching composition without using an additive.
도 4는 본 발명의 일실시예에 따라 제조한 에칭 조성물로 처리한 투명도전막(ITO막)의 단면을 나타낸 사진이다.4 is a photograph showing a cross section of a transparent conductive film (ITO film) treated with an etching composition prepared according to an embodiment of the present invention.
본 발명은 박막트랜지스터 액정표시장치의 투명도전막(ITO막)의 선택적인 에칭을 위해 사용되는 에칭 조성물에 관한 것으로, 더욱 상세하게는 경시변화가 적고 다른 금속배선에 영향을 최소로하여 안정적으로 식각할 수 있으며, 빠른 에칭속도를 갖고 사이드 에칭을 줄일 수 있는 박막트랜지스터 액정표시장치의 에칭 조성물에 관한 것이다.The present invention relates to an etching composition used for the selective etching of the transparent conductive film (ITO film) of the thin film transistor liquid crystal display device, and more particularly, it is possible to etch stably with little change over time and to minimize the influence on other metal wiring. The present invention relates to an etching composition of a thin film transistor liquid crystal display device capable of reducing the side etching.
투명도전막은 LCD와 PDP 등과 같은 평판 디스플레이용 표시장치에 널리 사용된다. 일반적으로 표시장치는 전기적인 신호를 시각 영상으로 변환시켜 인간이 직접 정보를 인식할 수 있도록 하는데 사용되는 전기광학적인 장치이다.Transparent conductive films are widely used in flat panel display devices such as LCD and PDP. In general, a display device is an electro-optical device used to convert an electrical signal into a visual image so that a human can directly recognize information.
이러한 표시장치 중 액정표시장치는 전계를 인가하여 액정분자의 배열을 변화시켜 액정의 광학적 성질을 이용하는 표시장치이다. 이때 전계를 인가하기 위해서는 전극이 필요하며, 이러한 전극은 도전성 및 투명성이 요구된다. 이에 적합한 물질로서는 투명도전막(ITO막)이 주로 사용되고 있다.Among such display devices, a liquid crystal display device is a display device that uses an optical property of a liquid crystal by changing an arrangement of liquid crystal molecules by applying an electric field. In this case, an electrode is required to apply an electric field, and the electrode requires conductivity and transparency. As a suitable material, a transparent conductive film (ITO film) is mainly used.
액정표시장치의 박막트랜지스터 기판은 금속으로 이루어진 배선을 형성하고, 배선을 덮는 보호막을 형성하고, 투명도전막(ITO막)을 적층하고 패터닝하여 투명전극을 형성하는 순서로 제조된다. 이때, 투명도전막(ITO막)을 형성하기 위해 원하는 미세패턴을 형성시키는 에칭공정이 필요하며, 여기서 기판상에 ITO막을 형성하고 포토레지스트를 이용하여 미세패턴을 그린 후 에칭한다.The thin film transistor substrate of the liquid crystal display device is manufactured in the order of forming a transparent electrode by forming a wiring made of metal, forming a protective film covering the wiring, stacking and patterning a transparent conductive film (ITO film). At this time, an etching process for forming a desired fine pattern is required to form a transparent conductive film (ITO film). Here, an ITO film is formed on a substrate and a fine pattern is drawn using a photoresist and then etched.
그러나, 투명도전막(ITO막)의 화학적 내성 때문에 투명도전막(ITO막)을 화학적으로 에칭하는 것은 상당히 어려운 작업으로 알려져 있으며, 지금까지 상기 에칭은 염산+초산 수용액, 염산+질산+초산 수용액, 옥살산 수용액, 염화제이철 수용액 등의 에칭액이 사용되어 왔다. However, due to the chemical resistance of the transparent conductive film (ITO film), it is known that the etching of the transparent conductive film (ITO film) chemically is quite difficult. And etching solutions such as ferric chloride aqueous solution have been used.
상기 염산+초산 수용액은 다른 금속배선에 영향을 주지 않으나, 경시변화가 크고 식각속도가 느리다는 문제점이 있으며, 염산+질산+초산 수용액은 다른 금속배선 중 특히 Mo계열에 영향을 준다는 문제점이 있다. 또한, 상기 염화제이철 수용액은 식각속도는 빠르지만 불안정하고 염산으로 분해되기 쉽다는 문제점이 있었다.The hydrochloric acid + acetic acid aqueous solution does not affect other metal wires, but there is a problem that the change over time is large and the etching speed is slow. In addition, the ferric chloride aqueous solution has a problem that the etching rate is fast but unstable and easily decomposed into hydrochloric acid.
따라서, 다른 금속배선에 영향을 주지 않으며 적절한 식각능력을 가지는 에칭 조성물에 대한 연구가 더욱 필요한 실정이다.Therefore, there is a need for further research on an etching composition having an appropriate etching ability without affecting other metal interconnections.
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 경시변화가 적고 다른 금속배선에 영향을 최소로하여 안정적으로 식각할 수 있으며, 빠른 에칭속도를 갖고 사이드 에칭을 줄일 수 있는 에칭 조성물을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art as described above, the present invention provides a etching composition that can be stably etched with little change over time and minimizes the influence on other metal wiring, and has a fast etching rate and can reduce side etching. For the purpose of
본 발명의 다른 목적은 다른 금속배선에 영향을 주지 않으면서 동시에 식각면이 정렬되고 잔사제거효율이 우수한 에칭 조성물을 제공하는 것이다.Another object of the present invention is to provide an etching composition having an etch surface aligned and excellent in residue removal efficiency without affecting other metal interconnections.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object, the present invention
a) 염산 12 내지 30 중량%;a) 12 to 30% by weight hydrochloric acid;
b) 초산 1 내지 15 중량%;b) 1 to 15% by weight acetic acid;
c) AgNO3, Al(NO3)3, Ba(NO3)2, Ca(NO3)2, Cd(NO3)2, Cd(NO3)3, Ce(NO3)3, Co(NO3)2, Cr(NO3)3, Cu(NO3)2, Eu(NO3)3, Fe(NO3)3, HgNO3, KNO3, La(NO3)3, Mg(NO3)2, NH4NO3, NaNO3, Ni(NO3)2, Pb(NO3)2, PtNO3, Tb(NO3)3, 및 Zn(NO3)2로 이루어지는 군으로부터 1 종 이상 선택되는 첨가제 0.1 내지 5 중량%; 및c) AgNO 3 , Al (NO 3 ) 3 , Ba (NO 3 ) 2 , Ca (NO 3 ) 2 , Cd (NO 3 ) 2 , Cd (NO 3 ) 3 , Ce (NO 3 ) 3 , Co (NO 3 ) 2 , Cr (NO 3 ) 3 , Cu (NO 3 ) 2 , Eu (NO 3 ) 3 , Fe (NO 3 ) 3 , HgNO 3 , KNO 3 , La (NO 3 ) 3 , Mg (NO 3 ) At least one selected from the group consisting of 2 , NH 4 NO 3 , NaNO 3 , Ni (NO 3 ) 2 , Pb (NO 3 ) 2 , PtNO 3 , Tb (NO 3 ) 3 , and Zn (NO 3 ) 2 . Additive 0.1 to 5 wt%; And
d) 잔량의 초순수d) residual ultrapure water
를 포함하는 박막트랜지스터 액정표시장치의 에칭 조성물을 제공한다.It provides an etching composition of the thin film transistor liquid crystal display device comprising a.
또한 본 발명은 상기 에칭 조성물로 에칭하는 단계를 포함하는 박막트랜지스 터 액정표시장치의 제조방법을 제공한다.In another aspect, the present invention provides a method for manufacturing a thin film transistor liquid crystal display device comprising the step of etching with the etching composition.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명의 박막트랜지스터 액정표시장치의 에칭 조성물은 a) 염산 12 내지 30 중량%, b) 초산 1 내지 15 중량%, c) AgNO3, Al(NO3)3, Ba(NO3)2, Ca(NO3)2, Cd(NO3)2, Cd(NO3)3, Ce(NO3)3, Co(NO3)2, Cr(NO3)3, Cu(NO3)2, Eu(NO3)3, Fe(NO3)3, HgNO3, KNO3, La(NO3)3, Mg(NO3)2, NH4NO3, NaNO3, Ni(NO3)2, Pb(NO3)2, PtNO3, Tb(NO3)3, 및 Zn(NO3)2로 이루어지는 군으로부터 1 종 이상 선택되는 첨가제 0.1 내지 5 중량%, 및 d) 잔량의 초순수를 포함하는 것을 특징으로 한다.The etching composition of the thin film transistor liquid crystal display device of the present invention comprises a) 12 to 30% by weight of hydrochloric acid, b) 1 to 15% by weight of acetic acid, c) AgNO 3 , Al (NO 3 ) 3 , Ba (NO 3 ) 2 , Ca (NO 3 ) 2 , Cd (NO 3 ) 2 , Cd (NO 3 ) 3 , Ce (NO 3 ) 3 , Co (NO 3 ) 2 , Cr (NO 3 ) 3 , Cu (NO 3 ) 2 , Eu ( NO 3 ) 3 , Fe (NO 3 ) 3 , HgNO 3 , KNO 3 , La (NO 3 ) 3 , Mg (NO 3 ) 2 , NH 4 NO 3 , NaNO 3 , Ni (NO 3 ) 2 , Pb (NO 3 ) 0.1 to 5% by weight of at least one additive selected from the group consisting of 2 , PtNO 3 , Tb (NO 3 ) 3 , and Zn (NO 3 ) 2 , and d) residual ultrapure water. .
본 발명에 사용되는 염산, 초산, 및 초순수는 반도체 공정용으로 사용가능한 순도의 것을 사용하는 것이 좋으며, 시판되는 것을 사용하거나 공업용 등급을 당업계에 통상적으로 공지된 방법에 따라 정제하여 사용할 수도 있다. The hydrochloric acid, acetic acid, and ultrapure water used in the present invention is preferably one of purity usable for the semiconductor process, and commercially available or industrial grades may be purified according to methods commonly known in the art.
본 발명에 사용되는 상기 a)의 염산은 에칭 조성물에 12 내지 30 중량%로 포함되는 것이 바람직하고, 더욱 바람직하게는 15 내지 20 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 ITO 식각 조건에서 다른 금속배선에의 영향을 최소로 할 수 있으며, 경시변화를 줄일 수 있는 효과가 있다.The hydrochloric acid of a) used in the present invention is preferably included in an etching composition of 12 to 30% by weight, more preferably 15 to 20% by weight. When the content is within the above range, the effect on other metal wirings in the ITO etching conditions can be minimized, and the change over time can be reduced.
본 발명에 사용되는 상기 b)의 초산은 반응 속도를 조절하는 완충제 작용을 한다.The acetic acid of b) used in the present invention acts as a buffer to control the reaction rate.
상기 초산은 에칭 조성물에 1 내지 15 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 5 내지 10 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 반응 속도를 적절히 조절하여 에칭 속도를 향상시키고, 이에 따라 생산성을 향상시킬 수 있는 효과가 있다.The acetic acid is preferably included in 1 to 15% by weight, more preferably 5 to 10% by weight in the etching composition. When the content is in the above range, the reaction rate is appropriately adjusted to improve the etching rate, thereby improving the productivity.
본 발명에 사용되는 상기 c)의 AgNO3, Al(NO3)3, Ba(NO3)2, Ca(NO3)2, Cd(NO3)2, Cd(NO3)3, Ce(NO3)3, Co(NO3)2, Cr(NO3)3, Cu(NO3)2, Eu(NO3)3, Fe(NO3)3, HgNO3, KNO3, La(NO3)3, Mg(NO3)2, NH4NO3, NaNO3, Ni(NO3)2, Pb(NO3)2, PtNO3, Tb(NO3)3, 및 Zn(NO3)2로 이루어지는 군으로부터 1 종 이상 선택되는 첨가제는 잔사제거효율을 향상시키는 작용을 하며, 특히 NH4NO3, NaNO3, KNO3, 및 Fe(NO3)3으로 이루어지는 군으로부터 1 종 이상 선택되는 첨가제를 사용하는 것이 더욱 바람직하다.AgNO 3 , Al (NO 3 ) 3 , Ba (NO 3 ) 2 , Ca (NO 3 ) 2 , Cd (NO 3 ) 2 , Cd (NO 3 ) 3 , Ce (NO) of c) used in the present invention 3 ) 3 , Co (NO 3 ) 2 , Cr (NO 3 ) 3 , Cu (NO 3 ) 2 , Eu (NO 3 ) 3 , Fe (NO 3 ) 3 , HgNO 3 , KNO 3 , La (NO 3 ) 3 , Mg (NO 3 ) 2 , NH 4 NO 3 , NaNO 3 , Ni (NO 3 ) 2 , Pb (NO 3 ) 2 , PtNO 3 , Tb (NO 3 ) 3 , and Zn (NO 3 ) 2 At least one additive selected from the group serves to improve residue removal efficiency, and in particular, at least one additive selected from the group consisting of NH 4 NO 3 , NaNO 3 , KNO 3 , and Fe (NO 3 ) 3 is used. More preferably.
상기 첨가제는 에칭 조성물에 0.1 내지 5 중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 0.1 내지 2 중량%로 포함되는 것이다. 그 함량이 상기 범위내일 경우에는 잔사제거효율이 더욱 좋다.The additive is preferably included in the etching composition 0.1 to 5% by weight, more preferably 0.1 to 2% by weight. If the content is within the above range, the residue removal efficiency is better.
본 발명에 사용되는 상기 d)의 초순수는 에칭 조성물에 잔량으로 포함되어 에칭 조성물을 희석하는 작용을 한다.The ultrapure water of d) used in the present invention is included in the etching composition as a residual amount to dilute the etching composition.
상기 초순수는 잔량의 이온교환수지를 통하여 여과한 순수를 사용하는 것이 바람직하며, 특히 비저항이 18 메가오옴(㏁) 이상인 초순수를 사용하는 것이 더욱 바람직하다.As the ultrapure water, it is preferable to use pure water filtered through a residual amount of ion exchange resin, and in particular, it is more preferable to use ultrapure water having a specific resistance of 18 megohms or more.
상기와 같은 성분으로 이루어지는 본 발명의 에칭 조성물은 e) 계면활성제를 추가로 포함할 수 있다.The etching composition of this invention which consists of such a component can further contain e) surfactant.
상기 계면활성제는 에칭 조성물의 표면장력을 낮추어 대형기판에 잘 퍼지게 함으로써 대형기판에서 에칭 균일성을 증가시키고, 잔사를 제거하는 작용을 한다. The surfactant lowers the surface tension of the etching composition and spreads well on the large substrate, thereby increasing etching uniformity on the large substrate and removing residue.
상기 계면활성제는 낮은 pH에 견딜 수 있으며, 산성조건에서 사용가능한 계면활성제이면 제한되지 않으나, 특히 CF 체인이 최소 8 개인 셀포네이트 그룹을 가지는 불소계 음이온성 계면활성제를 사용하는 것이 바람직하다.The surfactant is not limited as long as it can withstand low pH and can be used in acidic conditions, but in particular, it is preferable to use a fluorine-based anionic surfactant having at least eight cell chain groups having CF chains.
상기 계면활성제는 에칭 조성물에 10 내지 300 ppm으로 포함되는 것이 바람직하며, 그 함량이 상기 범위내일 경우에 잔사제거효율이 우수하면서 동시에 대형기판에서의 에칭 균일성을 향상시킬 수 있어 더욱 좋다.The surfactant is preferably included in the etching composition of 10 to 300 ppm, when the content is in the above range is excellent in the residue removal efficiency and at the same time can improve the etching uniformity on a large substrate.
또한 본 발명은 상기와 같은 성분으로 이루어지는 에칭 조성물로 에칭하는 단계를 포함하는 박막트랜지스터 액정표시장치의 제조방법을 제공하는 바, 상기와 같은 에칭 전후의 박막트랜지스터 액정표시장치의 제조방법에 적용되는 통상적인 공정들이 적용될 수 있음은 물론이다.In another aspect, the present invention provides a method for manufacturing a thin film transistor liquid crystal display device comprising the step of etching with an etching composition consisting of the above components, the conventional method applied to the manufacturing method of the thin film transistor liquid crystal display device before and after the etching Of course, phosphorous processes may be applied.
상기와 같은 본 발명에 따른 에칭 조성물은 경시변화가 적고 다른 금속배선에 영향을 최소로하여 안정적으로 식각할 수 있으며, 빠른 에칭속도를 갖고 사이드 에칭을 줄일 수 있을 뿐만 아니라, 동시에 식각면이 정렬되고 잔사제거효율이 우수한 잇점이 있다. 또한, 기포발생량이 종래 에칭 조성물에 비하여 현저히 적으므로 스프레이 방식의 에칭방식에 적용하기 용이한 효과가 있다.The etching composition according to the present invention as described above can be etched stably with little change over time and with minimal effect on other metallization, can reduce side etching with fast etching rate, and at the same time the etching surface is aligned It has the advantage of excellent residue removal efficiency. In addition, since the bubble generation amount is significantly smaller than that of the conventional etching composition, there is an effect that it is easy to apply to the etching method of the spray method.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것 은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
실시예 1Example 1
염산 12 중량%, 초산 3 중량%, 첨가제로 NH4NO3 0.1 중량%, 및 잔량의 초순수를 균일하게 혼합하여 에칭 조성물을 제조하였다.An etching composition was prepared by uniformly mixing 12 wt% hydrochloric acid, 3 wt% acetic acid, 0.1 wt% NH 4 NO 3 as an additive, and the remaining amount of ultrapure water.
실시예 2∼4, 및 비교예 1∼4Examples 2-4 and Comparative Examples 1-4
상기 실시예 1에서 하기 표 1에 나타낸 조성비로 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하여 에칭 조성물을 제조하였다. Except for using the composition ratio shown in Table 1 in Example 1 was carried out in the same manner as in Example 1 to prepare an etching composition.
또한, 유리기판상에 투명도전막(ITO막)을 스퍼터링을 통하여 형성시키 후, 포토레지스트를 코팅하고 현상하여 패턴을 형성시킨 시편에 상기 실시예 1 내지 4, 및 비교예 1 내지 4의 에칭 조성물을 45 ℃로 고정한 후, 90 초 동안 침지하여 에칭 성향을 측정하고 그 결과를 하기 표 1에 나타내었다. 이때, 표 1의 단위는 중량%이다.Further, after forming a transparent conductive film (ITO film) on a glass substrate through sputtering, the etching composition of Examples 1 to 4 and Comparative Examples 1 to 4 was applied to a specimen in which a photoresist was coated and developed to form a pattern. After fixing to ℃, it was immersed for 90 seconds to measure the etching propensity and the results are shown in Table 1 below. At this time, the unit of Table 1 is weight%.
상기 표 1을 통하여, 본 발명에 따라 제조한 실시예 1 내지 4의 에칭 조성물이 비교예 1 내지 4와 비교하여 잔사제거효율이 우수함을 확인할 수 있었다.Through Table 1, it was confirmed that the etching composition of Examples 1 to 4 prepared according to the present invention is superior in residue removal efficiency compared to Comparative Examples 1 to 4.
실시예 5∼13Examples 5 to 13
염산 15 중량%, 초산 5 중량%, 첨가제로 NH4NO3 1.0 중량%, 및 잔량의 초순수로 이루어지는 에칭 조성물에 하기 표 2에 나타낸 바와 같이 불소계 음이온성 계면활성제로 암모늄 퍼플루오로 옥틸 설포네이트를 0, 50, 100, 300, 500, 1,000 ppm으로 각각 달리 첨가한 후, 균일하게 혼합하여 에칭 조성물을 제조하였다. 이때, 표 2의 단위는 중량%이다.Ammonium perfluoro octyl sulfonate was added to the etching composition consisting of 15 wt% hydrochloric acid, 5 wt% acetic acid, 1.0 wt% NH 4 NO 3 as an additive, and the remaining amount of ultrapure water, as shown in Table 2 below. 0, 50, 100, 300, 500 and 1,000 ppm, respectively, were added differently, and then uniformly mixed to prepare an etching composition. At this time, the unit of Table 2 is weight%.
상기 실시예 5, 실시예 8, 및 실시예 10 내지 13에서 제조한 에칭 조성물을 이용하여 계면활성제의 농도에 따른 잔사제거효율을 측정하고 그 결과를 하기 표 3에 나타내었다. The residue removal efficiency according to the concentration of the surfactant was measured using the etching compositions prepared in Examples 5, 8, and 10 to 13, and the results are shown in Table 3 below.
상기 표 3을 통하여, 본 발명에 따라 제조한 에칭 조성물에 계면활성제를 첨가할 경우 더욱 효과적으로 잔사를 제거할 수 있음을 확인할 수 있으며, 특히 계면활성제의 농도가 10 내지 300 ppm일 경우 그 효과가 더욱 우수함을 알 수 있었다. Through Table 3, it can be seen that when the surfactant is added to the etching composition prepared according to the present invention, the residue can be more effectively removed, especially when the concentration of the surfactant is 10 to 300 ppm. It was found to be excellent.
또한, 상기 실시예 5 내지 10 및 실시예 12 내지 13에서 제조한 에칭 조성물을 계면활성제의 농도에 따른 표면장력을 측정하고 그 결과를 하기 표 4 및 도 1에 나타내었다.In addition, the surface tension of the etching compositions prepared in Examples 5 to 10 and Examples 12 to 13 according to the concentration of the surfactant was measured and the results are shown in Table 4 and FIG. 1.
상기 표 4 및 도 1을 통하여, 본 발명에 따른 에칭 조성물은 계면활성제의 농도가 높아질수록 표면장력이 저하됨을 확인할 수 있었으며, 특히 계면활성제의 농도가 10 내지 300 ppm일 경우 잔사제거효율이 우수한 동시에 표면장력을 낮추어 대형기판에서의 에칭 균일성을 향상시킬 수 있음을 확인할 수 있었다.Through the Table 4 and Figure 1, the etching composition according to the present invention was confirmed that the surface tension is lowered as the concentration of the surfactant is increased, especially when the concentration of the surfactant is 10 to 300 ppm excellent residue removal efficiency By lowering the surface tension, it was confirmed that the etching uniformity of the large substrate could be improved.
또한, 투명도전막(ITO막)을 상기 실시예 1, 비교예 1, 및 실시예 6에서 제조한 에칭 조성물로 에칭처리한 후, 단면을 주사현미경(SEM, S-4199, 히다찌사)으로 관찰하여 그 결과를 각각 도 2, 도 3, 및 도 4에 나타내었다. Further, after the transparent conductive film (ITO film) was etched with the etching compositions prepared in Examples 1, Comparative Examples 1 and 6, the cross section was observed with a scanning microscope (SEM, S-4199, Hitachi, Inc.). The results are shown in FIGS. 2, 3, and 4, respectively.
도 2 및 도 3에 나타낸 바와 같이 본 발명에 따라 첨가제를 포함하는 실시예 1의 에칭 조성물(도 2)은 첨가제를 사용하지 않은 비교예 1의 에칭 조성물(도 3)과 비교하여 잔사를 효과적으로 제거할 수 있었으며, 다른 금속배선에 영향을 주지 않고 안정적으로 식각할 수 있음을 확인할 수 있었다. 또한 본 발명의 에칭 조성물에 불소계 음이온성 계면활성제를 포함한 실시예 6(도 4)의 경우 계면활성제를 추가로 포함하여 잔사제거효율이 더욱 우수함을 확인할 수 있었다.As shown in Figures 2 and 3, the etching composition of Example 1 comprising an additive according to the present invention (FIG. 2) effectively removes residues compared to the etching composition of Comparative Example 1 (FIG. 3) without additives. It was possible to confirm that it can be etched stably without affecting other metal wiring. In addition, in the case of Example 6 (FIG. 4) including the fluorine-based anionic surfactant in the etching composition of the present invention, it was confirmed that the residue removal efficiency was further excellent by further including the surfactant.
발명에 따른 에칭 조성물은 경시변화가 적고 다른 금속배선에 영향을 최소로 하여 안정적으로 식각할 수 있으며, 빠른 에칭속도를 갖고 사이드 에칭을 줄일 수 있을 뿐만 아니라, 동시에 식각면이 정렬되고 잔사제거효율이 우수한 잇점이 있다. 또한, 기포발생량이 종래 에칭 조성물에 비하여 현저히 적으므로 스프레이 방식의 에칭방식에 적용하기 용이한 효과가 있다.The etching composition according to the present invention can be stably etched with little change over time and with minimal influence on other metal wirings, and has a fast etching speed and can reduce side etching, and at the same time, the etching surfaces are aligned and residue removal efficiency is improved. There is an advantage. In addition, since the bubble generation amount is significantly smaller than that of the conventional etching composition, there is an effect that it is easy to apply to the etching method of the spray method.
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| KR100771314B1 (en) * | 2006-11-16 | 2007-10-29 | 삼성전기주식회사 | Etching solution containing ceramic nano particles and process for forming circuits using the same |
| CN104388090A (en) * | 2014-10-21 | 2015-03-04 | 深圳新宙邦科技股份有限公司 | Oxalic acid-series ITO (Indium Tin Oxide) etching liquid, as well as preparation method and application thereof |
| US9477358B2 (en) | 2013-10-18 | 2016-10-25 | Samsung Display Co., Ltd. | Touch screen panel and method of manufacturing the same |
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| KR101160829B1 (en) * | 2005-02-15 | 2012-06-29 | 삼성전자주식회사 | Etchant composition and method for thin film transistor array panel |
| CN103255417B (en) * | 2011-12-16 | 2016-01-20 | 江阴润玛电子材料股份有限公司 | A kind of acid molybdenum aluminium-molybdenum etching liquid and preparation technology thereof |
| CN102732252A (en) * | 2012-06-21 | 2012-10-17 | 江阴润玛电子材料股份有限公司 | Novel aqua regia system ITO (indium tin oxide) etching solution and its preparation method |
| CN110564420A (en) * | 2019-08-22 | 2019-12-13 | 合肥中聚合臣电子材料有限公司 | ITO etching solution for advanced flat plate |
| CN114085671B (en) * | 2021-12-14 | 2022-09-02 | 合肥中聚和成电子材料有限公司 | ITO (indium tin oxide) etching liquid for IPS (in-plane switching) type liquid crystal panel and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3583583D1 (en) * | 1984-11-17 | 1991-08-29 | Daikin Ind Ltd | ACTION COMPOSITION. |
| JPH02135619A (en) * | 1988-11-17 | 1990-05-24 | Asahi Glass Co Ltd | Wet etching method |
| JP3458023B2 (en) * | 1995-08-01 | 2003-10-20 | メック株式会社 | Copper and copper alloy microetchants |
| JPH10110281A (en) * | 1996-10-03 | 1998-04-28 | Asahi Denka Kogyo Kk | Etching method for metallic oxide thin film |
| EP1187225B1 (en) * | 2000-09-08 | 2006-11-15 | Kanto Kagaku Kabushiki Kaisha | Etching liquid composition |
| JP4897148B2 (en) * | 2001-03-29 | 2012-03-14 | 富士技研工業株式会社 | Etching solution for transparent conductive film |
| KR100532080B1 (en) * | 2001-05-07 | 2005-11-30 | 엘지.필립스 엘시디 주식회사 | Echant for amorphous indium-tin-oxide and fabrication method using the same |
-
2005
- 2005-02-25 TW TW094105805A patent/TWI364072B/en not_active IP Right Cessation
- 2005-03-14 JP JP2005070912A patent/JP4778716B2/en not_active Expired - Fee Related
- 2005-03-16 KR KR1020050021921A patent/KR101226546B1/en active IP Right Grant
- 2005-03-17 CN CN2005100554183A patent/CN1670624B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100771314B1 (en) * | 2006-11-16 | 2007-10-29 | 삼성전기주식회사 | Etching solution containing ceramic nano particles and process for forming circuits using the same |
| US9477358B2 (en) | 2013-10-18 | 2016-10-25 | Samsung Display Co., Ltd. | Touch screen panel and method of manufacturing the same |
| CN104388090A (en) * | 2014-10-21 | 2015-03-04 | 深圳新宙邦科技股份有限公司 | Oxalic acid-series ITO (Indium Tin Oxide) etching liquid, as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI364072B (en) | 2012-05-11 |
| TW200603279A (en) | 2006-01-16 |
| CN1670624B (en) | 2012-11-14 |
| KR101226546B1 (en) | 2013-01-25 |
| CN1670624A (en) | 2005-09-21 |
| JP4778716B2 (en) | 2011-09-21 |
| JP2005268790A (en) | 2005-09-29 |
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