• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.293.1-293.1
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• 2013

탄소나노튜브(carbon nanotubes; CNTs)는 우수한 물성으로 인하여 전자소자, 에너지 저장매체, 투명전도막, 복합재료 등 매우 다양한 분야에 응용이 가능할 것으로 예측되고 있으며, 더욱이 이러한 특성은 구조변형, 화학적 도핑뿐만 아니라 표면처리를 통해서 제어가 가능하다고 알려져 있다. 이를 위해 기존에는 열처리를 통하여 CNTs를 표면처리한 결과들이 보고되었으나, 고온에서 장시간의 공정이 요구되는 열처리 공정의 단점을 보완하기 위하여 플라즈마 처리를 통해 상온에서 단시간의 공정으로 CNTs를 표면처리하는 방법이 제시되었다. 특히 최근에는, 향후 산업적 응용을 목적으로 종래의 진공 환경에서 벗어나 대기압 연속공정 개발을 위한 대기압 플라즈마 기반의 표면처리 공정에 대하여 관심이 집중되고 있는 상황이다. 본 연구에서는 대기압에서 플라즈마를 안정적으로 방전 및 유지 할 수 있는 플라즈마 토치 시스템을 구축하였고, 이를 이용하여 수직배향 CNTs를 표면 처리함으로써 그 영향을 살펴보았다. CNTs는 $SiO_2$ 웨이퍼 위에 증착한 철 촉매를 이용하여 $750^{\circ}C$에서 수직배향 합성하였으며, 원료가스로는 아세틸렌을 사용하였다. 대기압 플라즈마 장치의 경우 고전압 교류 전원장치를 이용하여 토치타입으로 제작하였다. 플라즈마는 아르곤과 질소가스를 시용하여 방전하고, 기판과의 거리 및 처리시간을 변수로 CNTs를 표면처리하였다. 플라즈마 처리 전후 접촉각 측정을 통하여 소수성이었던 CNTs 표면이 친수성으로 변화하는 것을 확인하였다. 또한 Raman 분석을 통하여 대기압 플라즈마의 처리조건에 따른 CNTs 의 구조적 결함 발생 정도를 정량화 시킬 수 있었다. 이를 통하여 대기압 플라즈마를 이용할 경우, CNTs의 구조적 손상을 최소화 하면서 효율적으로 표면특성을 변화시킬 수 있는 처리조건을 도출하였다.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.159-159
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• 2016

Vertically-aligned carbon nanotubes (VCNT) have attracted much attention due to their unique structural, mechanical and electronic properties, and possess many advantages for a wide range of multifunctional applications such as field emission displays, heat dissipation and potential energy conversion devices. Surface modification of the VCNT plays a fundamental role to meet specific demands for the applications and control their surface property. Recent studies have been focused on the improvement of the electron emission property and the structural modification of CNTs to enable the mass fabrication, since the VCNT considered as an ideal candidate for various field emission applications such as lamps and flat panel display devices, X-ray tubes, vacuum gauges, and microwave amplifiers. Here, we investigate the effect of surface morphology of the VCNT by water vapor exposure and coating materials on field emission property. VCNT with various height were prepared by thermal chemical vapor deposition: short-length around $200{\mu}m$, medium-length around $500{\mu}m$, and long-length around 1 mm. The surface morphology is modified by water vapor exposure by adjusting exposure time and temperature with ranges from 2 to 10 min and from 60 to 120oC, respectively. Thin films of SiO2 and W are coated on the structure-modified VCNT to confirm the effect of coated materials on field emission properties. As a result, the surface morphology of VCNT dramatically changes with increasing temperature and exposure time. Especially, the shorter VCNT change their surface morphology most rapidly. The difference of field emission property depending on the coating materials is discussed from the point of work function and field concentration factor based on Fowler-Nordheim tunneling.

• 한국정보디스플레이학회:학술대회논문집
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• 2002.08a
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• pp.678-680
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• 2002

Vertically aligned carbon nanotubes(CNTs) have been grown on Ni-coated TiN/Si substrate by microwave plasma chemical vapor deposition using $H_2/CH_4$ mixture gas. We have investigated the Effect of process parameters on the growth of CNT. During the growth, microwave power, pressure, and growth temperature were varied from 300 W to 700 W, 10 Torr to 30 Torr, and 300 $^{\circ}C$ to 700 $^{\circ}C$. respectively. Then we controlled the size of CNTs. The structure of CNT was sensitively dependent on the process parameters.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.11a
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• pp.26-26
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• 2009

Vertically aligned arrays of mm-long multi-walled carbon nanotubes (MWCNTs) on Si substrates have been synthesized by water-assisted thermal chemical vapor deposition (CVD). The growth of CNTs was investigated by changing the experimental parameters such as growth temperature, growth time, gas composition, annealing time, catalyst thickness, and Al underlayer thickness. The 0.5-nm-thick Fe served as catalyst, underneath which Al was coated as a catalyst support as well as a diffusion barrier on the Si substrate. We grew CNTs by adding a little amount of water vapor to enhance the activity and the lifetime of the catalyst. Al was very good at producing the nm-size catalyst particles by preventing "Ostwald ripening". The Al underlayer was varied over the range of 15~40 nm in thickness. The optimum conditions for the synthesis parameters were as follows: pressure of 95 torr, growth temperature of $815^{\circ}C$, growth for 30 min, 60 sccm Ar + 60 sccm $H_2$ + 20 sccm $C_2H_2$. The water vapor also had a great effect on the growth of CNTs. CNTs grew 5.03 mm long for 30 min with the water vapor added while CNTs were 1.73 mm long without water vapor at the same condition. As-grown CNTs were characterized by using scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. High-resolution transmission electron microscopy showed that the as-grown CNTs were of ~3 graphitic walls and ~6.6 nm in diameter.

• Electrical & Electronic Materials
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• v.12 no.7
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• pp.7-11
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• 1999

Fully sealed field emission display in size of 4.5 inch has been fabricated using single-wall carbon nanotubes-organic vehicle com-posite. The fabricated display were fully scalable at low temperature below 415$^{\circ}C$ and CNTs were vertically aligned using paste squeeze and surface rubbing techniques. The turn-on fields of 1V/${\mu}{\textrm}{m}$ and field emis-sion current of 1.5mA at 3V/${\mu}{\textrm}{m}$ (J=90${\mu}{\textrm}{m}$/$\textrm{cm}^2$)were observed. Brightness of 1800cd/$m^2$ at 3.7V/${\mu}{\textrm}{m}$ was observed on the entire area of 4.5-inch panel from the green phosphor-ITO glass. The fluctuation of the current was found to be about 7% over a 4.5-inch cath-ode area. This reliable result enables us to produce large area full-color flat panel dis-play in the near future. Carbon nanotubes (CNTs) have attracted much attention because of their unique elec-trical properties and their potential applica-tions [1, 2]. Large aspect ratio of CNTs together with high chemical stability. ther-mal conductivity, and high mechanical strength are advantageous for applications to the field emitter [3]. Several results have been reported on the field emissions from multi-walled nanotubes (MWNTs) and single-walled nanotubes (SWNTs) grown from arc discharge [4, 5]. De Heer et al. have reported the field emission from nan-otubes aligned by the suspension-filtering method. This approach is too difficult to be fully adopted in integration process. Recently, there have been efforts to make applications to field emission devices using nanotubes. Saito et al. demonstrated a car-bon nanotube-based lamp, which was oper-ated at high voltage (10KV) [8]. Aproto-type diode structure was tested by the size of 100mm $\times$ 10mm in vacuum chamber [9]. the difficulties arise from the arrangement of vertically aligned nanotubes after the growth. Recently vertically aligned carbon nanotubes have been synthesized using plasma-enhanced chemical vapor deposition(CVD) [6, 7]. Yet, control of a large area synthesis is still not easily accessible with such approaches. Here we report integra-tion processes of fully sealed 4.5-inch CNT-field emission displays (FEDs). Low turn-on voltage with high brightness, and stabili-ty clearly demonstrate the potential applica-bility of carbon nanotubes to full color dis-plays in near future. For flat panel display in a large area, car-bon nanotubes-based field emitters were fabricated by using nanotubes-organic vehi-cles. The purified SWNTs, which were syn-thesized by dc arc discharge, were dispersed in iso propyl alcohol, and then mixed with on organic binder. The paste of well-dis-persed carbon nanotubes was squeezed onto the metal-patterned sodalime glass throuhg the metal mesh of 20${\mu}{\textrm}{m}$ in size and subse-quently heat-treated in order to remove the organic binder. The insulating spacers in thickness of 200${\mu}{\textrm}{m}$ are inserted between the lower and upper glasses. The Y\ulcornerO\ulcornerS:Eu, ZnS:Cu, Al, and ZnS:Ag, Cl, phosphors are electrically deposited on the upper glass for red, green, and blue colors, respectively. The typical sizes of each phosphor are 2~3 micron. The assembled structure was sealed in an atmosphere of highly purified Ar gas by means of a glass frit. The display plate was evacuated down to the pressure level of 1$\times$10\ulcorner Torr. Three non-evaporable getters of Ti-Zr-V-Fe were activated during the final heat-exhausting procedure. Finally, the active area of 4.5-inch panel with fully sealed carbon nanotubes was pro-duced. Emission currents were character-ized by the DC-mode and pulse-modulating mode at the voltage up to 800 volts. The brightness of field emission was measured by the Luminance calorimeter (BM-7, Topcon).

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2004.04b
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• pp.60-63
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• 2004

Recently, carbon nanotubes(CNTs) have been demonstrated to possess remarkable mechanical and electronic properties, in particular, for field emission applications. Its high aspect ratio and extremely small diameter, hollowness, together with high mechanical strength and high chemical stability, are advantages for use in field emitter. In this paper, we demonstrate electrical discharge properties from carbon nanotube cathode electrodes to use as an emitter electrode of vacuum gauges. Vertically aligned $2{\times}2mm^2$ CNT arrays on the silicon substrate were synthesized by the thermal CVD method on Fe catalytic metal, and a glass patterning by the sand blast method and the silicon/glass anodic bonding processes were applied to make samples with 2 electrodes. The field emission was examined under the vacuum range of $10^{-3}$ Torr.

• Journal of the Korean Vacuum Society
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• v.14 no.4
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• pp.258-262
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• 2005

We report on the field emission properties from vertically aligned carbon nanotubes (CNTs) produced by a triode PECVD with a SiNx capping layer on metal catalyst. It is found that the CNTs density can be controlled by the capping layer thickness and decreases with increasing SiNx thickness. The CNT density of $\~$ 104/$cm^{2}$ exhibited highest electron emission characteristics, the threshold field of 1.2 V/$\mu$m and the current density of 0.17 mA/$cm^{2}$ at 3.6 V/$\mu$m. We have carried out investigation of electron emission stability under ambient gas of N2. The electron emission stability was improved with decreasing CNT density. Under $1\times$$10^{-5}$ Torr ambient pressure, the CNTs in 5 $\mu$m hole show electron emission current higher than $1\times$$10^{-4}$ A/cm2 and it's electron emission uniformity has $2\%$.

• Journal of the Korean Vacuum Society
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• v.17 no.4
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• pp.365-373
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• 2008

We have succeeded in synthesizing vertically aligned thin multi-walled carbon nanotubes (VA thin-MWCNTs) by a catalytic chemical vapor deposition (CCVD) method onto Fe/Al thin film deposited on a Si wafers using an optimum amount of hydrogen sulfide ($H_2S$) additive. Scanning electron microscope (SEM) images revealed that the as-synthesized CNT arrays were vertically well-oriented perpendicular to the substrate with relatively uniform length. Transmission electron microscope (TEM) observations indicated that the as-grown CNTs were nearly catalyst-free thin-MWCNTs with small outer diameters of less than 10nm. The average wall number is about 5. We suggested a possible growth mechanism of the VA thin-MWCNT arrays. The VA thin-MWCNTs showed a low turn-on electric field of about $1.1\;V/{\mu}m$ at a current density of $0.1\;{\mu}A/cm^2$ and a high emission current density about $2.5\;mA/cm^2$ at a bias field of $2.7\;V/{\mu}m$. Moreover, the VA thin-MWCNTs presented better field emission stability without degradation over 20 hours (h) at the emission current density of about $1\;mA/cm^2$.

• Journal of the Korean Vacuum Society
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• v.12 no.1
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• pp.70-77
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• 2003

It is well Down that the growth of carbon nanotubes (CNTs) by chemical vapor deposition (CVD) using a transition metal catalyst is greatly enhanced in a nitrogen environment. We show here that the enhanced growth is closely related to the activated nitrogen and it's incorporation into the CNT wall and cap during growth. This behavior is consistent with theoretical calculations of CNx thin films, showing that nitrogen incorporation to the graphitic basal plane reduces the elastic strain energy for curving the graphitic layer. Enhanced CNT growth by nitrogen incorporation is thus due to a decrease in the activation energies required for nucleation and growth of the tubular graphitic layer.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.21 no.5
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• pp.402-410
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• 2008

Single-walled carbon nanotubes (SWCNTs) were currently produced together with some contaminants such as a metallic catalyst, amorphous carbon, and graphitic nanoparticles, which should be sometimes purified for their applications. This study aimed to develop efficient, scalable purification processes but less harmful to SWCNTs. We designed three-step purification processes: acidic treatment, surface functionalization and soxhlet extraction, and heat treatment. During the soxhlet extraction using tetrahydrofuran, specifically, carbon impurities could be easily expelled through a glass thimble filter without any significant loss of CNTs. Finally, SWCNTs were left as a bulky paper on the filter through membrane filtration. Vertically aligned SWCNTs on one side of bulky paper were well developed in a speparation from the filter paper, which were formed by being sucked through the filter pores during the pressurized filtration. The bucky paper showed a very high peak current density of field emission up to $200\;mA/cm^2$ and uniform field emission images on phosphor, which seems very promising to be applied to vacuum microelectronics such as microwave power amplifiers and x-ray sources.