KR20010078862A - In-situ heat treatment system and methode for oxide deposition on plastic films - Google Patents
In-situ heat treatment system and methode for oxide deposition on plastic films Download PDFInfo
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Abstract
Description
본 발명은 터치 판넬 및 기타 디스플레이용 투명 전극으로 사용하는 ITO/플라스틱 필름 즉, 플라스틱 필름 기판 위에 투명한 전극인 ITO(인듐-주석 산화물) 박막을 수백 나노미터(nm) 두께로 얇게 제작하는 경우, 경시변화 및 열에 대한 안정성을 높이고, 기계적 특성 향상을 위해 진공 챔버에서 ITO 박막 또는 그 외의 산화물 박막을 제작하는 공정에서 증착 전에 AlxOy또는 TiNx등의 barrier 층을 성막하고, 연속으로 열처리하는 기술에 관한 것이다.In the present invention, when ITO / plastic film, which is used as a transparent electrode for a touch panel and other displays, that is, an ITO (indium tin oxide) thin film, which is a transparent electrode, is thinly formed to a thickness of several hundred nanometers (nm) on a plastic film substrate, In the process of manufacturing ITO thin film or other oxide thin film in the vacuum chamber to improve the stability against change and heat and improve the mechanical properties, a barrier layer such as Al x O y or TiN x is deposited before the deposition and continuously heat treated. It is about.
도 1은 기판으로 사용하는 PET 필름에 투명전극을 형성한 기본 구조를 나타낸다. Hard 코팅된 PET 필름 위에 ITO 증착를 스퍼터링 방식으로 수백 나노미터(nm) 정도의 두께로 증착한다. ITO를 증착하기 전에 하드 코팅층(1)이 형성된 PET 필름(2)의 반대 면에 산화물 증착 장치(17)의 고주파 전원으로 무기 모노머 또는 산화물 , 질화물 타겟을 사용하여 AlxOy또는 TiNx(3)로 증착하고, 그 위에 ITO박막(4)을 형성한다. ITO 박막 제작 공정은 우선 연속으로 권취된 롤(roll) 형태의 플라스틱 필름이 진공 용기에 장입되고, 수 mtorr의 압력에서 연속으로 필름을 권취하면서 ITO 박막을 증착한다.1 illustrates a basic structure in which a transparent electrode is formed on a PET film used as a substrate. ITO deposition on a hard coated PET film is deposited to a thickness of several hundred nanometers (nm) by sputtering. Before the deposition of ITO, Al x O y or TiN x (3) using an inorganic monomer or an oxide or nitride target using a high frequency power source of the oxide deposition apparatus 17 on the opposite side of the PET film 2 on which the hard coating layer 1 is formed. Evaporation), and the ITO thin film 4 is formed thereon. In the ITO thin film fabrication process, a rolled plastic film in a continuous form is first loaded into a vacuum container, and the ITO thin film is deposited while continuously winding the film at a pressure of several mtorr.
그런데 PET(polyethylene terephtalate) 필름과 같은 플라스틱 필름의 유리천이 온도가 80℃ 정도이고, 최고 사용 온도가 160℃ 정도로 낮기 때문에 투명 전극의 제작 공정 중에 받는 열 사이클 등에 의해 시간이 지남에 따라 증착된 ITO 박막의 전기적, 기계적 특성이 변하기 쉬운 단점이 있다.However, since the glass transition temperature of a plastic film such as a PET (polyethylene terephtalate) film is about 80 ° C. and the maximum operating temperature is about 160 ° C., the ITO thin film deposited over time due to thermal cycles received during the manufacturing process of the transparent electrode. Its electrical and mechanical properties are prone to change.
그러므로 열 사이클의 영향 때문에 종래 기술은 플라스틱 기판 위에 균일한 산화막을 입히기 위해 스퍼터링 방법을 사용하였으며, 내열성이 좋지 않아 별다른열처리 없이 제작하였다. 하지만 기존의 열처리 과정이 없이 제작한 박막은 결정성이 떨어지며 비저항이 크고 저항 변화율이 큰 단점이 있다.Therefore, due to the influence of the thermal cycle, the prior art used the sputtering method to coat a uniform oxide film on the plastic substrate, and the heat resistance was not good, so it was manufactured without any heat treatment. However, the thin film manufactured without the conventional heat treatment has a disadvantage of low crystallinity, large resistivity and large resistivity change rate.
따라서 본 발명에서는 내열 온도가 낮은 필름 뿐 만 아니라 200℃ 이상의 내열 필름을 사용한 ITO 박막 제작 공정도 적용할 수 있는 산화물 증착 플라스틱 필름의 연속 열처리 방법과 그 시스템을 제공하기 위한 것이다.Accordingly, the present invention is to provide a continuous heat treatment method and system of the oxide-deposited plastic film that can be applied not only to a film having a low heat temperature but also to an ITO thin film manufacturing process using a heat resistant film of 200 ° C. or more.
본 발명은 플라스틱 기판 위에 제작한 ITO 박막을 증착 중에서 연속으로 열처리를 해줌으로써 비저항을 낮추고 투과도를 종래의 필름보다 높이려고 한다. 제작시 열처리를 해주기 때문에 제작이 끝난 뒤에 열처리를 해줄 필요가 없고 경시변화 및 열에 대한 안정성이 높아지고, ITO박막의 기계적 특성을 향상시켜 준다.The present invention attempts to lower the specific resistance and increase the transmittance of the conventional film by heat-treating the ITO thin film prepared on the plastic substrate continuously during deposition. Because the heat treatment during manufacturing, there is no need to heat treatment after the production is finished, the stability over time and heat increases, and improves the mechanical properties of the ITO thin film.
또한 하드 코팅된 플라스틱 필름의 경우 진공 반응기에 장입하여 진공을 뽑을 때 다량의 가스가 서서히 방출되고 필름 내부에 잔류해 있던 가스는 진공 펌프의 용량을 큰 것으로 하여도 증착 도중에 계속해서 서서히 방출되는 특성을 가지고 있기 때문에 본 발명에서는 적외선 히터(IR heater)를 사용해서 증착 전에 플라스틱 필름의 내부에 있던 잔류 가스의 방출 속도를 높이고, 증착 후에는 증착된 ITO 박막의 내부응력 제거 및 비저항 향상을 위해 적외선 히터를 사용해서 열처리를 한다.In addition, in the case of hard-coated plastic film, a large amount of gas is gradually released when it is charged into a vacuum reactor and the vacuum is extracted, and the gas remaining in the film is gradually released during deposition even at a large capacity of the vacuum pump. In the present invention, using an infrared heater (IR heater) to increase the release rate of the residual gas inside the plastic film before deposition, and after the infrared heater to remove the internal stress of the deposited ITO thin film and improve the specific resistance Heat treatment.
도 1은 기판으로 사용하는 PET 필름에 기본 구조를 나타낸 단면도.1 is a cross-sectional view showing a basic structure in a PET film used as a substrate.
도 2는 본 발명에 의한 플라스틱 필름이 장입되어 박막을 증착하기 위한 진공 반응기 개념도.Figure 2 is a vacuum reactor conceptual diagram for depositing a thin film is loaded with a plastic film according to the present invention.
<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>
10 : 플라스틱 필름 20 : 반응기10 plastic film 20 reactor
11 ; 공급릴(Unwinder) 12 ; 권취릴(Rewinder)11; Unwinder 12; Rewinder
13 ; 냉각드럼 14 ; 플라스마 처리13; Cooling drum 14; Plasma treatment
15 ; 제1가열수단(IR heater) 16 ; 제2가열수단(IR heater)15; First heating means (IR heater) 16; Second heating means (IR heater)
17 ; 산화물 증착장치(PECVD or Sputter)17; Oxide Deposition Equipment (PECVD or Sputter)
이하 본 발명의 실시예를 첨부된 도면을 참조해서 상세히 설명하면 다음과 같다.Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
도 2는 본 발명에 의한 산화물 증착 플라스틱 필름의 연속 열처리 방법을 설명하기 위한 진공 반응기의 개념도이다. 이에 도시된 바와 같이, 플라스틱 필름(10)이 감겨있어 그 플라스틱 필름을 연속적으로 공급하기 위한 공급릴(11)과, ITO박막 증착 후 플라스틱 필름(10)을 감기 위한 권취릴(12)과, 그 공급 릴(11)과 권취릴(12) 사이에서 플라스틸 필름(10)을 안내하면서 플라스틱 필름을 냉각시키기 위한 냉각드럼(13)과, 상기 공급릴(11)과 냉각드럼(13) 사이에서 상기 공급릴(11)에서 공급되는 플라스틱 필름(10)의 표면 개질을 위한 플라즈마 처리를 하는 플라즈마 처리기(14)와, 그 플라즈마 처리기(14)를 통과한 플라스틱 필름(10)을 소정의 온도로 가열하여 필름 내부에 잔류된 가스 방출을 활성화시키기 위한 제1가열수단(15)과, 상기 냉각 릴(13)과 권취릴(12) 사이에서 플라스틱 필름(10)에 증착된 ITO박막의 계면 안정성을 높이도록 열처리하기 위한 제2가열수단(16)과, 상기 각 장치들이 내부에 설치되고 산화막형성 및 ITO막 형성을 위한 분위기를 조성하여 반응성 스퍼터링 방법등을 이용하여 산화막과 ITO막을 플라스틱 필름의 표면에 증착시키고 진공펌프를 이용하여 배기시킬 수 있도록 이루어진 반응기(20)로 이루어진다. 여기서 제1, 제2가열수단(15)(16)은 적외선 히터를 사용한다.2 is a conceptual diagram of a vacuum reactor for explaining a continuous heat treatment method of an oxide deposited plastic film according to the present invention. As shown therein, the plastic film 10 is wound, and a supply reel 11 for continuously supplying the plastic film, a winding reel 12 for winding the plastic film 10 after ITO thin film deposition, and A cooling drum 13 for cooling the plastic film while guiding the plastic film 10 between the supply reel 11 and the winding reel 12, and between the supply reel 11 and the cooling drum 13; Plasma processor 14 for plasma treatment for surface modification of the plastic film 10 supplied from the supply reel 11 and the plastic film 10 passed through the plasma processor 14 to a predetermined temperature In order to increase the interfacial stability of the ITO thin film deposited on the plastic film 10 between the first heating means 15 and the cooling reel 13 and the winding reel 12 for activating the gas discharge remaining in the film. Second heating means 16 for heat treatment, and each device The reactor 20 is installed inside the reactor 20 to form an atmosphere for oxide film formation and ITO film formation, and to deposit the oxide film and ITO film on the surface of the plastic film by using a reactive sputtering method, etc., and evacuate using a vacuum pump. Is done. Here, the first and second heating means 15 and 16 use an infrared heater.
상기와 같은 반응기 시스템을 이용한 본 발명에 의한 산화물 증착 플라스틱 필름의 연속 열처리 방법은, 플라즈마를 이용하여 플라스틱 필름의 표면을 개질할 수 있는 전처리 과정과; 플라스틱 필름을 소정 온도로 가열하여 필름 내부의 잔류가스를 배기시키기 위한 크로스 링킹 디그리(cross linking degree)를 증가시키는 가열과정과; 가열후 반응성 스퍼터링 방법을 이용하여 하드 코팅층이 형성된 플라스틱 필름의 반대 면에 극히 얇은 산화막을 박막으로 코팅하는 산화막 코팅과정과; 상기 플라스틱 필름의 표면 온도를 120℃로 유지하는 동시에 120℃ 정도로 가열된 Ar 가스와 산소를 일정량 주입시켜 플라스마 내의 ITO 성분과 산소와의 반응 속도를 증가시키면서 ITO막을 형성하는 ITO박막 형성 과정과; ITO박막 형성후 ITO 박막과 플라스틱 필름과의 내부 응력 제거 및 ITO 박막의 계면 안정성을 높이기 위하여 적외선 히터를 이용하여 열처리를 하는 열처리 과정으로 이루어진다.The continuous heat treatment method of the oxide-deposited plastic film according to the present invention using the reactor system as described above, the pre-treatment process that can modify the surface of the plastic film using a plasma; A heating step of heating the plastic film to a predetermined temperature to increase a cross linking degree for exhausting residual gas inside the film; An oxide film coating process of coating an extremely thin oxide film as a thin film on the opposite side of the plastic film on which the hard coating layer is formed by using a reactive sputtering method after heating; Forming an ITO film while maintaining a surface temperature of the plastic film at 120 ° C. and injecting a predetermined amount of Ar gas and oxygen heated to about 120 ° C. to increase the reaction rate between the ITO component and oxygen in the plasma; After the ITO thin film is formed, heat treatment is performed by using an infrared heater to remove internal stress between the ITO thin film and the plastic film and to improve interfacial stability of the ITO thin film.
여기서, 상기 박막 형성 과정은, ITO 성막시에 증착되는 필름 표면의 온도를 120℃로 유지하는 동시에 120℃ 정도로 가열된 Ar 가스와 산소를 일정량 주입시켜 플라스마 내의 ITO 성분과 산소와의 반응 속도를 증가시킨다.Here, the thin film formation process, while maintaining the temperature of the film surface to be deposited during ITO film formation at 120 ℃ while injecting a certain amount of Ar gas and oxygen heated to about 120 ℃ to increase the reaction rate of the ITO component and oxygen in the plasma Let's do it.
본 발명에서는 플라스틱 필름을 플라스마를 이용하여 전처리한다. 전처리 과정은 플라즈마 처리기(14)를 통하여 플라스틱 필름의 표면을 개질하는 과정으로서 이는 플라스틱 표면에 박막을 증착하기 위한 부착력 향상 및 강도를 향상시키는 전처리 과정이다. 공급릴(11)에서 공급되는 플라스틱 필름(10)을 전처리 하는 동시에, 적외선 히터인 제1가열수단(15)를 이용하여 80℃ 정도로 플라스틱 필름을 가열하여 크로스 링킹 디그리(cross linking degree)를 증가시킨다. 즉, 박막 증착 전에 플라스틱 필름의 내부에 있던 잔류 가스의 방출 속도를 높이도록 한다. 이때 배기펌프를 이용하여 반응기 내부의 진공도를 조절하므로 플라스틱 필름의 잔류 가스가 배기된다.In the present invention, the plastic film is pretreated using plasma. The pretreatment process is a process of modifying the surface of the plastic film through the plasma processor 14, which is a pretreatment process for improving adhesion and strength for depositing a thin film on the plastic surface. While pre-processing the plastic film 10 supplied from the supply reel 11, the plastic film is heated to about 80 ° C. using the first heating means 15, which is an infrared heater, to increase the cross linking degree. . That is, the release rate of the residual gas inside the plastic film before the thin film deposition is increased. At this time, since the degree of vacuum inside the reactor is controlled using an exhaust pump, the residual gas of the plastic film is exhausted.
이후에 반응성 스퍼터링 방법 또는 CVD(화학증착) 방법을 이용하여 극히 얇은 알루미늄 산화막(AlxOy)의 박막을 코팅한다. 굴절율이 1.7 정도로 기판과 유사하고, Al+3이온이 ITO의 캐리어로 작용하는 산소 정공의 이동도를 증가시켜 전극 특성을 향상한다. 그리고, 산화막 위에 ITO박막을 형성하는데, ITO 성막시에는 증착되는 필름 표면의 온도를 120℃로 유지하는 동시에 120℃ 정도로 가열된 Ar 가스와 산소를 일정량 주입시켜 플라스마 내의 ITO 성분과 산소와의 반응 속도를 증가시켰다.Thereafter, a thin film of an extremely thin aluminum oxide film (AlxOy) is coated by using a reactive sputtering method or a CVD (chemical vapor deposition) method. The refractive index is similar to that of the substrate at about 1.7, and Al + 3 ions increase the mobility of oxygen holes acting as carriers of ITO, thereby improving electrode characteristics. In addition, an ITO thin film is formed on the oxide film. During ITO film formation, the temperature of the surface of the film to be deposited is maintained at 120 ° C., and a predetermined amount of Ar gas and oxygen heated to about 120 ° C. is injected to react the reaction rate of ITO component and oxygen in the plasma. Increased.
마지막으로 냉각드럼(13)을 통과한 플라스틱 필름을 제2가열수단(16)인 적외선 히터(16)를 이용하여 소정온도로 가열하여 열처리 한다. 즉, ITO 증착 이후에는 ITO 박막과 플라스틱 필름과의 내부 응력 제거 및 ITO 박막의 계면 안정성을 높이기 위하여 적외선 히터(IR heater)를 이용해서 열처리를 한다.Finally, the plastic film passing through the cooling drum 13 is heated to a predetermined temperature using an infrared heater 16, which is the second heating means 16, to be heat treated. That is, after ITO deposition, heat treatment is performed using an IR heater to remove internal stress between the ITO thin film and the plastic film and to improve interfacial stability of the ITO thin film.
따라서, 본 발명은 플라스틱 필름에 박막 증착전과 증착후에 적외선 히터를 이용하여 낮은 온도(예; 80℃)로 가열하여 열처리하고, 박막 형성시 120℃ 정도의 온도에서 형성하므로, 내열성이 낮은 플라스틱 필름 뿐만 아니라 내열성이 높은 필름도 모두 동일한 공정으로 박막을 형성할 수 있게 된다. 또한, 플라스틱 필름을 가열하는 온도의 변화범위를 다르게 설정할 경우와 MF, RF, DC power의 변경시에도 적용한다. 본 발명은 PET 필름을 포함한 모든 플라스틱 기판에 적용이 가능하고, AlxOy외에 다른 물질을 증착할 경우에도 적용할 수 있다.Therefore, the present invention is heat-treated by heating to a low temperature (eg 80 ℃) using an infrared heater before and after the thin film deposition on the plastic film, and formed at a temperature of about 120 ℃ when forming a thin film, as well as a low heat resistance plastic film In addition, all the films having high heat resistance can form thin films in the same process. In addition, it applies to the case of setting the change range of the temperature for heating the plastic film differently and to the change of MF, RF, DC power. The present invention can be applied to all plastic substrates including PET film, and can be applied to depositing other materials besides Al x O y .
이상에서 설명한 바와 같이 본 발명에 의하면, 플라스틱 플름의 표면에 산화막 형성 및 ITO 박막을 형성하는 제작 공정에서 열처리를 해줌으로써 ITO박막의 내구성과 경도가 좋아진다. 또한 본 발명은 적외선 히터를 이용하여 박막 증착전 가열과 증착후 열처리를 낮은 온도로 처리하미르 내열 온도가 낮은 필름 뿐 만 아니라 200℃ 이상의 내열 필름을 사용한 ITO 박막 제작 공정도 적용할 수 있는 효과가 있으며, 터치 판넬과 핸드폰 액정등에 사용할 수 필름 제작에 이용할 수 있다.As described above, according to the present invention, the durability and hardness of the ITO thin film are improved by performing heat treatment in the production process of forming an oxide film and forming an ITO thin film on the surface of the plastic plume. In addition, the present invention has the effect that can be applied to the ITO thin film manufacturing process using a heat-resistant film of 200 ℃ or more, as well as a low heat resistance film to heat the thin film pre-heating and post-deposition heat treatment using an infrared heater at a low temperature. It can be used for film making, which can be used for touch panel and cell phone liquid crystal.
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