KR20060055900A - Copper electrode for liquid crystal display using metal cladding layer and fabrication thereof - Google Patents
Copper electrode for liquid crystal display using metal cladding layer and fabrication thereof Download PDFInfo
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- KR20060055900A KR20060055900A KR1020040095086A KR20040095086A KR20060055900A KR 20060055900 A KR20060055900 A KR 20060055900A KR 1020040095086 A KR1020040095086 A KR 1020040095086A KR 20040095086 A KR20040095086 A KR 20040095086A KR 20060055900 A KR20060055900 A KR 20060055900A
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- liquid crystal
- crystal display
- copper electrode
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- 239000010949 copper Substances 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000005253 cladding Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 238000007772 electroless plating Methods 0.000 claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229910019043 CoSn Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RSBNPUNXBGVNNB-UHFFFAOYSA-M S(=O)(=O)([O-])[O-].[NH4+].[Co+] Chemical compound S(=O)(=O)([O-])[O-].[NH4+].[Co+] RSBNPUNXBGVNNB-UHFFFAOYSA-M 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- VYQMXBMNWDFBHM-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate tetramethylazanium Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O VYQMXBMNWDFBHM-UHFFFAOYSA-K 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920002113 octoxynol Polymers 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 2
- 239000000956 alloy Substances 0.000 abstract description 9
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 palladium ions Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
- G02F1/136295—Materials; Compositions; Manufacture processes
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
본 발명은 액정 디스플레이 소자의 게이트 및 데이터 라인용 구리 전극 및 그 제조방법에 있어서, Co 또는 Ni 계열의 합금을 포함한 금속 피복막을 무전해 도금으로 증착시킨 액정 디스플레이의 게이트 및 데이터 라인용 구리 전극은 제조 공정 중 발생하는 열화(degradation) 현상을 방지하고 전자 이동 수명(electron migration lifetime)이 증가하여 액정 디스플레이의 신뢰성이 향상되며, 제품의 제조 수율 또한 증가하는 효과가 있다.In the present invention, a copper electrode for a gate and a data line of a liquid crystal display device and a method of manufacturing the same, a copper electrode for a gate and a data line of a liquid crystal display in which a metal coating film containing a Co or Ni-based alloy is deposited by electroless plating is manufactured. It is possible to prevent degradation during the process and to increase the electron migration lifetime, thereby improving the reliability of the liquid crystal display, and increasing the manufacturing yield of the product.
금속 피복막, 액정 디스플레이, 구리 전극, 게이트 전극, 데이터 전극, 무전해도금, 전자이동수명, 열화Metal coating film, liquid crystal display, copper electrode, gate electrode, data electrode, electroless plating, electron transfer life, deterioration
Description
도 1은 본 발명의 실시예에서 제조한 무전해 도금액을 이용하여 액정 디스플레이의 구리 게이트 전극에 금속 피복막을 적용하는 공정 흐름도이다.1 is a process flowchart of applying a metal coating film to a copper gate electrode of a liquid crystal display using an electroless plating solution prepared in an embodiment of the present invention.
* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
1: 유리 TFT 어레이 기판1: glass TFT array substrate
3: 구리 및 점착층3: copper and adhesive layer
5: 구리 게이트 전극5: copper gate electrode
7: 금속 피복막7: metal cladding
본 발명은 액정 디스플레이 소자에 사용되는 구리 전극 및 그 제조방법에 관한 것으로서, 더욱 상세하게는 액정 디스플레이 소자의 게이트 및 데이터 라인에 사용되는 구리 전극의 제조 공정 중 발생하는 열화(degradation) 현상을 방지하고 전자 이동 수명(electron migration lifetime)을 증가시키기 위하여 Co 계열 또는 Ni 계열 합금의 금속 피복막(metal cladding layer)을 구리 표면에 무전해 도금(electroless plate)을 이용하여 증착한 액정 디스플레이용 구리 전극 및 그 제조방법에 관한 것이다.BACKGROUND OF THE
구리(Cu)는 알루미늄에 비해 융점(boiling point)이 높고, 전기 이동 수명 등이 여타 금속 물질에 비해 길어, 최근에 반도체 배선 물질로 많이 사용되고 있다. 반도체의 경우와 마찬가지로 액정 디스플레이(LCD)의 게이트 및 데이터 전극으로 사용되는 금속도 저항-축전 지연(resistance-capacitance delay) 및 전류 밀도 특성이 우수한 구리가 기존의 전극 물질인 알루미늄에 비해 유리하다. SXGA(1280×1024)급 액정 디스플레이 소자의 게이트 전극으로 사용되기 시작한 구리 전극은 향후 액정 소자의 해상도와 크기의 향상으로 인해 그 수요가 크게 늘어날 것으로 예상된다.Copper (Cu) has a high melting point (boiling point) compared to aluminum, and the electrophoretic life is longer than other metal materials, and has been widely used as a semiconductor wiring material in recent years. As in the case of semiconductors, copper, which is used as a gate and data electrode of a liquid crystal display (LCD), has superior resistance-capacitance delay and current density to copper, compared to conventional electrode materials aluminum. Copper electrodes, which began to be used as gate electrodes of SXGA (1280 × 1024) class liquid crystal display devices, are expected to increase greatly in the future due to the improvement in resolution and size of liquid crystal devices.
그러나, 실제로 구리 배선 공정은 구리/유전체 인접부의 원자 수송(atomic transportation) 특성이 수송 전류 밀도의 크기를 크게 좌우하고, 제조 공정 중에 표면 부식과 같은 열화 현상이 발생하기 때문에, 반도체 소자에 악영향을 끼칠 수 있다는 결과들이 발표되고 있다. 또한, 액정 디스플레이 소자에서 사용되는 구리 전극도 실리콘 질화물(Si3N4)과 같은 유전체 및 표면 부식 등에 의해서 반도체 소자와 같은 문제가 발생할 가능성이 매우 높다. 더구나, 액정 디스플레이의 제조 공정에 패턴 형성 후에 표면에 노출되는 금속 게이트 및 데이터 전극의 표면적은 반도체의 구리 배선에 비해 10 ~ 20배가 넓기 때문에, 표면 열화 현상의 발생 빈도도 매우 높을 것으로 예상된다.However, in practice, the copper wiring process may adversely affect the semiconductor device because the atomic transportation characteristics of the copper / dielectric neighbor region greatly influence the magnitude of the transport current density, and deterioration such as surface corrosion occurs during the manufacturing process. Results are being announced. In addition, the copper electrode used in the liquid crystal display device is also very likely to cause problems such as semiconductor devices due to surface corrosion and the like dielectric such as silicon nitride (Si 3 N 4 ). Moreover, since the surface area of the metal gate and the data electrode exposed to the surface after pattern formation in the manufacturing process of the liquid crystal display is 10 to 20 times larger than that of the copper wiring of the semiconductor, the occurrence frequency of surface degradation is expected to be very high.
따라서, 표면 열화 현상을 방지하기 위한 구리 배선에 관한 기술이 연구되고 있다. 미국특허 제6,342,733호에서는 표면 코팅에 의한 구리 배선에 관한 기술이 개시되어 있다. 빌 리 등(Bill Lee et al.)은 Co계 합금인 CoWP 합금 층을 무전해 도금 공정을 이용하여 구리 배선 위에 선택적으로 증착하는 경우에 전자 이동 수명이 기존의 경우와 비교해서 10배 내지 최고 385배까지 향상되어 구리 배선의 열화 특성이 개선되는 효과가 있음을 발표하였다. 또한, 엔 페트로브 등(N. Petrov et al.)은 발표한 논문을 통해 (J. Electrochem. Soc, 149(4), C187-C194 (2002)) Co 계열의 합금은 열역학적으로 안정되게 얻을 수 있으며, 두 종류의 다른 텅스텐 착화합물을 사용하여 CoP 및 CoWP를 각각 무전해 도금 증착한 후에 각 금속 피복막의 특성을 조사하였다. 한편, 미국특허 제6,528,409호에서는 Co 계열 및 Ni 계열의 금속 피복막으로 이루어진 다공성 유전막을 절연막으로 사용하는 반도체 배선 공정에 응용할 수 있으며, 그 구조는 비정질(amorphous)이거나, 미세 다결정(micro-polycrystalline) 구조일 수 있다고 정리하고 있다.Therefore, the technique regarding the copper wiring for preventing surface deterioration phenomenon is researched. US Patent No. 6,342,733 discloses a technique for copper wiring by surface coating. Bill Lee et al. Reported that when the CoWP alloy layer, a Co-based alloy, is selectively deposited on copper wiring using an electroless plating process, the electron transfer life is 10 times higher than that of the conventional case. It has been reported that there is an effect of improving the deterioration characteristics of the copper wiring by improving up to 2 times. In addition, N. Petrov et al.'S paper ( J. Electrochem. Soc , 149 (4), C187-C194 (2002)) shows that the Co-based alloys can be obtained thermodynamically and stably. After the electroless plating deposition of CoP and CoWP using two different tungsten complexes, the characteristics of each metal coating film were investigated. On the other hand, US Patent No. 6,528,409 can be applied to a semiconductor wiring process using a porous dielectric film consisting of a Co-based and Ni-based metal coating film as an insulating film, the structure is amorphous or micro-polycrystalline It can be structured.
상기와 같은 문제점을 해결하기 위하여 본 발명은 액정 디스플레이 소자의 게이트 및 데이터 전극에 사용되는 구리 라인의 제조 공정 중 발생하는 열화 현상을 방지하고 전자 이동 수명을 증가시킬 수 있는 액정 디스플레이 소자의 구리 전극 및 그 제조방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention provides a copper electrode of a liquid crystal display device, which can prevent deterioration occurring during the manufacturing process of a copper line used for the gate and data electrodes of the liquid crystal display device, and increase the electron transfer life. It aims at providing the manufacturing method.
본 발명의 상기 목적 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모 두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기 목적을 달성하기 위하여, 본 발명은 액정 디스플레이의 게이트 및 데이터 라인용 구리 전극에 있어서, 상기 구리 전극 상에 Co 계열 또는 Ni 계열의 금속 피복막(metal cladding layer)이 증착된 것을 특징으로 하는 액정 디스플레이의 게이트 및 데이터 라인용 구리 전극을 제공한다.In order to achieve the above object, the present invention is a copper electrode for the gate and data line of the liquid crystal display, characterized in that the Co-based or Ni-based metal cladding layer (metal cladding layer) is deposited on the copper electrode Provided are copper electrodes for the gate and data lines of the display.
또한, 본 발명은 액정 디스플레이의 게이트 및 데이터 라인용 구리 전극의 제조방법에 있어서, 게이트 및 데이터 라인용 구리 전극의 구리 표면에 팔라듐 촉매를 증착시키는 단계; 및 상기 증착된 구리 전극에 무전해 도금을 실시하여 Co 계열 또는 Ni 계열의 금속을 피복시키는 단계;를 포함하여 이루어지는 것을 특징으로 하는 액정 디스플레이의 게이트 및 데이터 라인용 구리 전극의 제조방법을 제공한다.The present invention also provides a method of manufacturing a copper electrode for a gate and a data line of a liquid crystal display, comprising the steps of: depositing a palladium catalyst on a copper surface of a copper electrode for a gate and a data line; And coating the deposited copper electrode by electroless plating to coat a Co-based or Ni-based metal. The method of manufacturing a copper electrode for a gate and data line of a liquid crystal display, comprising:
상기 Co 계열의 금속은 CoP, CoWB, CoWPB, CoWP, CoW, CoSn 및 CoSnP로 이루어진 군으로부터 1종 이상 선택되며, Ni 계열의 금속은 NiP, NiMoP 및 NiWP으로 이루어진 군으로부터 1종 이상 선택될 수 있다.The Co-based metal is selected from the group consisting of CoP, CoWB, CoWPB, CoWP, CoW, CoSn and CoSnP, and the Ni-based metal may be selected from the group consisting of NiP, NiMoP and NiWP. .
상기 팔라듐 촉매의 증착단계에서 사용되는 팔라듐 촉매 용액은 팔라듐 클로라이드(palladium chloride), 불산(HF), 염산(HCl) 및 질산(HNO3)을 포함할 수 있다.The palladium catalyst solution used in the deposition step of the palladium catalyst may include palladium chloride (palladium chloride), hydrofluoric acid (HF), hydrochloric acid (HCl) and nitric acid (HNO 3 ).
상기 무전해 도금시 사용되는 무전해 도금액은 금속 피복막의 전구체, pH 조 절제, 환원제, 계면활성제 및 착화합물 형성제를 포함할 수 있다.The electroless plating solution used in the electroless plating may include a precursor of a metal coating film, a pH adjuster, a reducing agent, a surfactant, and a complex compound forming agent.
상기 금속 피복막의 전구체는 코발트 설페이트(cobalt sulfate), 코발트 클로라이드(cobalt chloride) 및 코발트 암모늄 설페이트(cobalt ammonium sulphate)로 이루어진 군으로부터 1종 이상 선택되는 Co 전구체; 암모늄 텅스테이트(ammonium tungstate), 소듐 텅스테이트(sodium tungstate) 및 테트라메틸 암모늄 텅스테이트(tetramethyl ammonium tungstate)로 이루어진 군으로부터 1종 이상 선택되는 W 전구체; 암모늄 하이포포스파이트(ammonium hypophosphite), 암모늄 디하이드로겐 포스페이트(ammonium dihydrogen phosphate) 및 H3PO4로 이루어진 군으로부터 1종 이상 선택되는 P 전구체; 틴 클로라이드(tin chloride) 또는 틴 설페이트(tin sulphate)인 Sn 전구체; 및, 니켈 설페이트(nickel sulphate), 니켈 설파메이트(nickel sulfamate) 및 니켈 클로라이드(nickel chloride)로 이루어진 군으로부터 1종 이상 선택되는 Ni 전구체;로 이루어진 군으로부터 2종 이상 선택될 수 있다.Precursors of the metal coating film is a co precursor selected from the group consisting of cobalt sulfate (cobalt sulfate), cobalt chloride (cobalt chloride) and cobalt ammonium sulphate (cobalt ammonium sulphate); W precursor selected from the group consisting of ammonium tungstate, sodium tungstate and tetramethyl ammonium tungstate; P precursor selected from the group consisting of ammonium hypophosphite, ammonium dihydrogen phosphate and H 3 PO 4 ; Sn precursors that are tin chloride or tin sulphate; And nickel precursors selected from the group consisting of nickel sulphate, nickel sulfamate, and nickel chloride.
상기 pH 조절제는 테트라메틸 암모늄 하이드록사이드(tetramethyl ammonium hydroxide, TMAH), 포타슘 하이드록사이드(potassium hydroxide, KOH) 및 암모늄 하이드록사이드(ammonium hydroxide)로 이루어진 군으로부터 선택될 수 있다.The pH adjusting agent may be selected from the group consisting of tetramethyl ammonium hydroxide (TMAH), potassium hydroxide (KOH) and ammonium hydroxide.
상기 환원제는 포름알데히드(formaldehyde) 또는 디메틸아민 보란(dimethylamine borane, DMAB)일 수 있다.The reducing agent may be formaldehyde or dimethylamine borane (DMAB).
상기 계면활성제는 RE-610, 트리톤(Triton)-X 및 폴리에틸렌글리콜(PEG)로 이루어진 군으로부터 선택될 수 있다.The surfactant may be selected from the group consisting of RE-610, Triton-X, and polyethylene glycol (PEG).
상기 착화합물 형성제는 암모늄 시트레이트(ammonium citrate), 소듐 시트레이트(sodium citrate), 테트라메틸 암모늄 시트레이트(tetramethyl ammonium citrate) 및 EDTA로 이루어진 군으로부터 선택될 수 있다.The complex forming agent may be selected from the group consisting of ammonium citrate, sodium citrate, tetramethyl ammonium citrate and EDTA.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 액정 디스플레이 소자의 게이트 및 데이터 전극으로 사용되는 구리 라인의 제조 공정 중 생기는 열화 현상과 전자 이동 수명을 개선하기 위해 구리 표면에 무전해 도금을 이용하여 금속 피복막을 증착하는 것에 관한 것이다.BACKGROUND OF THE
본 발명에서 언급하고 있는 금속 피복막 증착은 게이트 및 데이터 구리 전극 표면에 무전해 환원 반응을 통해 선택적으로 일어나며 다음의 2단계로 구성된다.Metal coating film deposition referred to in the present invention occurs selectively through the electroless reduction reaction on the gate and data copper electrode surface and consists of the following two steps.
1단계: 팔라듐 이온을 이용한 구리 표면의 선택적 활성화Step 1: Selective activation of copper surface with palladium ions
본 단계는 무전해 증착 공정에서 촉매로 사용되는 팔라듐을 구리 표면에 먼저 증착하는 단계이다. 후에 증착한 금속 피복막이 옆의 전극 라인과 통전(通電)되는 것을 막기 위해, 팔라듐 촉매가 구리 전극에만 흡착할 수 있도록 선택성이 있어야 한다.In this step, palladium, which is used as a catalyst in an electroless deposition process, is first deposited on a copper surface. In order to prevent the deposited metal coating film from being energized with the adjacent electrode line, the palladium catalyst should be selective so as to adsorb only to the copper electrode.
2단계: 무전해 환원반응을 이용한 금속 또는 합금의 선택적 증착Step 2: Selective Deposition of Metals or Alloys Using Electroless Reduction
팔라듐 촉매가 구리 표면에 흡착된 이후에 해당 금속을 피복하기 위해서 무전해 도금을 실시한다. 위의 반응은 팔라듐 촉매 표면에서만 일어나는 반응이다. 현재 CoP, CoWB, CoWPB, CoWP, CoW, CoSn 또는 CoSnP 등과 같은 Co 계열과 NiP 또는 NiWP 등과 같은 Ni 계열을 금속 피복막으로 사용할 수 있다. 이 중에서, 반도체 공정뿐 아니라 본 발명에서 가장 주목하고 있는 물질인 CoWP을 예로 각 금속의 원자 조성과 역할을 정리하면 다음과 같다. 코발트(Co, ca. 90at.%)는 구리 표면의 산화적 부식(oxidative corrosion)에 강하며, 텅스텐(W, ≤ 3at.%)는 비결정질 합금에 대한 열적 안정성(thermal stability), 내부식성(corrosion resistance) 및 치밀성(densification)을 부여하고, 인(P, ≥ 5at.%)은 유사-비결정질 합금(pseudo-amorphous alloy, Co3P)을 형성하는 역할을 한다.After the palladium catalyst is adsorbed on the copper surface, electroless plating is performed to coat the metal. The above reaction occurs only on the surface of the palladium catalyst. Currently, Co series such as CoP, CoWB, CoWPB, CoWP, CoW, CoSn or CoSnP and Ni series such as NiP or NiWP may be used as the metal coating film. Among them, the atomic composition and role of each metal are summarized as follows, for example, CoWP, which is not only a semiconductor process but also a material of interest in the present invention. Cobalt (Co, ca. 90at.%) Is resistant to oxidative corrosion of the copper surface, and tungsten (W, ≤ 3at.%) Is thermal stability and corrosion resistance to amorphous alloys. impart resistance and densification, and phosphorus (P, ≧ 5 at.%) serves to form pseudo-amorphous alloys (Co 3 P).
본 발명의 무전해 도금액을 이용하여 금속 피복막을 액정 디스플레이의 구리 게이트 및 데이터 전극에 적용하는 공정 흐름을 도 1에 나타내었다. 유리 TFT 어레이 기판(glass TFT array substrate, 1)에 구리를 증착시켜 구리 및 점착층(adhesion layer, 3)을 형성하고 리소그라피(lithography) 및 습식 식각(wet etching)을 실시하여 구리 게이트 또는 데이터 전극(5)을 제조한다. 이렇게 제조된 구리 게이트 또는 데이터 전극에 팔라듐 촉매를 흡착시켜 구리 표면을 선택적으로 활성화시키고, 무전해 도금을 실시하여 금속 또는 합금의 금속 피복막(7)을 선택적으로 증착시킨다.
The process flow of applying the metal coating film to the copper gate and data electrode of the liquid crystal display using the electroless plating solution of the present invention is shown in FIG. 1. Copper is deposited on a glass TFT array substrate (1) to form a copper and adhesion layer (3), and lithography and wet etching are performed to form a copper gate or data electrode ( 5) is prepared. A palladium catalyst is adsorbed on the copper gate or data electrode thus prepared to selectively activate the copper surface, and electroless plating is performed to selectively deposit a
다음은 본 발명의 이해를 돕기 위하여 바람직한 실시예 및 비교예를 제시한다. 그러나 하기의 실시예 및 비교예들은 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예 및 비교예에 한정되는 것은 아니다.The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples and comparative examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples and comparative examples.
[실시예]EXAMPLE
CoWP의 금속 피복막을 증착시킨 구리 전극의 제조Fabrication of Copper Electrode Deposited by CoWP Metal Coating Film
구리 금속 표면에 형성되어 있을 자연 구리 산화막을 제거하기 위해 NH4OH 0.05vol% 용액으로 0.5분 동안 세정하였다. 그리고, 하기 표 1과 같은 팔라듐 촉매 용액에 구리 전극을 담지시켜, 구리 표면에 팔라듐 촉매를 선택적으로 흡착시키고, 하기 표 2와 같은 무전해 도금액을 이용한 무전해 도금을 실시하여 CoWP가 증착된 구리 전극을 제조하였다. 무전해 도금액에 사용되는 전해액의 온도는 85℃로 유지하였다.In order to remove the native copper oxide film which may be formed on the copper metal surface, the resultant was washed for 0.5 minutes with a NH 4 OH 0.05 vol% solution. Further, the copper electrode was supported on the palladium catalyst solution as shown in Table 1, the palladium catalyst was selectively adsorbed on the copper surface, and the electroless plating using the electroless plating solution as shown in Table 2 was carried out to deposit CoWP. Was prepared. The temperature of the electrolyte solution used for the electroless plating solution was maintained at 85 ° C.
본 발명은 이상에서 상세히 설명한 바와 같이 구리 박막 표면의 부식을 비롯한 공정 중 발생하는 열화를 방지할 수 있으며, 전자 이동 수명의 증가와 같은 특성 개선에 따라 액정 디스플레이의 신뢰성이 향상되며 제조 수율 또한 증가하는 효과가 있다.As described in detail above, the present invention can prevent deterioration during the process including corrosion of the surface of the copper thin film, and the reliability of the liquid crystal display is improved and the manufacturing yield is also increased according to characteristics such as an increase in electron transfer life. It works.
상기에서 본 발명은 기재된 구체예를 중심으로 상세히 설명하였지만, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.
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