KR20010075932A - Gate electrode etching liquid in LCD display system - Google Patents
Gate electrode etching liquid in LCD display system Download PDFInfo
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Abstract
본 발명은 액정표시장치의 TFT(Thin Film Transitor)를 구성하는 게이트(Gate)전극용 금속배선재인 몰리브덴/알루미늄(Mo/Al) 이중층(Double Layer)의 포트레지스트(Photoresist)를 도포하지 않는 부분을 식각하여 원하는 미세패턴(Pattern)을 얻는 식각액에 관한 것이다.The present invention provides a portion in which a photoresist of a molybdenum / aluminum (Mo / Al) double layer, which is a metal wiring material for a gate electrode, which constitutes a TFT (thin film transistor) of a liquid crystal display device is not applied. The present invention relates to an etchant that is etched to obtain a desired fine pattern.
이러한 본 발명의 상기 식각액의 조성비율은 인산(60∼70wt.%) + 질산(5∼14wt.%) + 초산(5∼15wt.%) + 산화제(0.1∼10wt.%)로 이루어지고 상기 산화제는 HClO4또는 HlO4가 바람직하며 산화제 조성비는 실제로는 1∼6wt.%가 적합하고 식각액 조성의 잔여부분은 물(H2O)로 구성된다.The composition ratio of the etchant of the present invention is composed of phosphoric acid (60 ~ 70wt.%) + Nitric acid (5 ~ 14wt.%) + Acetic acid (5 ~ 15wt.%) + Oxidizing agent (0.1 ~ 10wt.%) And the oxidizing agent Is preferably HClO 4 or HlO 4 , and the oxidant composition ratio is actually 1 to 6 wt.%, And the remaining portion of the etchant composition is composed of water (H 2 O).
Description
본 발명은 액정표시장치의 TFT(Thin Film Transitor)를 구성하는 게이트(Gate)전극용 금속배선재인 몰리브덴/알루미늄(Mo/Al) 이중층(Double Layer)의 포트레지스트(Photoresist)를 도포하지 않는 부분을 식각하여 원하는 미세패턴(Pattern)을 얻는 식각액에 관한 것이다.The present invention provides a portion in which a photoresist of a molybdenum / aluminum (Mo / Al) double layer, which is a metal wiring material for a gate electrode, which constitutes a TFT (thin film transistor) of a liquid crystal display device is not applied. The present invention relates to an etchant that is etched to obtain a desired fine pattern.
종래에는 인산 + 질산 + 초산 + 물로 이루어진 정규의 Al 단일층 식각액을 사용하여 Mo/Al 이중층을 동시에 습식식각하거나 대한민국 특허공개 1999-0066167호에 제시되어 있는 바와 같이 염소(Cl2)+아르곤(Ar)+산소(O2)로 이루어진 혼합가스를 진공분위기에서 건식식각을 하여 원하는 패턴을 제조하였다.Conventionally, wet etching Mo / Al bilayers simultaneously using a regular Al monolayer etching solution consisting of phosphoric acid + nitric acid + acetic acid + water or chlorine (Cl 2 ) + argon (Ar as shown in Korean Patent Publication No. 1999-0066167). The desired pattern was prepared by dry etching the mixed gas consisting of) + oxygen (O 2 ) in a vacuum atmosphere.
건식식각을 하는 경우 고가의 진공장비에서 식각공정을 거친 후 식각공정중 표면의 일부경화된 포토레지스트를 제거하기 위해 산소 플라스마(Plasma)에 의한 애싱(Ashing)공정을 수행하고 그 후에 잔류 포토레지스트 제거를 위한 스트립핑(Stripping)공정과 별도의 클리닝(Cleaning)공정을 수행하는 등 공정단계가 복잡하므로, 실제로는 건식식각을 사용하지 않고 습식식각 및 클리닝 공정으로 이루어지는 습식식각 공정을 적용하는 경우가 대부분이다.In the case of dry etching, an etching process is performed in an expensive vacuum equipment, followed by an ashing process using an oxygen plasma to remove partially cured photoresist on the surface during the etching process, followed by removal of residual photoresist. Because the process steps are complicated such as stripping process and separate cleaning process, the wet etching process consisting of wet etching and cleaning process is not used in practice. to be.
일반적으로 액정표시장치의 TFT를 구성하는 게이트 전극용 금속배선재인 Mo/Al 이중층을 인산 + 질산 + 초산 + 물로 이루어진 종래의 식각액으로 식각하면 도 2 와 도 3 같은 형태로 균일한 Pattern이 제조되는데 부분적으로 도 1 과 같이 Mo 하부막인 Al 이 과잉식각(Over-Etch)되는 사례가 자주 발생한다.In general, when a Mo / Al double layer, which is a metal wiring material for a gate electrode, which forms a TFT of a liquid crystal display device is etched with a conventional etchant consisting of phosphoric acid, nitric acid, acetic acid, and water, a uniform pattern is manufactured in the form of FIGS. 2 and 3. As shown in FIG. 1, a case where Al, which is an Mo lower layer, is over-etched frequently occurs.
이러한 현상의 원인은 수용액중에서 두가지 금속이 접촉되어 있을 때 전위전극(Electrode Potential)이 비(Base)한 금속인 Al(E=-1.66V)이 양극이 되어 용해가 촉진되고 귀(Noble)한 금속인 Mo(E=-0.20V)가 음극이 되어 보호되어 상대적으로 용해(전기화학적 식각)가 지연되는 국부전지(Local Cell 또는 Galvanic Cell)에 의한 국부침식(Galvanic Corrosion)현상으로 해석된다.The cause of this phenomenon is that Al (E = -1.66V), a metal with a non-electrode potential, becomes an anode when two metals are in contact with each other in an aqueous solution, thereby promoting dissolution and noble metal. Phosphorus Mo (E = -0.20V) is interpreted as a galvanic corrosion phenomenon by local cells (Local Cell or Galvanic Cell), which is protected as a negative electrode and relatively dissolves (electrochemical etching).
이러한 국부침식 현상으로 인하여 게이트 전극의 패턴이 균일하게 형성되지 않으면 액정표시장치의 영상의 고해상도 및 선명한 색상구현이 어려워지는 문제점이 발생한다.If the pattern of the gate electrode is not uniformly formed due to the local erosion phenomenon, it is difficult to realize high resolution and vivid color of the image of the liquid crystal display.
본 발명이 이루고자 하는 기술적 과제는 인산 + 질산 + 초산 + 물의 조성물로 이루어진 종래의 식각액에 추가의 산화제가 첨가된 식각액을 사용하여 액정표시장치의 TFT를 구성하는 게이트 전극의 Mo/Al의 이중층을 균일한 패턴으로 습식식각할 수 있는 방법을 제공하기 위한 것이다.The technical problem to be achieved by the present invention is to uniformize the double layer of Mo / Al of the gate electrode constituting the TFT of the liquid crystal display using an etchant added to the conventional etchant consisting of a composition of phosphoric acid + nitric acid + acetic acid + water It is to provide a method for wet etching in a pattern.
도 1 은 기존 식각액에 의한 습식식각 공정 후의 포트레지스트와 게이트 전극재인 Mo/Al의 이중층 단면을 전자현미경으로 관찰한 사진도FIG. 1 is a photograph showing an electron microscope view of a cross-section of a double layer of Mo / Al, a photoresist and a gate electrode material, after a wet etching process using an existing etching solution.
도 2 는 본 발명의 식각액에 의한 습식식각 공정후의 포트레지스트와 게이트 전극재인 Mo/Al의 이중층 단면을 전자현미경으로 관찰한 사진도FIG. 2 is a photograph showing an electron microscope view of a cross-section of a double layer of Mo / Al as a port resist and a gate electrode material after a wet etching process using an etchant of the present invention. FIG.
도 3 은 본 발명의 식각액에 의한 습식식각 공정후의 포트레지스트와 게이트 전극재인 Mo/Al의 이중층 단면을 전자현미경으로 관찰한 사진도FIG. 3 is a photograph showing an electron microscope view of a cross-section of a double layer of Mo / Al as a port resist and a gate electrode material after a wet etching process using an etchant of the present invention. FIG.
본 발명은 균일한 프로파일(Profile)을 갖는 Mo/Al 이중층을 얻기 위하여 종래의 식각공정에서 사용하던 기존의 식각액인 인산 + 질산 + 초산 + 물의 조성물에 추가의 산화제를 첨가하여 Mo/Al 습식식각을 행하도록 한 것이다.In the present invention, an additional oxidant is added to the composition of the conventional etching solution, phosphate, nitric acid, acetic acid, and water, which is used in a conventional etching process, to obtain a Mo / Al double layer having a uniform profile. It was done.
기존의 식각액에 산화제를 첨가하여 습식식각을 행하면 Mo/Al의 균일한 경사각을 갖는 테이퍼식각(Taper Etching)이 가능한 결과를 얻었다.When wet etching was performed by adding an oxidizing agent to an existing etching solution, a taper etching with a uniform inclination angle of Mo / Al was obtained.
이 현상은 국부전지의 양극부분에서 발생하는 식 1과 같은 반응 메카니즘에 대하여 Al → Al3 ++ 3e---------------- (식 1)This phenomenon with respect to the reaction mechanism, such as the formula (1) occurring in the cathode portion of the local cell Al → Al 3 + + 3e - --------------- ( formula 1)
추가의 산화제를 첨가하여 (식 1)의 반응이 일반적으로 진행되는 양극인 Al 금속막 표면에 부분적으로 부동태산화막(Passivation Oxide Film)을 형성하여 식각속도를 감소시키며, 첨가되는 산화제의 역할은 양극부식억제제(Anodic Corrosion Inhibitor)라 한다.By adding an additional oxidant, a passivation oxide film is partially formed on the Al metal film surface, which is the anode in which the reaction of Equation 1 generally proceeds, thereby reducing the etching rate, and the role of the added oxidant is anode corrosion. It is called an Anodic Corrosion Inhibitor.
양극부식 억제제는 국부전지 효과에 의해서 전극전위가 상대적으로 비(Base)한 양극에서 용해(전기화학적 식각) 반응이 촉진되는 현상을 억제하기 위하여 인위적으로 여러가지 유기 혹은 무기화합물을 첨가하여 활성양극면적을 감소시켜 식각속도를 저감시키는 역할을 한다.In order to suppress the phenomenon that the dissolution (electrochemical etching) reaction is promoted in the anode where the electrode potential is relatively low by the effect of local battery, the anode corrosion inhibitor is artificially added with various organic or inorganic compounds to change the active anode area. It serves to reduce the etching rate by reducing.
본 발명의 경우에는 산화제를 사용했으므로 첨가한 산화제가 산화억제제(Oxidizing Inhibitor)의 역할을 한다.In the case of the present invention, since the oxidant is used, the added oxidant serves as an oxidizing inhibitor.
산화제를 첨가한 경우의 정량 측정방법은 식각액조정별로 산화환원전위(Oxidation Reduction Potential)를 측정한 결과로서 표시한다.The quantitative measurement method when oxidant is added is expressed as a result of measuring Oxidation Reduction Potential for each etching liquid adjustment.
종래의 식각액에 첨가할 수 있는 산화제로서는 H2O2, O2, K2Cr207, HClO, HClO2, HClO3, HlO4등이 가능하나 HClO4와 HlO4의 산화제가 바람직하다.The oxidizing agent which can be added to the conventional etching solution may be H 2 O 2 , O 2 , K 2 Cr 2 O 7 , HClO, HClO 2 , HClO 3 , HlO 4, etc., but oxidizing agents of HClO 4 and HlO 4 are preferable.
종래의 인산 + 질산 + 초산 + 물로 이루어진 식각액에 양극부식억제제로서 HClO4와 HlO4를 첨가한 경우 주요 정량측정 표시수단으로서 산화환원전위를 측정한 결과를 표 1과 표 2에 보였다.In the case of adding HClO 4 and HlO 4 as an anode corrosion inhibitor to the conventional etching solution consisting of phosphoric acid + nitric acid + acetic acid + water, the results of measuring the redox potential as the main quantitative measurement indicators are shown in Tables 1 and 2.
표 1. HClO4를 첨가한 경우 산화환원 전위Table 1. Redox potential when HClO 4 is added
표 2. HlO4를 첨가한 경우 산화환원 전위Table 2. Redox potential when HlO 4 is added
바람직한 식각액의 조성은 인산(60∼70wt.%), 질산(5∼14wt.%), 초산(5∼15wt.%) + HClO4(1∼6wt.%) 또는 인산(60∼70wt.%), 질산(5∼14wt.%), 초산(5∼15wt.%) + HlO4(1∼6wt.%)가 적합하다.Preferred compositions of the etchant are phosphoric acid (60-70 wt.%), Nitric acid (5-14 wt.%), Acetic acid (5-15 wt.%) + HClO 4 (1-6 wt.%) Or phosphoric acid (60-70 wt.%). Nitric acid (5-14 wt.%), Acetic acid (5-15 wt.%) + H10 (1-6 wt.%) Are suitable.
상기 식각액의 조성물 중 잔여부분은 물로 구성된다.The remainder of the composition of the etchant consists of water.
실시예 1. 종래의 식각액을 사용한 Mo/Al 일괄식각Example 1. Mo / Al batch etching using a conventional etchant
인산 + 질산 + 초산 + 물로 이루어진 종래의 식각액을 사용하여 습식식각공정을 수행한 결과 도 1 에서 표시한 Al 하부막이 Mo 상부막에 비해 과잉식각된 결과가 관찰되었다.As a result of performing a wet etching process using a conventional etchant consisting of phosphoric acid, nitric acid, acetic acid, and water, the Al underlayer shown in FIG. 1 was overetched compared to the Mo top layer.
실시예 2. 산화부식억제제로서 HClO4를 첨가한 경우 Mo/Al 일괄식각Example 2 Mo / Al Batch Etching When HClO 4 Is Added as an Oxidation Inhibitor
인산(60∼70wt.%) + 질산(5∼14wt.%) + 초산(5∼15wt.%) + 물의 조성범위를 갖는 종래의 식각액에 HClO4를 표 1 에 표시한 바와 같이 사례 2에서 사례 7의 함유율로 첨가하여 실시예 1 과 같은 조건으로 습식식각공정을 수행한 결과 도 2 와 도 3 에 표시한 결과와 같이 Al 하부막이 Mo 상부막에 비해 과잉식각되지 않은 테이퍼 식각(Taper Etching)된 결과가 관찰되었다.HClO 4 in a conventional etchant having a composition range of phosphoric acid (60 to 70 wt.%) + Nitric acid (5 to 14 wt.%) + Acetic acid (5 to 15 wt.%) + Water, as shown in Table 1 As a result of performing a wet etching process under the same conditions as in Example 1 with the addition of the content of 7, the lower Al film was tapered etched without excessive etching compared to the Mo upper film as shown in FIGS. 2 and 3. Results were observed.
실시예 3. 산화부식억제제로서 HlO4를 첨가한 경우 Mo/Al 일괄식각Example 3 Mo / Al Batch Etching When HlO 4 is Added as an Oxidation Inhibitor
인산(60∼70wt.%) + 질산(5∼14wt.%) + 초산(5∼15wt.%) + 물의 조성범위를 갖는 종래의 식각액에 HlO4를 표 2에 표시한 바와 같이 사례 2 에서 사례 7의 함유율로 첨가하여 실시예 1 과 같은 조건으로 습식식각공정을 수행한 결과 도 2 와 도 3 에 표시한 결과와 같이 Al 하부막이 Mo 상부막에 비해 과잉식각 되지 않은 테이퍼식각(Taper Etching)된 결과가 관찰되었다.HlO 4 in a conventional etchant having a composition range of phosphoric acid (60 to 70 wt.%) + Nitric acid (5 to 14 wt.%) + Acetic acid (5 to 15 wt.%) + Water, as shown in Table 2 As a result of performing the wet etching process under the same conditions as in Example 1 with the addition of the content of 7, as shown in FIGS. 2 and 3, the Al lower layer was not tapered etched without excessive etching compared to the Mo upper layer. The result was observed.
본 발명에 따른 액정표시장치의 TFT를 구성하는 게이트전극인 Mo/Al 이중층을 일괄식각할 수 있는 인산(60∼70wt.%) + 질산(5∼14wt.%) + 초산(5∼15wt.%) + HClO4혹은 HlO4(1∼6wt.%) + 물의 조정을 갖는 식각액을 사용하여 테이퍼 식각(Taper Etching)이 가능하며 균일한 패턴의 식각이 가능한 것이다.Phosphoric acid (60 to 70 wt.%) + Nitric acid (5 to 14 wt.%) + Nitric acid (5 to 15 wt.%) Capable of collectively etching the Mo / Al double layer, which is a gate electrode constituting the TFT of the liquid crystal display according to the present invention. Tapered etching is possible using an etching solution with the adjustment of) + HClO 4 or HlO 4 (1 ~ 6wt.%) + Water, and uniform pattern etching is possible.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003036377A1 (en) * | 2001-10-23 | 2003-05-01 | Samsung Electronics Co., Ltd. | A etchant for wires, a method for manufacturing the wires using the etchant, a thin film transistor array substrate and a method for manufacturing the same including the method |
| KR20030041694A (en) * | 2001-11-21 | 2003-05-27 | 테크노세미켐 주식회사 | Etchant for making gate electrode in TFT-LCD |
| KR100444345B1 (en) * | 2002-03-28 | 2004-08-16 | 테크노세미켐 주식회사 | Etchant for making metal electrodes of TFT in FPD |
| KR100685953B1 (en) * | 2002-08-20 | 2007-02-23 | 엘지.필립스 엘시디 주식회사 | Formation method of wiring for liquid crystal display device |
| KR100848109B1 (en) * | 2001-10-23 | 2008-07-24 | 삼성전자주식회사 | Wiring etchant, method for manufacturing wiring using same, and method for manufacturing thin film transistor array substrate comprising same |
| KR100944300B1 (en) * | 2001-10-22 | 2010-02-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching method of aluminum / molybdenum laminated film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101026808B1 (en) | 2004-04-30 | 2011-04-04 | 삼성전자주식회사 | Method of manufacturing thin film transistor array panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2673460B2 (en) * | 1990-02-26 | 1997-11-05 | キヤノン株式会社 | Liquid crystal display device |
| JPH04372934A (en) * | 1991-06-24 | 1992-12-25 | Toshiba Corp | Manufacture of array substrate for liquid crystal display device |
| JPH0764109A (en) * | 1993-08-25 | 1995-03-10 | Toshiba Corp | Liquid crystal display |
| JPH09127555A (en) * | 1995-11-01 | 1997-05-16 | Sony Corp | Method of forming laminated wiring |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100944300B1 (en) * | 2001-10-22 | 2010-02-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | Etching method of aluminum / molybdenum laminated film |
| WO2003036377A1 (en) * | 2001-10-23 | 2003-05-01 | Samsung Electronics Co., Ltd. | A etchant for wires, a method for manufacturing the wires using the etchant, a thin film transistor array substrate and a method for manufacturing the same including the method |
| KR100840333B1 (en) * | 2001-10-23 | 2008-06-20 | 삼성전자주식회사 | Wiring etchant, and method for manufacturing wiring using same and method for manufacturing thin film transistor array substrate using same |
| KR100848109B1 (en) * | 2001-10-23 | 2008-07-24 | 삼성전자주식회사 | Wiring etchant, method for manufacturing wiring using same, and method for manufacturing thin film transistor array substrate comprising same |
| KR20030041694A (en) * | 2001-11-21 | 2003-05-27 | 테크노세미켐 주식회사 | Etchant for making gate electrode in TFT-LCD |
| KR100444345B1 (en) * | 2002-03-28 | 2004-08-16 | 테크노세미켐 주식회사 | Etchant for making metal electrodes of TFT in FPD |
| KR100685953B1 (en) * | 2002-08-20 | 2007-02-23 | 엘지.필립스 엘시디 주식회사 | Formation method of wiring for liquid crystal display device |
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