KR20170112314A - Wet etching method for a single layer or multiple layer comprising Ag or Ag alloy, and etchant composition for a single layer or multiple layer comprising Ag or Ag alloy, and method for manufacturing a thin film transistor and a thin film transistor - Google Patents
Wet etching method for a single layer or multiple layer comprising Ag or Ag alloy, and etchant composition for a single layer or multiple layer comprising Ag or Ag alloy, and method for manufacturing a thin film transistor and a thin film transistor Download PDFInfo
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- KR20170112314A KR20170112314A KR1020160039206A KR20160039206A KR20170112314A KR 20170112314 A KR20170112314 A KR 20170112314A KR 1020160039206 A KR1020160039206 A KR 1020160039206A KR 20160039206 A KR20160039206 A KR 20160039206A KR 20170112314 A KR20170112314 A KR 20170112314A
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- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 51
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000010409 thin film Substances 0.000 title claims abstract description 15
- 239000002356 single layer Substances 0.000 title abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 238000001039 wet etching Methods 0.000 title description 8
- 239000010408 film Substances 0.000 claims abstract description 95
- 238000005530 etching Methods 0.000 claims abstract description 86
- 239000004332 silver Substances 0.000 claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 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 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000000174 gluconic acid Substances 0.000 claims abstract description 11
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910021332 silicide Inorganic materials 0.000 claims description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XSNQEMWVLMRPFR-UHFFFAOYSA-N silver nitride Chemical compound [N-3].[Ag+].[Ag+].[Ag+] XSNQEMWVLMRPFR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- 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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- 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
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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
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- 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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- H01L21/34—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 not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/469—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After-treatment of these layers
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- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
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Abstract
본 발명은 특정의 종방향 및 횡방향의 식각속도로 식각하는 것에 특징이 있는 식각방법; 식각액을 분사하는 분사 노즐을 특정의 속도로 스윙시켜서 식각하는 것에 특징이 있는 식각방법; 및 조성물 총 중량에 대해 인산 40 내지 60중량%, 질산 3 내지 8 중량%, 초산 5 내지 20중량%, 글루콘산 0.8 내지 1.2 중량% 및 잔량의 물을 포함하는 은 또는 은합금을 포함하는 단일막 또는 다층막용 식각액 조성물; 박막트랜지스터의 제조방법; 및 박막트랜지스터를 제공한다.The present invention relates to an etching method characterized by etching at specific longitudinal and transverse etching rates; An etching method characterized in that an injection nozzle for spraying an etchant is swung at a specific speed and etched; And a single layer comprising silver or silver alloy containing 40 to 60 wt% phosphoric acid, 3 to 8 wt% nitric acid, 5 to 20 wt% acetic acid, 0.8 to 1.2 wt% gluconic acid, and balance water, based on the total weight of the composition Or an etchant composition for a multilayer film; A method of manufacturing a thin film transistor; And a thin film transistor.
Description
본 발명은 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법, 및 은 또는 은합금을 포함하는 단일막 또는 다층막의 식각액 조성물, 및 상기 식각액 조성물을 사용하는 박막트렌지스터의 제조방법 및 상기 방법에 의해 제조된 박막트랜지스터에 관한 것이다. The present invention relates to a wet etching method for a single-layer or multi-layered film containing silver or silver alloy and a single-layer or multi-layered film containing silver or silver alloy, and a method for producing the thin- To a thin film transistor manufactured by the method.
표시 장치의 일 예로서 LCD(액정표시장치)는 어레이 기판과 컬러필터 기판, 그리고 두 기판 사이에 주입되어 있는 액정층으로 이루어진 액정패널을 포함한다. 상기 어레이 기판에는 액정층에 신호를 전달하기 위해 배선이 형성되어 있다. 어레이 기판의 배선은 게이트 배선과 데이터 배선을 포함한다.As an example of a display device, an LCD (liquid crystal display device) includes an array substrate, a color filter substrate, and a liquid crystal panel composed of a liquid crystal layer injected between two substrates. In the array substrate, wirings are formed to transmit signals to the liquid crystal layer. The wiring of the array substrate includes a gate wiring and a data wiring.
또한, OLED 디스플레이는 두 개의 반대 전극과 그 사이에 존재하는 다층의 반도체적 성질을 갖는 유기물의 박막들로 구성되는 유기발광다이오드(OLED, Organic Light Emitting Diode)를 포함한다. In addition, the OLED display includes an organic light emitting diode (OLED) composed of two opposing electrodes and thin films of organic materials having a multilayered semiconducting property existing therebetween.
이러한 배선 및 전극들은 금속 단일층 또는 합금 단일층으로 이루어질 수도 있고, 각 금속 또는 합금의 단점을 보완하고 원하는 물성을 얻기 위하여 다중층으로 형성될 수도 있다.These wirings and electrodes may consist of a single layer of metal or a single layer of alloy and may be formed in multiple layers to complement the disadvantages of each metal or alloy and to obtain desired properties.
배선 또는 전극을 형성하기 위해 일반적으로 알루미늄을 많이 사용하는데, 순수한 알루미늄은 화학약품에 대한 내식성이 약하고 후속공정에서 배선 결함문제를 야기할 수도 있으므로, 이를 보완하기 위해 알루미늄합금을 사용하거나 알루미늄 또는 알루미늄합금 위에 또 다른 금속층 예를 들어 몰리브덴, 크롬, 텅스텐, 주석 등의 금속층을 적층시킨 다중층을 사용하기도 한다.Aluminum is generally used to form wiring or electrodes. Pure aluminum is weak in corrosion resistance to chemicals and may cause wire defects in subsequent processes. To compensate for this, aluminum alloys are used, or aluminum or aluminum alloys A multilayer in which a metal layer such as molybdenum, chromium, tungsten, or tin is laminated may be used.
그러나 근래에 들어 표시장치의 고해상도 및 대형화에 대한 요구가 증대되어 왔으며, 이를 실현하기 위해서 알루미늄 보다 낮은 저항을 가지는 금속막을 사용하고자 하는 연구가 계속되어 왔다. 이에 따라 알루미늄(비저항: 2.65 uΩcm) 보다 낮은 저항을 가지는 은(비저항: 1.59 uΩcm) 을 사용하여 배선 또는 전극을 형성하는 기술이 진행되어 왔다.In recent years, however, there has been a growing demand for a high-resolution and large-sized display device. To achieve this, research has been continued to use a metal film having a resistance lower than that of aluminum. Accordingly, a technique of forming a wiring or an electrode using silver (resistivity: 1.59 u? Cm) having a lower resistance than aluminum (resistivity: 2.65 u? Cm) has been advanced.
한편, 투과형 액정표시장치는 실외처럼 외부광이 강한 경우에는 화면이 잘 보이지 않는 단점이 있고, 백라이트를 쓰기 때문에 저전력 소비를 실현하기가 어려우며, 따라서 이동성에도 제한을 받고 있다. 이런 단점을 극복하기 위해서, 백라이트 없이 외부광을 이용한 반사형 액정표시장치와 외부광과 백라이트를 동시에 이용하여 실외에서도 잘 볼 수 있는 반투과형 액정표시장치에 대한 개발이 활발히 진행되고 있다. 반사형 또는 반투과형 액정표시장치에서는 백라이트를 대신하거나 보조하기 위해 반사막이 패터닝되어야 한다. 일반적으로 종래 기술에서는 알루미늄 금속막(반사율: 83.3 %)이 사용되어 왔으나 보다 높은 반사율을 얻기 위해 은 또는 은합금(반사율: 96.4 %)을 도입하고 있는 실정이다.On the other hand, a transmissive liquid crystal display device has a disadvantage that a screen is not easily visible when external light is strong, such as an outdoor light, and it is difficult to realize low power consumption due to the use of a backlight. In order to overcome such disadvantages, a reflection type liquid crystal display device using external light without backlight and a semi-transmission type liquid crystal display device which can be seen even outdoors by simultaneously using external light and backlight are being actively developed. In reflective or semi-transmissive liquid crystal display devices, the reflective film must be patterned to replace or assist the backlight. In general, an aluminum metal film (reflectance: 83.3%) has been used in the prior art, but silver or silver alloy (reflectance: 96.4%) is introduced to obtain a higher reflectance.
이러한 배선, 전극, 및 반사막 등을 형성하기 위해서는 식각을 통하여 금속막을 패터닝하여야 하는데, 식각에는 건식식각과 습식식각이 있으며, 균일하게 식각되고 생산성이 높은 습식식각이 많이 사용된다.In order to form such a wiring, an electrode, and a reflective film, a metal film must be patterned through etching. Dry etch and wet etch are used for etching, and wet etch is uniformly etched and highly productive.
습식식각에 사용되는 은 또는 은합금 식각용액에 관한 종래의 기술로서 대한민국 공개공보 제10-2006-0069601호는 인산, 질산, 초산, 식각특성개선제를 포함하는 식각용액을 개시하고 있다. 그러나 상기 식각용액은 CD skew 값이 전혀 고려되지 않아 실제로 은 또는 은합금의 다양한 단일막 또는 다중막에 상기 식각용액을 적용할 경우 CD skew 0.5㎛ 이상으로 에칭 되어 미세패턴 사용이 불가능한 문제가 있었다.Korean Patent Laid-Open No. 10-2006-0069601 discloses an etching solution containing phosphoric acid, nitric acid, acetic acid and an etching property improving agent as a conventional technique for a silver or silver alloy etching solution used for wet etching. However, since the etching solution does not consider the CD skew value at all, in practice, when the etching solution is applied to various single or multiple films of silver or silver alloy, the CD skew is etched to 0.5 μm or more, which makes it impossible to use fine patterns.
본 발명은, 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로서, SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art,
우수한 식각프로파일을 형성하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a wet etching method of a single film or a multilayer film containing silver or silver alloy which forms an excellent etching profile.
또한, 본 발명은 은 또는 은합금을 포함하는 단일막 또는 다층막에 대한 식각속도가 우수하며, Pad 부에 노출된 데이타 배선을 손상시키지 않으며, 은의 재흡착을 최소화하며, 미세식각 균일성을 나타내는 식각액 조성물을 제공하는 것을 목적으로 한다.The present invention also provides a method of manufacturing a semiconductor device, which is excellent in an etching speed for a single film or a multilayer film including silver or silver alloy, does not damage the data wiring exposed to the pad portion, minimizes the re-adsorption of silver, And to provide a composition.
또한, 본 발명은 상기 식각액 조성물에 의한 식각공정을 포함하는 박막트랜지스터의 제조방법 및 상기 방법에 의해 제조된 박막트랜지스터를 제공하는 것을 목적으로 한다. It is another object of the present invention to provide a method of manufacturing a thin film transistor including an etching process using the etchant composition and a thin film transistor manufactured by the method.
본 발명은 The present invention
은 또는 은합금을 포함하는 단일막 또는 다층막의 식각에 있어서,In the etching of a single film or multilayer film containing silver or silver alloy,
400 Å/sec ~ 600 Å/sec의 종방향 식각속도 및 2 Å/sec ~ 6 Å/sec의 횡방향 식각속도로 식각공정을 수행하는 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법을 제공한다. Wherein the etch process is performed at a longitudinal etch rate of 400 A / sec to 600 A / sec and a lateral etch rate of 2 A / sec to 6 A / sec. Wet etching method.
또한, 본 발명은In addition,
조성물 총 중량에 대해 인산 40 내지 60중량%, 질산 3 내지 8 중량%, 초산 5 내지 20중량%, 글루콘산 0.8 내지 1.2 중량% 및 잔량의 물을 포함하는 은 또는 은합금을 포함하는 단일막 또는 다층막용 식각액 조성물을 제공한다.A single film comprising silver or silver alloy containing 40 to 60% by weight of phosphoric acid, 3 to 8% by weight of nitric acid, 5 to 20% by weight of acetic acid, 0.8 to 1.2% by weight of gluconic acid, Thereby providing an etchant composition for a multilayered film.
또한, 본 발명은,Further, according to the present invention,
(a)기판 상에 금속층을 형성하는 단계;(a) forming a metal layer on a substrate;
(b)상기 금속층을 식각하여 게이트 전극을 형성하는 단계;(b) etching the metal layer to form a gate electrode;
(c)상기 게이트 전극 상에 게이트 절연층을 형성하는 단계;(c) forming a gate insulating layer on the gate electrode;
(d)상기 게이트 절연층 상에 반도체층을 형성하는 단계;(d) forming a semiconductor layer on the gate insulating layer;
(e)상기 반도체층 상에 소스 및 드레인전극을 형성하는 단계; 및(e) forming source and drain electrodes on the semiconductor layer; And
(f)상기 소스 및 드레인전극 상에 화소전극을 형성하는 단계를 포함하며,(f) forming pixel electrodes on the source and drain electrodes,
상기 (b)단계 및 (e)단계 중 적어도 어느 한 단계에서는 상기 본 발명의 식각액 조성물을 사용하여 은 또는 은합금을 포함하는 단일막 또는 다층막을 식각하는 공정을 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법을 제공한다.Wherein at least one of the steps (b) and (e) includes a step of etching a single layer or a multilayer including silver or silver alloy using the etchant composition of the present invention. And a manufacturing method thereof.
또한, 본 발명은In addition,
상기 방법에 의해 제조되는 것을 특징으로 하는 박막트랜지스터를 제공한다.The thin film transistor is manufactured by the above method.
본 발명의 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법은 종방향 및 횡방향의 식각 속도를 조절함으로써 우수한 식각프로파일을 제공한다. The wet etching method of the single or multi-layered film containing silver or silver alloy of the present invention provides an excellent etching profile by controlling the longitudinal and lateral etching rates.
또한, 본 발명의 식각액 조성물은 은 또는 은합금을 포함하는 단일막 또는 다층막에 대한 우수한 식각속도, Pad 부에 노출된 데이타 배선에 대한 손상방지, 은의 재흡착 방지 효과를 제공하며, 미세식각 균일성을 제공한다.In addition, the etchant composition of the present invention provides an excellent etching rate for a single layer or a multilayer including silver or silver alloy, prevention of damages to data wiring exposed to the pad portion, and prevention of re-adsorption of silver, .
본 발명의 박막트랜지스터의 제조방법은 게이트 전극 및 소스/드레인 전극에 대한 효과적인 식각이 가능하므로, 성능이 우수한 박막트랜지스터를 제공한다. The method of manufacturing a thin film transistor according to the present invention can effectively etch gate electrodes and source / drain electrodes, thereby providing a thin film transistor having excellent performance.
도 1은 본 발명의 실시예 1에서 종방향 및 횡방향의 식각속도 조절에 의하여 시편을 식각한 결과를 촬영하여 나타낸 SEM 이미지이다.FIG. 1 is an SEM image of a sample obtained by etching a specimen by adjusting the etching rate in the longitudinal and lateral directions according to the first embodiment of the present invention. FIG.
본 발명은 은 또는 은합금을 포함하는 단일막 또는 다층막의 식각에 있어서, 400 Å/sec ~ 600 Å/sec의 종방향 식각속도 및 2 Å/sec ~ 6 Å/sec의 횡방향 식각속도로 식각공정을 수행하는 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법에 관한 것이다. The present invention relates to a method of etching a single-layer or multi-layered film including silver or silver alloy using a longitudinal etch rate of 400 A / sec to 600 A / sec and a lateral etch rate of 2 A / sec to 6 A / The present invention relates to a wet etching method for a single-layer or multi-layered film including silver or silver alloy.
상기에서 450 Å/sec ~ 550 Å/sec의 종방향 식각속도 및 3 Å/sec ~ 5 Å/sec의 횡방향 식각속도로 식각이 실시되는 경우 더욱 바람직할 수 있다.It may be more preferable that the etching is performed at a longitudinal etching rate of 450 Å / sec to 550 Å / sec and a lateral etching rate of 3 Å / sec to 5 Å / sec.
본 발명에 있어서, 종방향 식각속도가 400 Å/sec 미만이 되면 식각 시간이 너무 길어져서 식각효율이 저하되며, 횡방향 식각량이 증가하여 테이퍼 각이 너무 작아지며, 600 Å/sec를 초과하면 테이퍼 각이 너무 커져서 바람직하지 않다. In the present invention, when the longitudinal etching rate is less than 400 ANGSTROM / sec, the etching time becomes too long to lower the etching efficiency, the lateral etching rate increases, and the taper angle becomes too small. When the longitudinal etching rate exceeds 600 ANGSTROM / sec, The angle is too large to be desired.
또한, 본 발명에 있어서, 횡방향 식각속도가 2 Å/sec 미만이 되면 테이퍼 각이 너무 커져서 바람직하지 않으며, 횡방향 식각속도가 6 Å/sec를 초과하면 테이퍼 각이 너무 작아져서 바람직하지 않다. In the present invention, when the transverse etching rate is less than 2 Å / sec, the taper angle becomes too large, and when the transverse etching rate exceeds 6 Å / sec, the taper angle becomes too small.
상기 본 발명의 식각 방법에 있어서 식각에 사용될 수 있는 식각액 조성물로는 예를 들어, 조성물 총 중량에 대해 인산 40 내지 60중량%, 질산 3 내지 8 중량%, 초산 5 내지 20중량%, 글루콘산 0.8 내지 1.2 중량% 및 잔량의 물을 포함하는 식각액 조성물을 들 수 있으며, 상기 식각액으로 식각이 실시되는 경우 바람직한 효과가 얻어질 수 있다. In the etching method of the present invention, the etchant composition which can be used for etching includes, for example, 40 to 60% by weight of phosphoric acid, 3 to 8% by weight of nitric acid, 5 to 20% by weight of acetic acid, 0.8 To 1.2% by weight of water and a residual amount of water, and a desirable effect can be obtained when the etching is performed with the etching solution.
상기 본 발명의 식각 방법에 있어서 은합금은, 은과 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 중 1종 이상의 금속을 포함하여 이루어지는 합금 형태; 또는 은의 질화물막, 규화물막, 탄화물막 또는 산화물 형태일 수 있다. In the etching method of the present invention, the silver alloy may be in the form of an alloy comprising silver and one or more metals selected from the group consisting of Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti; Or a silver nitride film, a silicide film, a carbide film, or an oxide.
또한, 상기 단일막은 예를 들어, 은으로 구성된 단일막 또는 은합금으로 구성된 단일막일 수 있다.Further, the single film may be a single film composed of, for example, silver or a single film composed of silver alloy.
상기 다층막은 상기 단일막과 하나 이상의 금속산화물막이 함께 적층된 형태일 수 있다. 상기 금속산화물막은 예를 들어 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO), 산화갈륨아연인듐(IGZO) 등 일 수 있으며, 보다 구체적으로는 ITO/Ag/ITO, IZO/Ag/IZO, ITZO/Ag/ITZO, IGZO/Ag/IGZO, ITO/Ag합금막/ITO, IZO/Ag합금막/IZO, ITZO/Ag합금막/ITZO, 또는 IGZO/Ag합금막/IGZO 등 일 수 있다. The multi-layered film may be formed by stacking the single film and at least one metal oxide film together. The metal oxide film may be, for example, indium tin oxide (ITO), zinc oxide indium (IZO), zinc indium tin oxide (ITZO), gallium gallium indium (IGZO) Ag alloy film / ITO, IZO / Ag alloy film / IZO, ITZO / Ag alloy film / ITZO, or IGZO / Ag alloy film / ITO / Ag / IZO / Ag / IZO / IGZO, and the like.
또한, 본 발명은 조성물 총 중량에 대해 인산 40 내지 60중량%, 질산 3 내지 8 중량%, 초산 5 내지 20중량%, 글루콘산 0.8 내지 1.2 중량% 및 잔량의 물을 포함하는 은 또는 은합금을 포함하는 단일막 또는 다층막용 식각액 조성물에 관한 것이다.In addition, the present invention relates to a method for producing a silver halide photographic light-sensitive material, which comprises applying silver or silver alloy containing 40 to 60 wt% of phosphoric acid, 3 to 8 wt% of nitric acid, 5 to 20 wt% of acetic acid, 0.8 to 1.2 wt% of gluconic acid, To an etchant composition for a single film or multilayer film.
본 발명의 식각액 조성물은 은, 은합금막, 투명전도막 각각에 대한 식각이 가능하며, 예컨대, 투명전도막/Ag/투명전도막으로 구성되는 3중막에 대한 일괄 에칭도 가능한 특징을 갖는다. 본 발명에서 상기 투명전도막은 금속산화물막으로 형성될 수 있다. The etchant composition of the present invention is capable of etching each of silver, a silver alloy gold film, and a transparent conductive film, and is also capable of batch etching for a triple-layered film composed of, for example, a transparent conductive film / Ag / transparent conductive film. In the present invention, the transparent conductive film may be formed of a metal oxide film.
또한, 본 발명의 식각액은 상부 투명전도막을 다른 식각액으로 에칭 후 본 식각액으로 은(은합금) 및 하부 투명전도막을 에칭하는 2 step 에칭공정에도 사용이 가능하며, 상부 투명전도막을 다른 식각액으로 에칭 한 후 본 식각액으로 은(은합금)막을 에칭한 후 다른 식각액으로 하부 투명전도막을 에칭하는 3step 에칭공정에서 사용이 가능하다.In addition, the etching solution of the present invention can be used in a two-step etching process in which an upper transparent conductive film is etched with another etchant, and then the silver (silver alloy) and the lower transparent conductive film are etched with the present etching solution, and the upper transparent conductive film is etched with another etchant It can be used in the 3 step etching process in which the silver (silver alloy) film is etched with the subsequent etching solution and the lower transparent conductive film is etched with the other etching solution.
본 발명의 식각액 조성물에 의하면 표시 장치의 제조 시, 배선, 전극, 및 반사막으로 사용되는 은(Ag) 또는 은합금으로 이루어진 단일막 및 기 단일막과 투명전도막으로 구성된 다층막에 대해 본 발명의 식각액 조성물을 사용하는 경우, Pattern 부의 배선 및 반사막에 대한 미세 식각 균일성을 나타내고 Pad부 Data배선의 손상으로부터 발생하는 Ag 재흡착 문제도 개선할 수 있다. According to the etchant composition of the present invention, a multilayer film composed of a single film and a single film and a transparent conductive film made of silver (Ag) or silver alloy used as a wiring, an electrode, and a reflective film at the time of manufacturing a display device, In the case of using the composition, it is possible to improve the problem of Ag reattachment caused by damage to the pad portion data wiring, which shows the fine etching uniformity with respect to the wiring and the reflective film in the pattern portion.
상기 본 발명의 식각액 조성물에 있어서 은합금은, 은과 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 중 1종 이상의 금속을 포함하여 이루어지는 합금 형태; 또는 은의 질화물막, 규화물막, 탄화물막 또는 산화물 형태일 수 있다. In the etchant composition of the present invention, the silver alloy may be in the form of an alloy comprising silver and one or more metals selected from the group consisting of Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti; Or a silver nitride film, a silicide film, a carbide film, or an oxide.
또한, 상기 단일막은 예를 들어, 은으로 구성된 단일막 또는 은합금으로 구성된 단일막일 수 있다.Further, the single film may be a single film composed of, for example, silver or a single film composed of silver alloy.
상기 다층막은 상기 단일막과 하나 이상의 금속산화물막이 함께 적층된 형태일 수 있다. 상기 금속산화물막은 예를 들어 산화주석인듐(ITO), 산화아연인듐(IZO), 산화주석아연인듐(ITZO), 산화갈륨아연인듐(IGZO) 등일 수 있으며, 보다 구체적으로는 ITO/Ag/ITO, IZO/Ag/IZO, ITZO/Ag/ITZO, IGZO/Ag/IGZO, ITO/Ag합금막/ITO, IZO/Ag합금막/IZO, ITZO/Ag합금막/ITZO, 또는 IGZO/Ag합금막/IGZO 등 일 수 있다. The multi-layered film may be formed by stacking the single film and at least one metal oxide film together. The metal oxide film may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc indium tin oxide (ITZO), gallium gallium indium (IGZO) IZO / Ag / IZO, ITZO / Ag / ITZO, IGZO / Ag / IGZO, ITO / Ag alloy film / ITO, IZO / Ag alloy film / IZO, ITZO / Ag alloy film / And the like.
본 발명의 식각액에 포함되는 인산(H3PO4)은 주산화제로 사용되는 성분으로서, 은 또는 은합금을 산화시켜 식각하는 역할을 하며, 예컨대, 투명전도막/Ag/투명전도막으로 구성되는 삼중막에서는 은(Ag)과 투명전도막을 산화시켜 식각하는 역할을 수행한다. Phosphoric acid (H 3 PO 4 ) contained in the etchant of the present invention is a component used as a main oxidizing agent. It serves to oxidize and etch silver or silver alloy, and for example, a transparent conductive film / Ag / transparent conductive film In the triple film, silver (Ag) and transparent conductive film are oxidized and etched.
상기 인산(H3PO4)은 식각액 조성물 총 중량에 대하여 40~60 중량%로 포함될 수 있다. 인산의 함량이 40 중량% 미만인 경우에는 은의 식각속도 저하와 식각 프로파일의 불량을 야기시킬 수 있으며, 60 중량%를 초과하는 경우에는 투명전도막의 식각 속도는 저하되고, 은의 식각 속도는 너무 빨라져 상하부 투명전도막의 팁(Tip)이 발생하게 되어 후속공정에서 문제를 야기할 수 있다. The phosphoric acid (H 3 PO 4 ) may be contained in an amount of 40 to 60% by weight based on the total weight of the etchant composition. If the content of phosphoric acid is less than 40% by weight, the etching rate of silver may be lowered and the etching profile may be defective. If the content exceeds 60% by weight, the etching rate of the transparent conductive film is lowered, A tip of the conductive film may be generated, which may cause a problem in a subsequent process.
본 발명의 식각액에 포함되는 질산(HNO3)은 보조 산화제로 사용되는 성분으로서, 은 또는 은합금을 산화시켜 식각하는 역할을 하며, 예컨대, 투명전도막/Ag/투명전도막으로 구성되는 삼중막에서는 은(Ag)과 투명전도막을 산화시켜 식각하는 역할을 수행한다. The nitric acid (HNO 3 ) contained in the etchant of the present invention is a component used as a co-oxidizing agent and serves to oxidize and etch silver or silver alloy. For example, a triple layer composed of a transparent conductive film / Ag / (Ag) and the transparent conductive film.
질산(HNO3)은 식각액 조성물 총 중량에 대하여 3~8 중량%로 포함될 수 있다. 질산의 함량이 3 중량% 미만인 경우에는 은(Ag)과 투명전도막(예: ITO)의 식각 속도 저하가 발생하며 이로써 기판내의 식각 균일성(Uniformity)이 불량해지므로 얼룩이 발생하며, 8 중량%를 초과하는 경우에는 상하부 투명전도막의 식각 속도가 가속화 되어 상하부 투명전도막의 언더컷 발생으로 후속 공정에 문제가 발생된다.The nitric acid (HNO 3 ) may be included in an amount of 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 etch rate of silver (Ag) and the transparent conductive film (for example, ITO) is lowered to cause unevenness of etch uniformity in the substrate, , The etching speed of the upper and lower transparent conductive films accelerates and undercuts of the upper and lower transparent conductive films cause a problem in the subsequent process.
본 발명의 식각액에 포함되는 아세트산(CH3COOH)은 보조 산화제로 사용되는 성분으로서 은 또는 은합금을 산화시켜 식각하는 역할을 수행한다. 아세트산(CH3COOH)은 식각액 조성물 총 중량에 대하여 5~20 중량%로 포함될 수 있다. 아세트산의 함량이 5 중량% 미만일 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.Acetic acid (CH 3 COOH) contained in the etchant of the present invention is a component used as a co-oxidant and oxidizes and oxidizes silver or silver alloy. Acetic acid (CH 3 COOH) may be included in an amount of 5 to 20% by weight based on the total weight of the etchant composition. When the content of acetic acid is less than 5% by weight, unevenness of the etching rate in the substrate may cause unevenness. When the content of acetic acid exceeds 20% by weight, foaming may occur. If such a bubble is present in the substrate, Which can cause problems in subsequent processes.
본 발명의 식각액 중의 글루콘산은 첨가제로 사용되는 성분으로서, 습식 식각 시 박막에 대한 CD 스큐(CD Skew)를 감소시키고 또한 균일하게 식각되도록 식각 속도를 조절한다. 글루콘산은 식각액 조성물 총 중량에 대하여 0.8~1.2 중량%로 포함될 수 있다. 글루콘산 함량이 0.8중량% 미만일 경우에는 기판 내의 식각 균일성(Uniformity)이 저하되고, 기판 내에 부분적으로 은 잔사가 생길 수 있으며, 1.2 중량%를 초과하는 경우에는 식각 속도가 저하되어 원하는 식각 속도를 구현할 수 없으므로 공정상에 문제가 될 수 있다.Gluconic acid in the etchant of the present invention is a component used as an additive and controls the etching rate so as to reduce the CD skew for the thin film and to uniformly etch the thin film during wet etching. The gluconic acid may be contained in an amount of 0.8 to 1.2% by weight based on the total weight of the etchant composition. When the content of gluconic acid is less than 0.8% by weight, the uniformity of the substrate is lowered and a part of the substrate may be left in the substrate. If the content of the gluconic acid exceeds 1.2% by weight, the etching rate is lowered, It can not be implemented, which can cause problems in the process.
또한, 본 발명은 In addition,
(a)기판 상에 금속층을 형성하는 단계;(a) forming a metal layer on a substrate;
(b)상기 금속층을 식각하여 게이트 전극을 형성하는 단계;(b) etching the metal layer to form a gate electrode;
(c)상기 게이트 전극 상에 게이트 절연층을 형성하는 단계;(c) forming a gate insulating layer on the gate electrode;
(d)상기 게이트 절연층 상에 반도체층을 형성하는 단계;(d) forming a semiconductor layer on the gate insulating layer;
(e)상기 반도체층 상에 소스 및 드레인전극을 형성하는 단계; 및(e) forming source and drain electrodes on the semiconductor layer; And
(f)상기 소스 및 드레인전극 상에 화소전극을 형성하는 단계를 포함하며,(f) forming pixel electrodes on the source and drain electrodes,
상기 (b)단계 및 (e)단계 중 적어도 어느 한 단계에서는 상기 본 발명의 식각액 조성물을 사용하여 은 또는 은합금을 포함하는 단일막 또는 다층막을 식각하는 공정을 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법에 관한 것이다. Wherein at least one of the steps (b) and (e) includes a step of etching a single layer or a multilayer including silver or silver alloy using the etchant composition of the present invention. And a manufacturing method thereof.
또한, 본 발명은In addition,
상기의 방법으로 제조되는 것을 특징으로 하는 박막트랜지스터에 관한 것이다And a thin film transistor manufactured by the above method
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예 및 비교예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made.
실시예Example 1: One: 식각속도Etching rate 조절에 의한 Controlled 식각Etching 방법의 실시 Conduct of the method
기판상에 a-ITO/Ag/a-ITO 삼중막을 형성하고 다이아몬드 칼을 이용하여 10×10mm로 절단하여 시편을 준비하였다.The a-ITO / Ag / a-ITO triplet was formed on the substrate and cut into 10 × 10 mm using a diamond knife to prepare a specimen.
분사식 식각 방식의 실험장비(SEMES사 제조)를 사용하여 하기 표 1의 실시예 1-1 내지 1-5 및 비교예 1-1 내지 1-4에 따라 종방향 및 횡방향 식각속도를 조절하여 상기 시편의 식각을 진행하였다. 구체적으로 분사식 식각 방식의 실험장비(SEMES사 제조)에 하기 표 1의 식각액을 넣고 온도를 40℃로 설정하여 가온한 후, 온도가 40±0.1℃에 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 vertical and lateral etching rates were controlled in accordance with Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 in Table 1 by using an experimental apparatus of a spray-type etching system (manufactured by SEMES) The sample was etched. Specifically, the etching solution shown in the following Table 1 was placed in an experimental apparatus of a spray-type etching system (manufactured by SEMES), the temperature was set at 40 占 폚, and the etching process was performed when the temperature reached 40 占 0.1 占 폚. The total etch time was 50% over etch based on end point detection (EPD).
상기 기판들을 식각이 이루어진 후에 꺼내어 탈이온수로 세정한 후, 열풍(熱風)건조장치를 이용하여 건조하고, 전자주사현미경(SEM; HITACHI사 제조, 모델명: S-4700)을 이용하여 테이퍼 각을 측정하고 그 결과를 하기 표 1에 나타내었다. 또한, 실시에 1-2의 방법에 따라 식각된 시편의 프로파일 단면을 SEM으로 촬영하여 도 1에 나타내었다.The substrates were taken out after etching, washed with deionized water, dried using a hot air drying apparatus, and measured for taper angle using a scanning electron microscope (SEM; model: S-4700, manufactured by Hitachi) The results are shown in Table 1 below. In addition, the profile section of the etched sample according to the method of 1-2 is photographed by SEM and is shown in Fig.
(단위: 중량%)(Unit: wt%)
[Ag 테이퍼각 평가 기준][Evaluation criteria of Ag taper angle]
○: 우수 (20o ≤ 테이퍼각 < 35o)○: Excellent (20 o ≤ taper angle <35 o )
△: 양호 (35o ≤ 테이퍼각 < 50o)?: Good (35 o ? Taper angle <50 o )
Ⅹ: 불량 (50o ≤ 테이퍼각)X: Defective (50 o ≤ taper angle)
상기 표 1의 시험 결과에 따르면, 본 발명의 식각 방법에 따라 종방향 식각속도(400 Å/sec ~ 600 Å/sec)와 횡방향 식각속도(2 Å/sec ~ 6 Å/sec)를 조절하여 식각을 실시하는 경우(실시예 1-1 내지 1-5), 우수한 테이퍼 각이 얻어지는 것을 확인할 수 있다. 반면, 본 발명의 식각속도 범위를 벗어나서 식각을 실시하는 경우(비교예 1-1 내지 1-4)에는 불량한 테이퍼 각이 얻어지는 것을 확인할 수 있다. According to the test results shown in Table 1, the longitudinal etching rate (400 Å / sec to 600 Å / sec) and the lateral etching rate (2 Å / sec to 6 Å / sec) were adjusted according to the etching method of the present invention In the case of performing the etching (Examples 1-1 to 1-5), it can be confirmed that an excellent taper angle is obtained. On the other hand, it can be confirmed that a poor taper angle is obtained when the etching is performed outside the etching rate range of the present invention (Comparative Examples 1-1 to 1-4).
또한, 상기와 같은 사실은 도 1에 첨부된 SEM 이미지로부터도 확인된다. The above fact is also confirmed from the SEM image attached to FIG.
실시예Example 2: 2: 식각액Etchant 조성물의 제조 및 The preparation of the composition and 식각Etching 특성 평가 Character rating
(1)(One) 실시예Example 2-1 내지 2-9 및 2-1 to 2-9 and 비교예Comparative Example 2-1 내지 2-8: 2-1 to 2-8: 식각액Etchant 조성물식각액The composition etchant 조성물의 제조 Preparation of composition
하기 표 1에 기재된 성분을 해당 함량으로 혼합하여 식각액 조성물 180kg을 제조하였다.180 kg of an etchant composition was prepared by mixing the components listed in Table 1 below in the respective amounts.
(2) (2) 식각Etching 특성 평가 시험 Characteristic evaluation test
기판상에 a-ITO/Ag/a-ITO 삼중막을 형성하고 다이아몬드 칼을 이용하여 10×10mm로 절단하여 시편을 준비하였다.The a-ITO / Ag / a-ITO triplet was formed on the substrate and cut into 10 × 10 mm using a diamond knife to prepare a specimen.
분사식 식각 방식의 실험장비(SEMES사 제조) 내에 실시예 2-1 내지 2-9 및 비교예 2-1 내지 2-8의 식각액 조성물을 넣고 온도를 30℃로 설정하여 가온한 후, 온도가 30±0.1℃에 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 etching composition compositions of Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-8 were placed in an experimental apparatus of a spray-type etching system (manufactured by SEMES), the temperature was set at 30 DEG C, The etching process was performed when the temperature reached ± 0.1 ° C. The total etch time was 50% over etch based on end point detection (EPD).
상기 기판들을 식각이 이루어진 후에 꺼내어 탈이온수로 세정한 후, 열풍(熱風)건조장치를 이용하여 건조하고, 전자주사현미경(SEM; HITACHI사 제조, 모델명: S-4700)을 이용하여 시편의 프로파일 단면을 촬영하고, Ag의 식각량 및 Ag 재흡착 정도를 평가하여 하기 표 2에 나타내었다.After the substrates were etched, the substrates were washed with deionized water, dried using a hot air drying apparatus, and subjected to a profile cross section of the specimen using a scanning electron microscope (SEM; model: S-4700, And the etching amount of Ag and the degree of Ag adsorption were evaluated. The results are shown in Table 2 below.
[Ag 식각량 평가 기준][Ag etching rate evaluation criteria]
◎: 매우 우수 (Side Etch < 0.1㎛)⊚: Excellent (Side Etch <0.1 탆)
○: 우수 (0.1㎛ ≤ Side Etch < 0.2㎛)Good: Excellent (0.1 占 퐉? Side Etch <0.2 占 퐉)
△: 양호 (0.2㎛ ≤ Side Etch ≤ 0.3㎛)?: Good (0.2 탆? Side Etch? 0.3 탆)
Ⅹ: 불량 (Side Etch: > 0.3㎛)X: Bad (Side Etch: > 0.3 mu m)
[Ag 재흡착 평가 기준] [Evaluation criteria of Ag re-adsorption]
◎: 매우 우수 (50개 이하)◎: Very good (less than 50)
○: 우수 (80개 이하)○: Excellent (less than 80)
△: 양호 (100개 이하)?: Good (less than 100)
Ⅹ: 불량 (100개 이상)X: Defective (more than 100)
(단위: 중량%)(Unit: wt%)
상기 표 2에서 확인되는 바와 같이, 본 발명의 식각액 조성물을 사용한 실시예 2-1 내지 2-9의 경우 Ag 식각량 및 Ag 재흡착량에 있어서 모두 우수한 효과를 나타냈다. 반면, 비교예의 식각액 조성물을 사용한 경우는 Ag 식각량 및 Ag 재흡착량의 모든 면에서 실시예의 시각액 조성물과 비교하여 저조한 효과를 나타내었으며, 특히, Ag 식각량 및 Ag 재흡착량 중의 어느 하나는 불량한 효과를 나타내었다.As shown in Table 2, in Examples 2-1 to 2-9 using the etchant composition of the present invention, both the Ag etching amount and the Ag adsorption amount showed excellent effects. On the other hand, in the case of using the etchant composition of the comparative example, the Ag etch amount and the Ag re-adsorption amount were inferior to the visual liquid compositions of the examples in all respects, and in particular, And showed a bad effect.
Claims (9)
400 Å/sec ~ 600 Å/sec의 종방향 식각속도 및 2 Å/sec ~ 6 Å/sec의 횡방향 식각속도로 식각공정을 수행하는 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법. In the etching of a single film or multilayer film containing silver or silver alloy,
Wherein the etch process is performed at a longitudinal etch rate of 400 A / sec to 600 A / sec and a lateral etch rate of 2 A / sec to 6 A / sec. Lt; / RTI >
상기 식각 방법의 식각은 조성물 총 중량에 대해 인산 40 내지 60중량%, 질산 3 내지 8 중량%, 초산 5 내지 20중량%, 글루콘산 0.8 내지 1.2 중량% 및 잔량의 물을 포함하는 식각액 조성물로 이루어지는 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법.The method according to claim 1,
Wherein the etching of the etch process comprises etching the etching composition comprising 40 to 60 wt% phosphoric acid, 3 to 8 wt% nitric acid, 5 to 20 wt% acetic acid, 0.8 to 1.2 wt% gluconic acid, and residual water, ≪ / RTI > wherein at least one layer of silver or silver alloy comprises at least one of silver and silver alloy.
상기 은합금은, 은과 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 중 1종 이상의 금속을 포함하여 이루어지는 합금형태; 또는 은의 질화물, 규화물막, 탄화물 또는 산화물 형태인 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법.The method according to claim 1,
Wherein the silver alloy comprises at least one metal selected from the group consisting of silver and Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti; Or a nitride of silver, a silicide film, a carbide or an oxide of silver, or a silver alloy or a silver alloy.
상기 다층막은 은 또는 은합금을 포함하는 단일막과 하나 이상의 금속산화물막이 함께 적층된 형태인 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막의 습식 식각 방법.The method according to claim 1,
Wherein the multilayered film is a laminate of a single film containing silver or silver alloy and at least one metal oxide film. ≪ RTI ID = 0.0 > 18. < / RTI >
상기 은합금은, 은과 Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W 및 Ti 중 1종 이상의 금속을 포함하여 이루어지는 합금형태; 또는 은의 질화물, 규화물막, 탄화물 또는 산화물 형태인 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막용 식각액 조성물.The method of claim 5,
Wherein the silver alloy comprises at least one metal selected from the group consisting of silver and Nd, Cu, Pd, Nb, Ni, Mo, Ni, Cr, Mg, W and Ti; Or a nitride of silver, a silicide film, a carbide, or an oxide of silver.
상기 다층막은 ITO/Ag/ITO, IZO/Ag/IZO, ITZO/Ag/ITZO, IGZO/Ag/IGZO, ITO/Ag합금막/ITO, IZO/Ag합금막/IZO, ITZO/Ag합금막/ITZO, 또는 IGZO/Ag합금막/IGZO인 것을 특징으로 하는 은 또는 은합금을 포함하는 단일막 또는 다층막용 식각액 조성물.The method of claim 5,
Ag / IZO, IZO / Ag / IZZO, ITO / Ag alloy film / ITO, IZO / Ag alloy film / IZO, ITZO / Ag alloy film / ITZO / Ag / IZO , Or an IGZO / Ag alloy film / IGZO. The etchant composition for a single film or multilayer film,
(b)상기 금속층을 식각하여 게이트 전극을 형성하는 단계;
(c)상기 게이트 전극 상에 게이트 절연층을 형성하는 단계;
(d)상기 게이트 절연층 상에 반도체층을 형성하는 단계;
(e)상기 반도체층 상에 소스 및 드레인전극을 형성하는 단계; 및
(f)상기 소스 및 드레인전극 상에 화소전극을 형성하는 단계를 포함하며,
상기 (b)단계 및 (e)단계 중 적어도 어느 한 단계에서는 청구항 5의 식각액 조성물을 사용하여 은 또는 은합금을 포함하는 단일막 또는 다층막을 식각하는 공정을 포함하는 것을 특징으로 하는 박막트랜지스터의 제조방법.(a) forming a metal layer on a substrate;
(b) etching the metal layer to form a gate electrode;
(c) forming a gate insulating layer on the gate electrode;
(d) forming a semiconductor layer on the gate insulating layer;
(e) forming source and drain electrodes on the semiconductor layer; And
(f) forming pixel electrodes on the source and drain electrodes,
Wherein at least one of the steps (b) and (e) includes a step of etching a single film or a multilayer film containing silver or silver alloy by using the etching liquid composition of claim 5. Way.
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