KR20040074428A - a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma - Google Patents
a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma Download PDFInfo
- Publication number
- KR20040074428A KR20040074428A KR1020030010183A KR20030010183A KR20040074428A KR 20040074428 A KR20040074428 A KR 20040074428A KR 1020030010183 A KR1020030010183 A KR 1020030010183A KR 20030010183 A KR20030010183 A KR 20030010183A KR 20040074428 A KR20040074428 A KR 20040074428A
- Authority
- KR
- South Korea
- Prior art keywords
- alignment layer
- plasma
- negative photoresist
- substrate
- glass substrate
- Prior art date
Links
Classifications
-
- 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
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
- E03D1/30—Valves for high or low level cisterns; Their arrangement ; Flushing mechanisms in the cistern, optionally with provisions for a pre-or a post- flushing and for cutting off the flushing mechanism in case of leakage
- E03D1/34—Flushing valves for outlets; Arrangement of outlet valves
- E03D1/35—Flushing valves having buoyancy
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D1/00—Water flushing devices with cisterns ; Setting up a range of flushing devices or water-closets; Combinations of several flushing devices
- E03D1/02—High-level flushing systems
- E03D1/14—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves
- E03D1/142—Cisterns discharging variable quantities of water also cisterns with bell siphons in combination with flushing valves in cisterns with flushing valves
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D3/00—Flushing devices operated by pressure of the water supply system flushing valves not connected to the water-supply main, also if air is blown in the water seal for a quick flushing
- E03D3/12—Flushing devices discharging variable quantities of water
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
- E03D5/00—Special constructions of flushing devices, e.g. closed flushing system
- E03D5/02—Special constructions of flushing devices, e.g. closed flushing system operated mechanically or hydraulically (or pneumatically) also details such as push buttons, levers and pull-card therefor
- E03D5/09—Special constructions of flushing devices, e.g. closed flushing system operated mechanically or hydraulically (or pneumatically) also details such as push buttons, levers and pull-card therefor directly by the hand
- E03D5/092—Special constructions of flushing devices, e.g. closed flushing system operated mechanically or hydraulically (or pneumatically) also details such as push buttons, levers and pull-card therefor directly by the hand the flushing element, e.g. siphon bell, being actuated through a lever
-
- 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
- G02F1/1316—Methods for cleaning the liquid crystal cells, or components thereof, during manufacture: Materials therefor
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Public Health (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Aviation & Aerospace Engineering (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal (AREA)
Abstract
Description
본 발명은 LCD나 TFT(Thin Film transistor)-LCD 등에 사용되는 유리기판을 재생하는 방법에 관한 것으로서, 보다 상세하게는 LCD, TFT-LCD 등의 글래스 기판 위에 형성된 네가티브 포토레지스트 위에 도포된 폴리이미드 유기 배향막을 건식플라즈마를 이용하여 선택적으로 제거함으로써 글래스 기판을 재생하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for reproducing glass substrates used in LCDs or thin film transistor (LCD) -LCDs. More specifically, the present invention relates to polyimide organic materials coated on negative photoresists formed on glass substrates such as LCD and TFT-LCDs. A method of regenerating a glass substrate by selectively removing the alignment film using dry plasma.
각종 평판표시소자의 발달과 더불어 LCD, TFT-LCD의 개발 및 생산이 늘어나고 있다. 이와 같은 LCD소자는 기본적으로 글래스로 이루어져 서로 대향하는 기판 내면에 전극을 도포하고 그 위에 포스트 스페이서(post spacer)나 프로트루젼(protrusion) 또는 수지를 이용한 블랙매트릭스(resin BM)를 형성한 다음, 그 위에 다시 폴리이미드 유기 배향막을 도포한 후 그 사이에 액정을 주입하고 이를 밀봉함으로써 구성된다.With the development of various flat panel display devices, the development and production of LCD and TFT-LCD are increasing. Such an LCD element is basically composed of glass to apply the electrode on the inner surface of the substrate facing each other, and to form a black matrix (resin BM) using a post spacer (protrusion) or resin thereon, It is comprised by apply | coating a polyimide organic aligning film on it again, injecting a liquid crystal between it, and sealing it.
이 중에서 배향막의 도포 과정을 살펴보면, 일단 포스트 스페이서 등이 형성된 글래스 기판을 세정한 후 폴리이미드를 인쇄하고 예비 소성(Pre curing)을 한 다음, 배향막의 상태를 검사한 후 양호한 상태이면 2차 소성을 완료하고, 이어서 액정 배열을 위한 러빙(Rubbing)을 하게 된다. 상기 공정에 있어서, 예비 소성된 기판을 검사하고 만약 불량이 발생하면 이를 기판 재생 공정으로 넘겨 기판을 재생하여 사용하게 되는데, 이것은 2차 소성을 거친 후에도 마찬가지이다.In the application process of the alignment film, once the glass substrate on which the post spacers are formed is cleaned, the polyimide is printed and pre-cured, and the state of the alignment film is inspected. This is followed by rubbing for the liquid crystal array. In the above process, the pre-fired substrate is inspected and if a defect occurs, it is transferred to the substrate regeneration process to regenerate the substrate, which is the same even after the secondary firing.
이와 같이, 액정표시소자의 제조공정에 있어서 폴리이미드 유기 배향막을 기판에 도포한 후에 기판을 재생해야 할 경우가 많이 발생한다. 기판 재생 공정에서는 포스트 스페서 등이 형성된 글라스 기판에 도포된 폴리이미드 배향막을 제거해야 하는데, 종래에는 전적으로 습식공정에 의해 폴리이미드 유기 배향막이 제거되었다.Thus, in the manufacturing process of a liquid crystal display element, many cases generate | occur | produce a board | substrate after apply | coating a polyimide organic aligning film to a board | substrate. In the substrate regeneration process, the polyimide alignment film applied to the glass substrate on which the post spacer or the like is formed must be removed. In the past, the polyimide organic alignment film was completely removed by a wet process.
즉, 폴리이미드 배향막을 제거하기 위한 종래의 습식공정으로서, 재생될 기판에 도포된 폴리이미드 배향막에 테트라메틸암모늄하이드록사이드(Tetra Methyl Ammonium Hydroxide)와 같은 용매를 가하여 폴리이미드 배향막을 박리시킨다(스트립공정). 이어서, 배향막이 박리된 기판을 브러싱(Brushing) 하고 중성용액으로 세정한 후, 스핀드라이(Spin Dry)에 의해 건조시킴으로써 기판을 재생하게 된다.That is, as a conventional wet process for removing the polyimide alignment layer, a solvent such as tetramethyl ammonium hydroxide is added to the polyimide alignment layer coated on the substrate to be regenerated to peel off the polyimide alignment layer (strip fair). Subsequently, the substrate on which the alignment layer has been peeled off is brushed and washed with a neutral solution, and then dried by spin dry to regenerate the substrate.
그러나 위와 같은 종래의 습식공정에 있어서는 다음과 같은 문제점이 있었다.However, the above-described conventional wet process has the following problems.
첫째, 위와 같이 용매에 의한 폴리이미드 유기 배향막의 박리 방법은 배향막을 완전히 제거하기가 어려우므로 재생한 기판의 품질이 우수하지 못하였다. 습식공정에서 재생기판에 가해진 용매는 기판과 폴리이미드 사이로 침투하여 박리를 시키게 되는데, 이 과정에서 최초 침투하기 시작한 부위의 박리량과 나중에 침투한 부분에서의 박리량이 차이가 발생하여 불균일한 박리가 일어나는 문제점을 초래하였다. 특히, 폴리이미드 도포 후 예비 소성 단계에서 재생되는 것은 폴리이미드 배향막의 제거가 비교적 용이하나, 2차 소성을 거친 후에는 배향막이 견고히 형성되어 있으므로 배향막을 제거하기가 어려워 완전한 기판의 재생이 불가능하였다.First, the peeling method of the polyimide organic alignment layer by the solvent as described above is difficult to remove the alignment layer completely, the quality of the regenerated substrate was not excellent. In the wet process, the solvent applied to the regenerated substrate penetrates between the substrate and the polyimide to exfoliate. In this process, the exfoliation amount of the first penetration site and the later penetration area are different, resulting in uneven peeling. It caused a problem. In particular, it is relatively easy to remove the polyimide alignment layer after the polyimide coating, but after the second firing, since the alignment layer is firmly formed, it is difficult to remove the alignment layer and thus it is impossible to completely reproduce the substrate.
둘째, 습식공정은 각 공정별로 라인설비 및 공정에 소요되는 비용이 많으며 작업 공간이 클 뿐만 아니라 유기 용매를 다량 사용하게 되므로, 폐수처리 또는 재사용을 위한 설비에 막대한 비용이 소요되며, 그렇지 않을 경우에는 환경오염을 유발하는 문제마저 안고 있었다.Second, the wet process requires a lot of costs for line equipment and processes for each process, as well as a large work space, and uses a large amount of organic solvents, and therefore, a huge cost is required for a facility for wastewater treatment or reuse. There was even a problem that caused environmental pollution.
셋째, 습식공정에 사용되는 유기용매로는 배향막 밑에 전체적으로 또는 부분적으로 존재하는 포스트 스페이서(post spacer)나 프로트루젼(protrusion) 또는 수지를 이용한 블랙매트릭스(resin BM) 등의 네가티브 포토레지스트를 그대로 존치시키면서 폴리이미드 배향막만을 선택적으로 박리시키는 것은 불가능하다. 따라서, 습식공정에 의한 재생공정을 거친 기판은 포스트 스페이서 등의 네가티브 포토레지스트를 다시 형성해야 하는 문제점이 있다.Third, as an organic solvent used in the wet process, a negative photoresist such as a post spacer, a protruding resin, or a black matrix using a resin, which is present in whole or in part under the alignment layer, is maintained as it is. It is impossible to selectively peel off only the polyimide alignment film while making it. Therefore, a substrate that has undergone a regeneration by a wet process has a problem in that a negative photoresist such as a post spacer must be formed again.
본 발명은 상기와 같은 문제점을 해결하기 위해 창안된 것으로서, 종래의 습식공정이 아닌 건식 플라즈마를 이용하여 LCD, TFT-LCD 등의 글래스 기판 위에 형성된 네가티브 포토레지스트 위에 도포된 폴리이미드 유기 배향막만을 선택적으로 제거하여 기판을 효율적으로 재생하는 방법을 제공하는데 그 목적이 있다.The present invention was devised to solve the above problems, and selectively uses only a polyimide organic alignment layer coated on a negative photoresist formed on a glass substrate such as an LCD or a TFT-LCD using a dry plasma rather than a conventional wet process. It is an object of the present invention to provide a method of efficiently regenerating a substrate by removing the substrate.
본 발명에 따르면, 폴리이미드 배향막은 2차 소성을 거친 후에도 용이하게 제거될 수 있을 뿐만 아니라 유기용매가 아닌 플라즈마를 이용한 건식방법으로 폴리이미드 배향막을 효율적으로 제거하는 동시에 그 아래에 존재하는 네가티브 포토레지스를 그대로 존치시킴으로서 기판 재생 효율을 높일 수 있다.According to the present invention, the polyimide alignment layer can be easily removed even after the secondary firing, and the negative photoresist existing thereunder while efficiently removing the polyimide alignment layer by a dry method using plasma instead of an organic solvent. The substrate regeneration efficiency can be improved by keeping the as is.
도 1은 본 발명에 따른 폴리이미드 배향막 제거 및 기판 재생을 위해 채용되는 플라즈마 장치의 일 예를 나타낸 것이다.1 shows an example of a plasma apparatus employed for removing a polyimide alignment layer and regenerating a substrate according to the present invention.
<도면의 주요참조부호의 설명><Description of main reference symbols in the drawings>
10..반응챔버 11..제1 전극 12..제2 전극10. Reaction chamber 11. First electrode 12. Second electrode
13..인출전극 14..절연부 15..전원13. Leading electrode 14. Insulation 15. Power supply
16..유입구 17..배출구 100..피처리체16. Inlet 17. Outlet 100. Target
상기와 같은 목적을 달성하기 위해 본 발명에 따른 기판의 재생방법은 전극에 인가되는 고주파전원에 의해 플라즈마를 발생하는 반응챔버를 구비하는 플라즈마 장치를 이용하여 글라스 기판 상에 형성된 네가티브 포토레지스트 위에 도포된 폴리이미드 유기 배향막을 선택적으로 제거하고 글라스 기판을 재생하는 방법으로서, 상기 폴리이미드 유기 배향막이 도포된 네가티브 포토레지스트 형성 글라스 기판을 상기 반응챔버 내에 투입하고 100 ∼ 900 mTorr로 압력을 유지시키는 단계;상기 반응챔버 내에 O2/N2혼합가스를 투입하면서 상기 압력을 유지시키는 단계; 및 상기 플라즈마 반응장치의 전극에 1 ∼ 20 kwatt의 전원을 인가하여 플라즈마를 발생시키므로서 선택적으로 상기 폴리이미드 유기 배향막을 분해하는 단계;를 포함한다. 반응챔버 내에 투입되는 O2/N2혼합가스의 혼합비율은 2:1 내지 1:2부피비인 것이 바람직하다.In order to achieve the above object, a method of regenerating a substrate according to the present invention is applied on a negative photoresist formed on a glass substrate using a plasma apparatus having a reaction chamber for generating a plasma by a high frequency power source applied to an electrode. A method of selectively removing a polyimide organic alignment layer and regenerating a glass substrate, comprising: introducing a negative photoresist forming glass substrate coated with the polyimide organic alignment layer into the reaction chamber and maintaining a pressure at 100 to 900 mTorr; Maintaining the pressure while introducing an O 2 / N 2 mixed gas into the reaction chamber; And selectively decomposing the polyimide organic alignment layer by generating a plasma by applying a power of 1 to 20 kwatts to the electrode of the plasma reactor. The mixing ratio of the O 2 / N 2 mixed gas introduced into the reaction chamber is preferably 2: 1 to 1: 2 by volume.
이하, 첨부된 도면을 참조로 본 발명의 바람직한 실시예를 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.
도 1에는 본 발명에 따른 플라즈마를 이용한 기판의 배향막 제거 및 기판 재생 방법을 적용하기 위한 플라즈마 장치가 도시되어 있다. 본 발명이 도시된 플라즈마 장치의 구성에 한정되는 것은 아니며 본 발명의 목적을 달성할 수 있는 범위내에서 다양하게 변형된 장치들이 채용될 수 있는 것으로 이해되어야 한다.1 shows a plasma apparatus for applying a method of removing an alignment layer and regenerating a substrate using a plasma according to the present invention. It is to be understood that the present invention is not limited to the configuration of the illustrated plasma device, and that various modifications can be made within the scope of achieving the object of the present invention.
본 실시예에 예시된 플라즈마 반응장치를 간략하게 살펴보면, 반응챔버(10)내에는 평행 평판 전극 중의 하나인 제1전극(11)이 설치되고, 이와 대향되는 상부에는 제2 전극(12)이 설치되며, 제1 전극(11) 위에는 피처리체(100)가 놓인다. 상기 피처리체(100)는, 예를 들어 TFT-LCD의 기판 제조 과정에서 불량으로 판정되어 재생되는 것으로서, 글래스 기판(101) 위에는 조립공정시에 대향하는 기판(미도시)과 간격을 유지하기 위한 복수개의 포스트 스페이서(post spacer), 광시야각 확보를 위한 MVA 모드의 프로트루젼(protrusion) 또는 수지를 이용한 블랙매트릭스(resin BM) 등의 네가티브 포토레지스트(103)가 형성되어 있다. 상기 네가티브 포토레지스트(103)는 통상적으로 적용되는 포토레지스터를 사용하여 포토리소그래피 공정으로 제조될 수 있다.Looking briefly at the plasma reactor illustrated in the present embodiment, the first electrode 11, which is one of the parallel plate electrodes, is installed in the reaction chamber 10, and the second electrode 12 is installed on the upper portion opposite thereto. The object to be processed 100 is placed on the first electrode 11. The object to be processed 100 is, for example, judged to be defective in the TFT-LCD substrate manufacturing process and is reproduced. The glass substrate 101 is disposed on the glass substrate 101 to maintain a distance from an opposing substrate (not shown) during the assembly process. A negative photoresist 103 such as a plurality of post spacers, MVA mode protrusion for securing a wide viewing angle, or a black matrix using a resin (resin BM) is formed. The negative photoresist 103 may be manufactured by a photolithography process using a conventionally applied photoresist.
상기 제1 전극(11)은 반응챔버(10) 외부로 연장된 인출전극(13)과 연결되어 있으며 이 인출전극(13)은 다시 전원(15)과 접속되어 플라즈마를 생성시키기 위한 고주파전원을 공급받는다. 상기 인출전극(13)은 절연부(14)에 의해 반응챔버(10)와 절연되어 있다.The first electrode 11 is connected to the drawing electrode 13 extending out of the reaction chamber 10, and the drawing electrode 13 is connected to the power supply 15 again to supply high frequency power for generating plasma. Receive. The lead electrode 13 is insulated from the reaction chamber 10 by the insulating portion 14.
또한, 상기 반응챔버(10) 내의 제1 전극(11)과 대향되는 측에는 제2 전극이 설치되어 후술하는 바와 같이 반응용기(10) 내의 반응가스를 여기시켜 플라즈마를 생성한다.In addition, a second electrode is provided on the side opposite to the first electrode 11 in the reaction chamber 10 to excite the reaction gas in the reaction vessel 10 to generate a plasma as described later.
상기 반응챔버(10)에는 플라즈마 생성을 위해 반응가스를 투입하기 위한 유입구(16)와 반응이 끝난 가스들을 배출시키기 위한 배출구(17)가 형성되어 있다.The reaction chamber 10 is formed with an inlet 16 for injecting a reaction gas for plasma generation and an outlet 17 for discharging the gasses.
그러면, 이상과 같은 장치를 사용하여 본 발명에 따른 기판의 배향막 제거 공정을 살펴보기로 한다.Then, the process of removing the alignment layer of the substrate according to the present invention using the above apparatus will be described.
먼저, 반응챔버(10) 내에 상기 피처리체(100)가 투입된다. 이때, 반응기 내의 압력은 100 mTorr ∼ 900mTorr 정도로 유지된다. 이어서, 상기 반응챔버(10) 내에는 가스 유입구(16)를 통해 반응가스가 유입되는데, 이때 가스로는 O2와 N2의 혼합 가스가 사용된다. 이때, 상기 가스 유입시에도 반응챔버(10) 내의 압력은 그대로 유지된다.First, the object 100 to be processed is introduced into the reaction chamber 10. At this time, the pressure in the reactor is maintained at about 100 mTorr ~ 900 mTorr. Subsequently, the reaction gas is introduced into the reaction chamber 10 through the gas inlet 16, wherein a mixed gas of O 2 and N 2 is used as the gas. At this time, the pressure in the reaction chamber 10 is maintained as it is even when the gas is introduced.
이어서, 전원(15)으로부터 상기 전극(11)에 1 ∼ 20 kwatt의 고주파전원을 인가하여 O2/N2플라즈마를 생성시킨다. 그러면, 상기 고반응성가스는 다음과 같이 해리, 여기 및 이온화된다.Subsequently, a high frequency power source of 1 to 20 kwatts is applied from the power supply 15 to the electrode 11 to generate an O 2 / N 2 plasma. The highly reactive gas is then dissociated, excited and ionized as follows.
O2+ e→O2 *+ e O2→O2 ++ eO 2 + e → O 2 * + e O 2 → O 2 + + e
O2→2O++ 2e 2O2 +→O-+ O3 O 2 → 2O + + 2e 2O 2 + → O - + O 3
O + e →O-O + 2e →O2 - O + e → O - O + 2e → O 2 -
N2→N + N N + e→N*+ eN 2 → N + NN + e → N * + e
N2+ e→N2 *+ e N2→N2 ++ eN 2 + e → N 2 * + e N 2 → N 2 + + e
N2→2N++ 2e N+ e →N- N 2 → 2N + + 2e N + e → N -
N + 2e →N2-N + 3e →N3- N + 2e → N 2- N + 3e → N 3-
이러한 반응 단계는 2차, 3차 반응이 혼재되어 나타나게 되며, 상기 O2 +, O-, O3, N-, N2-, N3-등은 다시 순간적으로 전자를 얻어 O*, O2 *, O3 *, N*, N2 *등과 같이 불안정하고 반응성이 높은 라디칼(Radical)들이 생성된다.This reaction step is displayed the second, third reaction mixture is, the O 2 +, O -, O 3, N -, N 2-, N 3- , etc. is obtained to again momentarily e * O, O 2 Unstable and highly reactive radicals such as * , O 3 * , N * , N 2 * are produced.
생성된 라디칼들은 피처리체(100)의 배향막(102)를 구성하는 폴리이미드의 분자결합을 파괴하여 질소, 산소, 탄소의 유기분자로 분해한다. 분해된 폴리이미드 유기분자들은 반응챔버 내에 존재하는 산소, 질소와 결합하여 CO, CO2, NO, NO2, H2O 등으로 되어 기체상으로 배출구(17)를 통해 배출되는데, 이때의 화학 반응식을 살펴보면 아래와 같다.The generated radicals break down molecular bonds of the polyimide constituting the alignment layer 102 of the object 100 to decompose into organic molecules of nitrogen, oxygen, and carbon. The decomposed polyimide organic molecules are combined with oxygen and nitrogen present in the reaction chamber to form CO, CO 2 , NO, NO 2 , H 2 O, etc., and are discharged through the outlet 17 in the gas phase. Looking at it as follows.
O-+ O+→O2 O - + O + → O 2
N-+ O2 +→NO2 N - + O 2 → NO 2 +
N-+ O+→NON - + O → NO +
본 발명에 따르면 이러한 반응은 기판 전체에 걸쳐 고르게 발생한다.According to the invention this reaction occurs evenly across the substrate.
한편, 상기 라디칼 이온들은 기판의 배향막(102) 아래에 부분적으로 또는 전체적으로 존재하는 포스트 스페이서(post spacer), 광시야각 확보를 위한 MVA 모드의 프로트루젼(protrusion) 또는 수지를 이용한 블랙매트릭스(resin BM) 등의 네가티브 포토레지스트(103)에 대하여 제한된 반응성을 갖는다. 즉, 네가티브 포토레지스트(103)는 바인더, 광가교제, 광개시제, 용제, 기타 첨가제를 포함하는 조성물로서, 포지티브 포토레지스트와는 달리 노광에 의해 가교, 광이량화 등의 반응으로 바인더의 분자량이 크게 증가하면서 열적 특성, 내화학성, 반응안정성 등이 현저하게 증가하므로 라디칼에 대한 분해가 잘 이루어지지 않으며, 특히 혼합된 N2가스는 이러한 네가티브 포토레지스트의 라디칼 이온에 대한 내분해성을 더욱 향상시켜 네가티브 포토레지스트를 존치시키게 한다. 형성된 네가티브 포토레지스트의 주성분인 바인더로는 폴리비닐알코올계, 폴리이소프렌계 고분자 외에 (메타)아크릴레이트계 고분자가 주로 사용되는데, 이 외에도 대한민국 공개특허공보 제1998-22330호 등에 개시된 바와 같은 다양한 종류의 고분자를 사용할 수 있으며, 본 발명의 목적에 따라 노광에 의해 가교 등의 반응으로 라디칼에 대한 내분해성이 향상되는 네가티브 포토레지스트라면 모두 사용이 가능하다. 폴리이미드 배향막에 대한 분해성과 네가티브 포토레지스트의 내분해성을 고려할 때, 가장 적절한 O2/N2혼합가스의 혼합비율은 2:1 내지 1:2부피비이다.Meanwhile, the radical ions may be partially or entirely present under the alignment layer 102 of the substrate, a black matrix using a resin or MVA mode protrusion or a resin for securing a wide viewing angle. Has a limited reactivity with respect to the negative photoresist 103, such as). That is, the negative photoresist 103 is a composition including a binder, a photocrosslinker, a photoinitiator, a solvent, and other additives, and unlike the positive photoresist, the molecular weight of the binder is greatly increased by a reaction such as crosslinking and photodimerization by exposure. While thermal properties, chemical resistance, and reaction stability are significantly increased, the decomposition of radicals is difficult to perform. Especially, the mixed N 2 gas further improves the decomposition resistance of radical negative ions of the negative photoresist to negative photoresist. Let them survive. The main component of the formed negative photoresist is a (meth) acrylate polymer is mainly used in addition to the polyvinyl alcohol-based and polyisoprene-based polymers. In addition, various kinds of binders as disclosed in Korean Patent Application Publication No. 1998-22330 A polymer may be used, and any negative photoresist having an improved decomposition resistance to radicals by reaction such as crosslinking by exposure may be used according to the object of the present invention. In consideration of the decomposability to the polyimide alignment film and the decomposability of the negative photoresist, the most suitable O 2 / N 2 mixed gas mixing ratio is 2: 1 to 1: 2 by volume.
이와 같이, 글래스 기판 위에 도포된 폴리이미드 배향막(102)은 O2/N2플라즈마 에칭에 의해 상기 배향막 아래에 부분적으로 또는 전체적으로 존재하는 네가티브 포토레지스트 물질을 존치시키면서 선택적으로 균일하게 제거될 수 있다. 본 발명의 효과는 다음 실험을 통해 더욱 명확하게 이해될 수 있을 것이다.As such, the polyimide alignment layer 102 applied over the glass substrate may be selectively and uniformly removed while maintaining the negative photoresist material partially or wholly present under the alignment layer by O 2 / N 2 plasma etching. The effect of the present invention will be more clearly understood through the following experiment.
[실험예]Experimental Example
사이즈 600×700×0.7mm3의 글래스 기판 위에 스핀코팅방식으로 색을 함유한 안료분산형 네가티브 포토레지스트(바인더로서 일본 Fuji Film Arch사의 벤질 메타크릴레이트/메타크릴산을 함유하는)로 이루어진 칼라필터층과 500Å 두께로 폴리이미드 배향막이 연속적으로 형성된 피처리체를 내용적 100리터(liter) 크기의 플라즈마 반응기 내에 투입하고 진공상태를 만든 후 O2/N2혼합가스(1:1)를 1,500sccm(Standard Cubic Centimeter per Minute; 0℃,1기압에서의 양)으로 투입하면서 전극에 2 kwatt의 전원을 인가하여 플라즈마를 생성시켜 40초 동안 반응시켰다.Color filter layer consisting of pigment-dispersion type negative photoresist (containing benzyl methacrylate / methacrylic acid from Fuji Film Arch, Japan) as a spin coating method on a glass substrate of size 600 × 700 × 0.7 mm 3 And a 500 μm thick polyimide alignment layer were continuously injected into a plasma reactor having a volume of 100 liters, and vacuum was formed. The mixed O 2 / N 2 gas (1: 1) was 1,500 sccm (Standard Cubic Centimeter per Minute (quantity at 0 ° C., 1 atm) was applied to the electrode with a power of 2 kwatt to generate a plasma and reacted for 40 seconds.
이어서, 반응이 끝난 후 반응기로부터 기판을 꺼내어 그 표면을 관찰하였다. 그 결과, 폴리이미드 배향막층은 모두 제거되었음을 확인하였고, 기판의 1024×765개의 셀(cell)에 대해 결함(defect)도 없는 것으로 나타났다. 또한, 기판의 배향막 아래에 형성된 칼라필터층의 색감도 변화를 측정한 결과 2% 미만인 것으로 관찰되어 거의 그대로 존치되고 있음을 확인하였다.Subsequently, after completion of the reaction, the substrate was taken out of the reactor and the surface thereof was observed. As a result, it was confirmed that all of the polyimide alignment layer was removed, and there were no defects for 1024 × 765 cells of the substrate. In addition, when the color sensitivity change of the color filter layer formed under the alignment film of the board | substrate was measured, it was observed that it was less than 2%, and it confirmed that it remained almost as it was.
본 발명에 따른 기판의 유기 배향막 제거 방법은 다음과 같은 이점을 가진다.The organic alignment film removing method of the substrate according to the present invention has the following advantages.
첫째, 본 발명은 플라즈마 반응기 내에서 건식공정으로 폴리이미드 유기 배향막을 제거하므로 대형 설비가 필요없고 운전비용이 저렴할 뿐만 아니라 유지와 운용이 종래의 습식공정에 비해 쉽고 용이하다.First, since the present invention removes the polyimide organic alignment layer by a dry process in the plasma reactor, it does not need a large sized equipment and the operation cost is low, and the maintenance and operation is easier and easier than the conventional wet process.
둘째, 종래의 습식공정에서는 폴리이미드 배향막을 2차 소성한 후에는 그 제거가 어려웠으나 본 발명에 따르면 2차 소성 후에도 폴리이미드 막의 완전한 제거가 가능하다. 이것은 종래 배향막의 제거가 어려워 폐기되던 기판을 보다 효과적으로 재생할 수 있음을 의미한다.Second, in the conventional wet process, it is difficult to remove the polyimide alignment layer after secondary firing, but according to the present invention, the polyimide membrane can be completely removed even after secondary firing. This means that it is difficult to remove the conventional alignment film, so that the discarded substrate can be reproduced more effectively.
셋째, 본 발명은 플라즈마 건식공정으로 폴리이미드 배향막을 제거하므로 종래의 습식공정에서 사용하던 다량의 유기용매를 사용할 필요가 없어 환경오염 등의 문제를 방지할 수 있다.Third, since the polyimide alignment layer is removed by a plasma dry process, there is no need to use a large amount of organic solvents used in the conventional wet process, thereby preventing problems such as environmental pollution.
넷째, 본 발명에 따라 분해된 폴리이미드 유기 배향막의 성분은 기상으로 제거하므로 재생된 기판을 중성용액으로 세정하고 이를 건조시키는 등의 부가공정이 필요치 않게 된다.Fourth, since the components of the polyimide organic alignment film decomposed according to the present invention are removed in a gaseous phase, an additional step such as washing the regenerated substrate with a neutral solution and drying it is unnecessary.
다섯째, 종래의 습식공정에 있어서는 유기용매로 인하여 박리현상이 일어나는 기판의 모서리 부분과 중심부에서의 배향막 제거 정도에 차이가 있어 재생이 불균일할 뿐만 아니라 재생불량율이 비교적 높았으나 본 발명의 경우에는 플라즈마를 이용한 화학반응으로 배향막을 전체적으로 일시에 제거하므로 제거 정도의 차이가 발생하지 않고 그로 인한 불량율 또한 현저히 줄일 수 있다.Fifth, in the conventional wet process, there is a difference in the degree of removal of the alignment film at the corners and the center of the substrate where the peeling phenomenon occurs due to the organic solvent, so that the regeneration is not uniform and the regeneration failure rate is relatively high. By removing the alignment layer as a whole by the chemical reaction used, there is no difference in the degree of removal and the defect rate can be significantly reduced.
여섯째, 종래의 습식공정은 용해성이 강한 유기용매를 다량으로 사용함으로인하여 폴리이미드 배향막 뿐만 아니라 그 아래에 부분적으로 또는 전체적으로 존재하는스페이서와 같은 네가티브 포토레지스트 물질까지 모두 제거하였으나, 본 발명에서는 O2/N2혼합가스를 사용하여 네가티브 포토레지스트와의 반응성을 제한함으로써, 배향막을 선택적으로 제거하는 것이 가능하다. 이로 인해, 기판 재생 효율을 향상시키고 후속적인 제조 공정을 단축시킬 수 있다.Sixth, the conventional wet process removes not only the polyimide alignment layer but also negative photoresist materials such as a spacer partially or wholly present by using a large amount of highly soluble organic solvent, but in the present invention, O 2 / By limiting the reactivity with the negative photoresist using the N 2 mixed gas, it is possible to selectively remove the alignment film. This can improve substrate regeneration efficiency and shorten subsequent manufacturing processes.
Claims (2)
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020030010183A KR20040074428A (en) | 2003-02-18 | 2003-02-18 | a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma |
PCT/KR2003/001138 WO2004074915A1 (en) | 2003-02-18 | 2003-06-10 | Method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using plasma |
CNA038259869A CN1742226A (en) | 2003-02-18 | 2003-06-10 | Method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using plasma |
AU2003237047A AU2003237047A1 (en) | 2003-02-18 | 2003-06-10 | Method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using plasma |
JP2004568522A JP2006514328A (en) | 2003-02-18 | 2003-06-10 | Method for selectively removing a polyimide organic alignment film applied on a glass substrate on which a negative photoresist is formed using plasma and regenerating the glass substrate |
TW092116784A TW200416458A (en) | 2003-02-18 | 2003-06-20 | Method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using plasma |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020030010183A KR20040074428A (en) | 2003-02-18 | 2003-02-18 | a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma |
Publications (1)
Publication Number | Publication Date |
---|---|
KR20040074428A true KR20040074428A (en) | 2004-08-25 |
Family
ID=36093984
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020030010183A KR20040074428A (en) | 2003-02-18 | 2003-02-18 | a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP2006514328A (en) |
KR (1) | KR20040074428A (en) |
CN (1) | CN1742226A (en) |
AU (1) | AU2003237047A1 (en) |
TW (1) | TW200416458A (en) |
WO (1) | WO2004074915A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102092205B (en) * | 2010-12-16 | 2013-05-01 | 贺术春 | Method for manufacturing LCD (liquid crystal display) sample |
WO2012083542A1 (en) * | 2010-12-23 | 2012-06-28 | 深圳市华星光电技术有限公司 | Device for repairing alignment layer and method for repairing alignment layer |
CN105524627B (en) * | 2015-12-03 | 2017-12-01 | 阜阳欣奕华材料科技有限公司 | A kind of purification process and purification devices of liquid crystal aligning liquid waste liquid |
CN105629587A (en) | 2016-03-25 | 2016-06-01 | 京东方科技集团股份有限公司 | Display panel, preparing method of display panel and display device |
RU2643172C2 (en) * | 2016-05-11 | 2018-01-31 | федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет" (ФГБОУ ВО "ВГУ") | Method for removing photoresist films from surface of optical glasses |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4492764B2 (en) * | 1999-05-24 | 2010-06-30 | 日本ゼオン株式会社 | Plasma reaction gas and method for producing the same |
KR100407725B1 (en) * | 2001-03-14 | 2003-12-01 | 주식회사 엘리아테크 | Plasma treatment system |
-
2003
- 2003-02-18 KR KR1020030010183A patent/KR20040074428A/en not_active IP Right Cessation
- 2003-06-10 WO PCT/KR2003/001138 patent/WO2004074915A1/en active Application Filing
- 2003-06-10 CN CNA038259869A patent/CN1742226A/en active Pending
- 2003-06-10 AU AU2003237047A patent/AU2003237047A1/en not_active Abandoned
- 2003-06-10 JP JP2004568522A patent/JP2006514328A/en active Pending
- 2003-06-20 TW TW092116784A patent/TW200416458A/en unknown
Also Published As
Publication number | Publication date |
---|---|
TW200416458A (en) | 2004-09-01 |
WO2004074915A1 (en) | 2004-09-02 |
JP2006514328A (en) | 2006-04-27 |
AU2003237047A1 (en) | 2004-09-09 |
CN1742226A (en) | 2006-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3011385B1 (en) | Liquid crystal display device and method of manufacturing the same | |
CN103091903B (en) | Preparation method, liquid crystal display (LCD) substrate and device for photolysis-type alignment film | |
KR100518105B1 (en) | Thin film coater, coating method, and method for manufacturing liquid crystal display element | |
KR20100070087A (en) | Composition for photoresist stripper and method of fabricating thin film transistor array substrate | |
CN1637614A (en) | Method and apparatus for fabricating flat panel display | |
CN102260437A (en) | Ink for black matrix and method of manufacturing substrate using the same | |
KR20040074428A (en) | a method for selectively removing polyimide alignment layer coated on negative photoresist formed on a substrate and recycling the same using a plasma | |
KR101030533B1 (en) | method for manufacturing of liquid crystal display device | |
JP2008004911A (en) | Apparatus and method of fabricating thin film pattern | |
CN1846173B (en) | Liquid photoresist remover composition, process for producing pattern with the same, and display employing the same | |
JP2005506562A (en) | Method of removing organic alignment film applied on substrate using plasma and regenerating it | |
KR20030046809A (en) | manufacturing method of a liquid crystal display device | |
EP1040876A4 (en) | Process for the production of monomolecular chemisorption film, and processes for the production of liquid crystal alignment films and liquid crystal displays by using the chemisorption film | |
US20030058518A1 (en) | Electrode plate for color display unit and production method therefor | |
US6929967B2 (en) | Method of forming pattern | |
US20030038914A1 (en) | Fabricating method of a liquid crystal display device | |
CN102445838A (en) | Method for reforming photo-resist pattern | |
CN107134434A (en) | A kind of method, array base palte and display panel for improving array base palte mask charge stripping efficiency | |
KR101010486B1 (en) | An alignment strip device and the stripping method | |
TWI285769B (en) | Regeneration method of liquid crystal display device | |
JPS58139123A (en) | Removing method of unnecessary part of film for orientation of liquid crystal | |
KR101252084B1 (en) | Method for manufacturing LCD | |
KR19980086559A (en) | Contact hole formation method of active matrix substrate | |
KR100840678B1 (en) | Apparatus for removing of photoresist and method for removing photoresist the using | |
JP2001246243A (en) | Method for modifying surface of base material and method for producing organic thin film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
AMND | Amendment | ||
E601 | Decision to refuse application | ||
AMND | Amendment | ||
J201 | Request for trial against refusal decision | ||
E801 | Decision on dismissal of amendment | ||
B601 | Maintenance of original decision after re-examination before a trial | ||
J301 | Trial decision |
Free format text: TRIAL DECISION FOR APPEAL AGAINST DECISION TO DECLINE REFUSAL REQUESTED 20051125 Effective date: 20061020 |
|
S901 | Examination by remand of revocation | ||
E902 | Notification of reason for refusal | ||
S601 | Decision to reject again after remand of revocation | ||
J201 | Request for trial against refusal decision | ||
J301 | Trial decision |
Free format text: TRIAL DECISION FOR APPEAL AGAINST DECISION TO DECLINE REFUSAL REQUESTED 20070611 Effective date: 20080508 |