KR100464221B1 - Electric field emission material using carbon nano tubes and manufacturing method thereof - Google Patents
Electric field emission material using carbon nano tubes and manufacturing method thereof Download PDFInfo
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- KR100464221B1 KR100464221B1 KR10-2000-0072274A KR20000072274A KR100464221B1 KR 100464221 B1 KR100464221 B1 KR 100464221B1 KR 20000072274 A KR20000072274 A KR 20000072274A KR 100464221 B1 KR100464221 B1 KR 100464221B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/30—Cold cathodes, e.g. field-emissive cathode
- H01J1/304—Field-emissive cathodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
- H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
Abstract
본 발명은 평판형 표시장치에 사용되는 탄소나노튜브의 가늘고 뽀족한 구조와 전자전달이 용이한 특성을 이용한 전계방출소자에 관한 것으로서, 종래의 구조에 비해 탄소나노튜브와 하부기판 사이의 결합력을 증대시키고 전자전달이 용이하여 전계방출효과가 우수한 특성을 지닌 전계방출소자를 제공하는 것을 그 목적으로 한 것이다.The present invention relates to a field emission device using a thin and sharp structure of carbon nanotubes used in a flat panel display device and easy to transfer electrons, and to increase the bonding force between the carbon nanotubes and the lower substrate as compared to the conventional structure. It is an object of the present invention to provide a field emission device having excellent characteristics of excellent field emission effect due to easy electron transfer.
본 발명은 상기 목적을 달성하기 위해, 하부기판상에 미세 배열된 원형구멍 바닥에 금 박막을 형성시키고 상기 금 박막에 티올로 개질된 탄소나노튜브를 자기조립에 의해 직립상으로 결합하고, 상부기판 하부에는 ITO층과 패턴화된 형광체를 적층시키며, 상기 하부기판과 상부기판 사이에는 게이트와 스페이서를 배설하고 접합 밀봉한 구조의 탄소나노튜브를 이용한 전계방출소자를 개시한다.In order to achieve the above object, the present invention forms a gold thin film on the bottom of a circular hole finely arranged on a lower substrate, and combines carbon nanotubes modified with thiol on the gold thin film by self-assembly, and the upper substrate. Disclosed is a field emission device using carbon nanotubes having a structure in which an ITO layer and a patterned phosphor are stacked on the lower substrate, and a gate and a spacer are disposed between the lower substrate and the upper substrate and bonded and sealed.
Description
본 발명은 평판형 표시장치에 이용되는 전계방출소자에 관한 것으로서, 특히탄소나노튜브의 가늘고 뾰족한 구조와 전자 전달이 용이한 특성을 이용한 전계방출소자에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a field emission device for use in a flat panel display, and more particularly to a field emission device using a thin and pointed structure of carbon nanotubes and easy electron transfer.
도 3에는 한국공개특허 제 99-43770호에 나타나 있는 종래의 전계방출소자의 일 단면도를 예시하였는바, 이 전계 방출소자는 산화실리콘막(4)이 표면에 형성되어 있는 하부 실리콘 기판(2)에 미리 만들어진 마이크론 크기의 원형 구멍내에 원형구멍의 기하학적 구조와 원형 구멍의 바닥면과 표면의 실리콘산화막(4) 사이의 선택적인 결합력 차이에 의해 탄소나노튜브(3)가 채워져 있으며, 여기에 그리드 (10)와 패턴화된 형광체(7)가 장착된 구조로 되어 있는데, 이와 같은 구조로 된 전계방출소자는 탄소나노튜브와 실리콘 기판 사이의 결합력이 약해서 실제 사용시 나노튜브가 기판에서 쉽게 분리될 수 있고, 전자 전달에 있어서 저항이 크다는 단점을 지니고 있다.FIG. 3 illustrates a cross-sectional view of a conventional field emission device shown in Korean Patent Application Laid-Open No. 99-43770. The field emission device includes a lower silicon substrate 2 having a silicon oxide film 4 formed on its surface. The carbon nanotubes 3 are filled in the micron-sized circular holes in the pre-made micro-sized circular holes by the differential coupling force between the circular hole geometry and the bottom surface of the circular hole and the silicon oxide film 4 on the surface. 10) and the patterned phosphor (7) is mounted, the field emission device having such a structure has a weak bonding force between the carbon nanotubes and the silicon substrate can be easily separated from the substrate in actual use However, it has a disadvantage of high resistance in electron transfer.
또한 도 4에는 Science and application of nanotubes지 (Kluwer Academic, New Yock, 2000)와 Science지(V. 286 N. 5447, 1999)에 나와 있는 또 다른 종래의 전계방출소자를 이용한 전계방출디스플레이가 도시되어 있는데, 여기에서는 뾰족한 탄소나노튜브(3)를 표면에 형성시키기 위해 탄소나노튜브와 금속분말 및 유기물을 섞고 일정 용량 짜낸 후 소성하여 유기물을 제거함으로써 표면에 있는 탄소나노튜브(3)가 밖으로 솟아나와 있도록 하였다. 그러나, 이 경우에는 탄소나노튜브가 솟아나온 방향이 일정하지 않고 또 소성시 남아있는 유기물에서 미세가스가 방출되었 고 진공시 전계방출을 방해하여 나노튜브와 기판(2)사이의 물리적인 접촉으로 인해 전기적 저항이 발생하는 등의 단점을 지니고 있다.Figure 4 also shows a field emission display using another conventional field emission device shown in Science and application of nanotubes (Kluwer Academic, New Yock, 2000) and Science (V. 286 N. 5447, 1999). In this case, in order to form the pointed carbon nanotubes (3) on the surface, carbon nanotubes (3) on the surface of the carbon nanotubes, metal powder and organics are mixed and squeezed to a certain capacity, and then fired to remove the organics. It was made. In this case, however, the direction in which the carbon nanotubes bulge is not constant, and the fine gas is released from the organic materials remaining during firing, and the physical field between the nanotubes and the substrate 2 is prevented due to the interference of the field emission during the vacuum. It has disadvantages such as electrical resistance.
이와 같이 종래의 전계방출소자는 탄소나노튜브와 하부기판 사이의 연결이 단순히 물리적인 접착이나 전기적인 결합으로 인해 탄소나노튜브와 하부기판 결합의 불안정성, 전기적 저항 발생 등의 문제점을 지닌다.As described above, the conventional field emission device has a problem in that the connection between the carbon nanotubes and the lower substrate is simply caused by physical bonding or electrical coupling, instability of the carbon nanotubes and the lower substrate, and the generation of electrical resistance.
본 발명은 상기와 같은 종래의 문제점을 해결하기 위해 안출된 것으로서, 특히 탄소나노튜브와 하부기판 사이의 결합력을 증대시키고 전자전달을 용이하게 하여 전계방출 효과가 우수한 특성을 지닌 전계방출소자를 제공하는 것을 그 목적으로 한 것이다.The present invention has been made to solve the conventional problems as described above, in particular to increase the bonding force between the carbon nanotubes and the lower substrate and to facilitate the electron transfer to provide a field emission device having excellent characteristics of the field emission effect. It is for that purpose.
도 1은 본 발명에 따른 전계방출소자의 구조를 나타낸 일 예시도1 is an exemplary view showing a structure of a field emission device according to the present invention
도 2는 본 발명에 따른 전계방출소자내 개질된 탄소나노튜브의 금 박막과의 결합을 나타내는 개략도Figure 2 is a schematic diagram showing the binding of the modified carbon nanotubes to the gold thin film in the field emission device according to the present invention
도 3은 종래의 탄소나노튜브를 이용한 전계방출소자의 단면도3 is a cross-sectional view of a field emission device using a conventional carbon nanotube
도 4는 종래의 탄소나노튜브를 이용한 전계방출디스플레이의 단면도이다.4 is a cross-sectional view of a field emission display using a conventional carbon nanotube.
〈도면의 주요 부분에 대한 부호의 설명〉<Explanation of symbols for main parts of drawing>
1 : 박막 2 : 하부기판1: thin film 2: lower substrate
3 : 탄소나노튜브 4 : 산화실리콘막3: carbon nanotube 4: silicon oxide film
5 : 게이트 6 : 스페이서5: gate 6: spacer
7 : 패턴화된 형광체 8 : ITO층7: patterned phosphor 8: ITO layer
9 : 상부기판 10 :그리드9: upper substrate 10: grid
본 발명은 하부기판 상부에 미세 배열된 마이크론 크기의 원형구멍 바닥에 금(Au)을 증착시켜 금 박막을 형성시킨 후 말단이 티올로 개질된 탄소나노튜브를 원형 구멍 바닥의 상기 금 박막상에 자기조립시키는 방법으로 직립 결합시켜 채우고, 하부기판과 상부기판과의 사이에 게이트와 스페이서를 설치하고 상부기판에는 ITO층과 형광체를 적층시킨 구조의 전계방출소자에 관한 것으로서, 이하에서 첨부된 도면에 의거 본 발명을 구체적으로 설명한다.The present invention forms a gold thin film by depositing gold (Au) on the bottom of a micron-sized circular hole finely arranged on the upper side of the lower substrate, and magnetically modified carbon nanotubes on the gold thin film of the bottom of the circular hole. It relates to a field emission device having a structure in which the assembly is filled upright by the assembly method, the gate and the spacer between the lower substrate and the upper substrate, and the ITO layer and the phosphor laminated on the upper substrate, based on the accompanying drawings The present invention will be described in detail.
도 1은 본 발명에 따른 전계방출소자에 대한 일 예시도로써, 표면에 산화실리콘막(4)이 형성되어 있는 하부기판(2)상에는 미세 배열된 원형구멍 바닥에 대략 0.1∼1㎛ 두께의 금 박막(1)이 형성되어 있고 상기 금 박막상에 말단이 티올로 개질된 탄소나노튜브(3)가 자기 조립에 의해 직립상으로 결합되어 있으며, 상부기판(9) 하부에는 ITO(Indium Tin Oxide)층(8)과 패턴화된 형광체(7)가 차례로적층되어 있으며, 상기 하부기판(2)과 상부기판(9)사이에는 게이트(5)와 스페이서(spacer)(6)가 배설되어 있는 구조로 되어 있는 전계방출소자가 도시되어 있다.FIG. 1 is an exemplary view of a field emission device according to the present invention, wherein a gold oxide having a thickness of approximately 0.1 to 1 μm is formed on a bottom of a circular hole finely arranged on a lower substrate 2 having a silicon oxide film 4 formed on a surface thereof. A thin film 1 is formed, and carbon nanotubes 3 whose ends are modified with thiols on the gold thin film are bonded upright by self-assembly, and indium tin oxide (ITO) below the upper substrate 9 The layer 8 and the patterned phosphor 7 are sequentially stacked, and a gate 5 and a spacer 6 are disposed between the lower substrate 2 and the upper substrate 9. A field emission device is shown.
이때 탄소나노튜브는 길이 0.05∼1㎛, 지름 5∼200㎚ 범위의 단층 또는 다층의 나노튜브를 사용하며 탄소나노튜브(3)의 개질과 금 박막(1)상에의 결합은 다음과 같은 방법이 사용될 수 있다. 즉, 아크 방전으로 얻어진 탄소나노튜브를 황산과 질산의 혼합물 속에서 산화시키면서 초음파 진동을 통해 탄소나노튜브의 말단을 카르복실 그룹으로 치환하여 짧은 탄소나노튜브를 얻고 증류수로 세척한 다음 BH3-THF를 이용해 OH기로 환원시킨 후 SOCl2를 이용해 -Cl로 치환하고, 다시 KSH를 이용해 말단을 -SH기로 개질시킨 후, 이를 에탄올에 분산시킨 후 미세 구멍 바닥이 금 박막(1)으로 되어있는 하부기판(2)을 상기 용액속에서 1∼96시간동안 흔들어 주어 탄소나노튜브(3)들이 도2에 나타낸 형상과 같은 모양으로 자기조립(Self-assembly)되도록 하므로써 개질된 탄소나노튜브를 금 박막상에 직접 결합시키거나 또는 콘쥬게이트화 이중결합에 의해 연결시킨다. 이때 금 박막과 탄소나노튜브는 전자전달이 용이하도록 티오에테르 결합(-S-)으로 직접 연결됨으로써 결합이 용이하고 결합력도 강하다.In this case, the carbon nanotubes use single or multilayer nanotubes having a length of 0.05-1 μm and a diameter of 5-200 nm, and the modification of the carbon nanotubes (3) and the bonding on the gold thin film (1) are as follows. This can be used. That is, the carbon nanotubes obtained by the arc discharge are oxidized in a mixture of sulfuric acid and nitric acid, and the ends of the carbon nanotubes are replaced with carboxyl groups by ultrasonic vibration to obtain short carbon nanotubes, and washed with distilled water, followed by BH 3 -THF. After reducing to OH group using SOCl 2 to replace with -Cl, using KSH to modify the end of the -SH group, and then dispersed in ethanol, the bottom substrate with a fine hole bottom of the gold thin film (1) Shake (2) in the solution for 1 to 96 hours so that the carbon nanotubes (3) are self-assembly in the same shape as shown in FIG. Direct linking or linkage by conjugated double bonds. At this time, the gold thin film and the carbon nanotube are directly connected by a thioether bond (-S-) to facilitate electron transfer, thereby facilitating bonding and having a strong bonding force.
한편 상기 하부기판(2)과 상부기판(9)사이에는 게이트(5)와 스페이서(6)가 배설된 상태에서 접합밀봉되거나 또는 하부기판(2)에 설치되는 진공배기 유리관을 통해 방전개스를 주입한 후 접합밀봉된다.On the other hand, the discharge gas is injected between the lower substrate 2 and the upper substrate 9 through a vacuum-exhaust glass tube provided in the state in which the gate 5 and the spacer 6 are disposed or sealed or installed in the lower substrate 2. After that, the joint is sealed.
이와 같은 구조로 된 전계방출소자는 상기 상부기판과 하부기판의 전극에 전압을 인가하면 탄소나노튜브에서 방출된 전자가 형광체를 통과하면서 전계방출 효과를 일으키게 되는 것이다.In the field emission device having such a structure, when a voltage is applied to the electrodes of the upper substrate and the lower substrate, electrons emitted from the carbon nanotubes pass through the phosphor and cause a field emission effect.
상기와 같이 구성된 본 발명에 따른 전계방출소자는 탄소나노튜브를 하부기판상의 미세구멍속에 증착된 금 박막에 자기조립에 의해 수직적으로 화학결합하여 탄소나노튜브가 물리화학적으로 안정하고 전자 전달이 용이하며 길이가 일정한 탄소나노튜브를 배열할 수 있는 특성을 지니기 때문에 종래의 전계방출소자에 비해 우수한 전계방출효과를 나타낸다.The field emission device according to the present invention configured as described above is chemically bonded to the carbon nanotubes vertically by self-assembly to the gold thin film deposited in the micropores on the lower substrate, the carbon nanotubes are physicochemically stable and easy to transfer electrons. Since the carbon nanotubes can be arranged to have a constant length, they exhibit excellent field emission effects compared to conventional field emission devices.
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