KR100415947B1 - Formulation of Cr Etchant - Google Patents
Formulation of Cr Etchant Download PDFInfo
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- KR100415947B1 KR100415947B1 KR10-2001-0019954A KR20010019954A KR100415947B1 KR 100415947 B1 KR100415947 B1 KR 100415947B1 KR 20010019954 A KR20010019954 A KR 20010019954A KR 100415947 B1 KR100415947 B1 KR 100415947B1
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- chromium
- ammonium nitrate
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- etchant
- etching
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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
- C23F1/26—Acidic compositions for etching refractory metals
Abstract
본 발명은 박막트랜지스터 액정표시장치의 TFT(Thin Film Transistor)를 구성하는 게이트(Gate), 소스(Source) 및 드레인(Drain) 전극용 금속 배선재 및 칼라필터용 크롬(Cr)막의 에칭액 조성물에 관한 것으로서, 종래의 질산계 및 과염소산계 크롬에천트 조성물에 추가로 열안정성 제고를 위한 완충제로 질산암모늄(NH4NO3)을 첨가해서 크롬에천트에 일정농도의 질산암모늄이 함유하도록 하는 것을 특징으로 한다. 이때 질산 암모늄의 농도는 0.5-30wt%이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching solution composition of a metal wiring material for a gate, a source and a drain electrode, and a chromium (Cr) film for a color filter constituting a thin film transistor (TFT) of a thin film transistor liquid crystal display device. In addition, ammonium nitrate (NH 4 NO 3 ) is added to the conventional nitric acid- and perchloric acid-based chromium etchant composition as a buffer for enhancing thermal stability, so that a certain concentration of ammonium nitrate is contained in the chromium etchant. . At this time, the concentration of ammonium nitrate is 0.5-30wt%.
이러한 본 발명은 종래의 크롬에천트에 완충제로 질산암모늄을 일정농도 함유하도록 함으로써, 종래의 크롬에천트의 문제점인 크롬에칭시 잔사 발생현상을 제거하여 공정수율 향상 및 크롬 에천트의 사용 주기를 연장시켜 제조원가 절감 효과를 가져오게 된다.In the present invention, by containing a certain concentration of ammonium nitrate as a buffer in the conventional chromium etchant, by removing the residue generated when chromium etching, a problem of the conventional chromium etchant improves the process yield and extends the use cycle of the chromium In this case, the manufacturing cost is reduced.
Description
본 발명은 박막트랜지스터 액정표시장치 등에서 게이트(Gate), 소스(Source) 및 드레인(Drain) 전극용의 금속 배선재 및 칼라필터용 크롬막의 에칭액 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching solution composition of a metal wiring material for gate, source and drain electrodes and a chromium film for color filters in a thin film transistor liquid crystal display device.
크롬막은 박막트랜지스터 액정표시장치등의 평판디스플레이용 표시장치에 폭넓게 사용되고 있는 박막으로서, 액정표시장치용등의 크롬막을 형성하기 위해서는 원하는 미세 패턴을 형성시키는 에칭공정이 필요하다.The chromium film is a thin film widely used in flat panel display devices such as thin film transistor liquid crystal displays, and in order to form a chromium film for liquid crystal displays, an etching process for forming a desired fine pattern is required.
상기 크롬막의 사용은 유리등의 기판 위에 크롬막을 형성시킨 다음 포토레지 스터를 마스크로서 도포한 후 크롬막을 에칭하게 되는 것으로 종래의 크롬막용에천트는 질산제2세륨암모늄과 질산과 물 또는 질산제2세륨암모늄과 과염소산과 물의 조성물로 된 크롬에천트이며, 이러한 종래의 크롬에천트들은 열안정성이 낮아서 에칭시 주기적으로 잔사가 발생하는 문제점을 내재하고 있다.The use of the chromium film is to form a chromium film on a substrate such as glass, and then to apply a photoresist as a mask and then to etch the chromium film. Conventional chromium film etchant includes ammonium nitrate nitrate, nitric acid and water or nitrate 2 It is a chromium etchant made of a composition of cerium ammonium, perchloric acid and water, and these conventional chromium etchants have a problem of low residues due to low thermal stability.
본 발명은 종래의 크롬에천트인 질산제2세륨암모늄과 질산과 물의 조성물 또는 질산제2세륨암모늄과 과염소산과 물의 조성물이 열적 안정성이 낮아서 발생되는에칭시 잔사 발생현상의 문제점을 해결할 수 있는 크롬막용 에천트의 조성물을 제공하기 위한 것으로, 본 발명의 조성물은 질산제2세륨암모늄과 질산과 질산암모늄과 물 또는 질산제2세륨암모늄과 과염소산과 질산암모늄과 물로 구성되어 있으며 열적안정성이 우수한 것을 특징으로 하고 있다.The present invention is a chromium film for chromium film that can solve the problem of residues generated during etching due to the low thermal stability of the composition of cerium ammonium nitrate and nitric acid and water or the composition of dicerium ammonium and perchloric acid and water. In order to provide a composition of the etchant, the composition of the present invention is composed of dicerium ammonium nitrate and ammonium nitrate and ammonium nitrate and water or dicerium nitrate ammonium and perchloric acid and ammonium nitrate and water and characterized by excellent thermal stability. Doing.
본 발명의 조성물은 열적안정성이 우수하기 때문에 종래의 크롬에천트의 문제점인 에칭시 잔사발생현상이 제거되어 크롬막 에칭 공정에서의 에칭 불량율을 감소시켜 공정수율을 향상시키도록 할뿐만 아니라 크롬에천트의 열안정성을 제고시킴으로써 크롬에천트의 사용 주기도 연장시키는 효과를 가져올 수 있다.Since the composition of the present invention has excellent thermal stability, residues generated during etching, which is a problem of the conventional chromium etchant, are removed, thereby reducing the etching failure rate in the chromium film etching process, thereby improving the process yield, as well as the chromium etchant. By improving the thermal stability of the chromium etchant can also be extended to extend the life cycle.
본 발명은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 전극 및 칼라필터용 크롬막의 패턴에칭시 적용되는 크롬에천트의 조성물에 관한 것으로서, 에칭액의 경시변화 부문과 에칭의 제반 특성이 양호하고 에칭시 잔사발생을 억제하는 크롬막용 수용성 에칭액인 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition of a chromium etchant applied to pattern etching of electrodes of a flat panel display including a thin film transistor liquid crystal display and a chromium film for a color filter. It is a water-soluble etching liquid for chromium films which suppresses the occurrence of residues during etching.
이러한 본 발명의 크롬막용 에칭액은 5-30wt%의 질산제2세륨암모늄과 3-30 wt%의 질산과 0.5-30wt%의 질산암모늄과 물의 조성물 또는 5-30wt% 질산제2세륨암모늄과 3-30wt%의 과염소산과 0.5-30wt%의 질산암모늄과 물의 조성물이다.The etching solution for the chromium film of the present invention is a composition of 5-30 wt% diammonium nitrate, 3-30 wt% nitric acid, 0.5-30 wt% ammonium nitrate, water or 5-30 wt% dicerium ammonium nitrate and 3- 30 wt% perchloric acid, 0.5-30 wt% ammonium nitrate and water.
본 발명의 크롬에천트의 특징은 종래의 크롬에천트의 조성물에 주 반응제인 질산제2세륨암모늄의 열안정성을 개선할 수 있는 방안으로 일정농도의 질산암모늄을 에칭액의 함유하게 함으로써 열안정성을 향상시켜 세륨이 잔사로 떨어지는 것을 억제하는 것이다. 이때 질산암모늄을 본 발명의 크롬에천트 중에 함유하게 하는 방법으로서는 종래의 크롬에천트의 조성물에 질산암모늄을 첨가하는 방법 또는 암모니아 가스를 주입하여 질산과의 중화반응으로 질산암모늄을 형성시키는 방법 또는 암모니아수를 첨가하여 질산과의 중화반응으로 질산암모늄을 형성시키는 방법 등이 있다.A feature of the chromium etchant of the present invention is to improve the thermal stability of the composition of the conventional chromium etchant as the main reactant dicerium nitrate ammonium nitrate. This prevents the cerium from falling into the residue. At this time, as a method for containing ammonium nitrate in the chromium etchant of the present invention, a method of adding ammonium nitrate to the composition of the conventional chromium etchant or a method of forming ammonium nitrate by neutralization reaction with nitric acid by injecting ammonia gas or ammonia water And the like to form ammonium nitrate by neutralization with nitric acid.
실시예 1 :Example 1:
10wt%의 (NH4)2Ce(NO3)6에 5wt%의 HNO3와 4wt%의 NH4NO3와 물을 첨가하여 크롬에칭액을 제조하였다.A chromium etching solution was prepared by adding 5 wt% HNO 3 , 4 wt% NH 4 NO 3, and water to 10 wt% of (NH 4 ) 2 Ce (NO 3 ) 6 .
이 에칭액을 사용하여 포토레지스터로 패턴을 형성한 크롬막 기판(크롬막두께 2000Å)을 32℃에서 1분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의 해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, the chromium film substrate (chromium film thickness 2000Å) formed with a photoresist was sprayed at 32 ° C. for 1 minute to be etched, washed with ultrapure water for about 1 minute, and dried using nitrogen. .
이와같이 에칭을 완료 한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았으며 크롬막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and the chromium film was well etched.
실시예 2 :Example 2:
10wt%의 (NH4)2Ce(NO3)6에 15wt%의 HClO4와 6wt%의 NH4NO3와 물을 첨가하여 크롬에칭액을 제조하였다.Chromium etching solution was prepared by adding 15 wt% of HClO 4 , 6 wt% of NH 4 NO 3, and water to 10 wt% of (NH 4 ) 2 Ce (NO 3 ) 6 .
이 에칭액을 사용하여 포토레지스터로 패턴을 형성한 크롬막 기판(크롬막두께 2000Å)을 32℃에서 1분간 스프레이하여 에칭을 한 후에 약 1분간 초순수에 의 해 수세를 행한 후 질소를 사용하여 건조시켰다.Using this etching solution, the chromium film substrate (chromium film thickness 2000Å) formed with a photoresist was sprayed at 32 ° C. for 1 minute to be etched, washed with ultrapure water for about 1 minute, and dried using nitrogen. .
이와같이 에칭을 완료 한 후 기판 표면을 전자현미경에 의해 관찰해 본 결과, 기판 표면에 어떠한 잔사도 보이지 않았으며 크롬막은 양호하게 에칭이 된 것을 확인할 수 있었다.After the etching was completed, the surface of the substrate was observed by electron microscopy. As a result, no residue was observed on the surface of the substrate, and the chromium film was well etched.
실시예 3 :Example 3:
종래의 질산계 크롬에칭액과 본 발명의 질산계 크롬에칭액과의 열안정성 테스터를 통하여 열안정성을 비교하였다.Thermal stability was compared through a thermal stability tester between the conventional nitrate chromium etch solution and the nitrate chromium etch solution of the present invention.
열 안정성 테스터 조건과 방법은 먼저 10wt%의 (NH4)2Ce(NO3)6와 5wt%의 HNO3와 물로 이루어진 종래의 질산계 크롬에천트의 조성물과 10wt%의 (NH4)2Ce(NO3)6와 5wt% HNO3와 4wt%의 NH4NO3와 물로 이루어진 본 발명의 질산계 크롬에칭액의 조성물을 각각 제조하여 사용하였고, 침적테스터 온도는 80℃이며, 잔사가 발생하기 시작하는 시간을 확인하는 방법의 테스터를 수행하였다. 열안정성 비교테스터의 결과는 아래의 표1과 같다.Thermal stability tester conditions and methods were first prepared with a composition of conventional nitrate-based chromium nitrate consisting of 10 wt% (NH 4 ) 2 Ce (NO 3 ) 6 , 5 wt% HNO 3, and water and 10 wt% (NH 4 ) 2 Ce. (NO 3 ) 6 and 5wt% HNO 3 and 4wt% NH 4 NO 3 The composition of the nitrate-based chromium etch solution of the present invention was prepared and used, respectively, the deposition tester temperature is 80 ℃, residues start to occur The tester of the method to confirm the time to perform. The results of the thermal stability tester are shown in Table 1 below.
표1)Table 1
실시예 4 :Example 4:
종래의 과염소산계 크롬에칭액과 본 발명의 과염소산계 크롬에칭액과의 열안정성 테스터를 통하여 열안정성을 비교하였다.Thermal stability was compared through a thermal stability tester between the conventional perchloric acid-based chromium etching solution and the perchloric acid-based chromium etching solution of the present invention.
열안정성 테스터 조건과 벙법은 먼저 10wt%의 (NH4)2Ce(NO3)6와 15wt%의 HClO4와 물로 이루어진 종래의 과염소산계 크롬에칭액의 조성물과 10wt%의 (NH4)2Ce(NO3)6와 15wt%의 HClO4와 6wt% NH4NO3와 물로 이루어진 본 발명의 과염소산계 크롬에칭액의 조성물을 각각 제조하여 사용하였고, 침적테스터 온도는 80℃이며, 잔사가 발생하기 시작하는 시간을 확인하는 방법의 테스터를 수행하였다. 열안정성 비교테스터의 결과는 아래의 표2와 같다.The thermal stability tester conditions and method were first composed of 10 wt% of (NH 4 ) 2 Ce (NO 3 ) 6 , 15 wt% of HClO 4 and water, and 10 wt% of (NH 4 ) 2 Ce ( NO 3 ) 6 and 15 wt% of HClO 4 , 6 wt% NH 4 NO 3, and a composition of the perchloric acid-based chromium etching solution of the present invention were prepared and used, respectively, and the deposition tester temperature was 80 ° C., and residues began to occur. A tester of how to confirm the time was performed. The results of the thermal stability tester are shown in Table 2 below.
표2)Table 2)
본 발명의 크롬막용 에칭액은 박막트랜지스터 액정표시장치를 포함한 평판디스플레이용 표시장치의 전극 및 칼라필터용 크롬막의 패턴 에칭을 위하여 적용할 경우 종래의 크롬막용 에칭액과는 달리 열안정성이 우수하여 에칭시 잔사 발생 현상의 문제점이 제거되어 공정수율 향상과 제조원가 절감 효과를 가져오게 된다.The etching solution for chromium film of the present invention is excellent in thermal stability, unlike the conventional chromium film etching solution, when applied for pattern etching of the electrode of a flat panel display including a thin film transistor liquid crystal display and a chromium film for color filters. The problem of occurrence is eliminated, resulting in improved process yield and manufacturing cost.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05271967A (en) * | 1992-03-24 | 1993-10-19 | The Ink Tec Kk | Liquid etchant composition and method for etching chromium thin film |
| JPH1010585A (en) * | 1996-06-27 | 1998-01-16 | Seiko Epson Corp | Production of liquid crystal display device and liquid crystal display device |
| JPH11131263A (en) * | 1997-10-27 | 1999-05-18 | Nec Kagoshima Ltd | Etching of chromium film |
| JP2002064101A (en) * | 2000-08-21 | 2002-02-28 | Casio Comput Co Ltd | Method of forming wiring having chromium layer |
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- 2001-04-13 KR KR10-2001-0019954A patent/KR100415947B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05271967A (en) * | 1992-03-24 | 1993-10-19 | The Ink Tec Kk | Liquid etchant composition and method for etching chromium thin film |
| JPH1010585A (en) * | 1996-06-27 | 1998-01-16 | Seiko Epson Corp | Production of liquid crystal display device and liquid crystal display device |
| JPH11131263A (en) * | 1997-10-27 | 1999-05-18 | Nec Kagoshima Ltd | Etching of chromium film |
| JP2002064101A (en) * | 2000-08-21 | 2002-02-28 | Casio Comput Co Ltd | Method of forming wiring having chromium layer |
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