플라즈마 질화처리한 사출금형소재의 비정질 탄소계 박막 증착에 따른 기계적 특성 향상 효과

김혜민,김대욱 한국표면공학회 2023 한국표면공학회지 Vol.56 No.5

The carbon-based films have various properties, which have been widely applied in industrial application. However, it has critical drawback for poor adhesion between films and metal substrate. In the present work, we have deposited carbon-based films on injection mold steel by plasma assisted chemical vapor deposition (PACVD). In order to improve adhesion, prior to film deposition, the substrate was nitriding-treated using PACVD. And its effect on the adhesion was investigated. Due to the pre-nitriding, the amorphous carbon nitride (a-CN:H) films presented 10 times higher adhesion (34.9 N) than that of un-nitirided. In addition, a friction coefficient was decreased from 0.29 to 0.15 for the amorphous carbon (a-C:H) due to improved adhesion. The obtained results demonstrated that pre-nitriding considerably improved the adhesion, and the relationship among adhesion, hardness, and surface roughness was discussed in detail.

대향 타겟 스퍼터링 방법으로 제작한 비정질 질화 탄소의 전자선 처리효과

이성엽,이형락,김홍탁,이만우 한국물리학회 2019 New Physics: Sae Mulli Vol.69 No.11

In this study, amorphous carbon nitride (a-CN) films were deposited on glass substrates by using the facing target sputtering technique, and the effects of electron beam (e-beam) treatment on the a-CN films were investigated. The results of the XPS and the Raman analysis showed that the e-beam treatment seldom caused any change in bonding structure between the carbon elements. However, the value of [N]/[C+N] decreased from 18.4% to 16.7% after the treatment, and the ratio of double bonded nitrogen (Nd, =N) and triple-bonded nitrogen (Nt, –N<) was also found to have changed. The value of [Nt]/[Nd + Nt] has decreased from 15.6% to 8.2%. From these results, the e-beam treatment is thought to affect strongly the chemical bonding between nitrogen and carbon. The introduction of a high-energy e-beam caused a change from Nt to Nd, and some nitrogen components disappeared in the form of N2 gas. In conclusion, these changes play major roles in the opto-electronic properties of the films. 본 연구에서는 대향 타겟 스퍼터링 방법을 이용하여 비정질 질화 탄소를 증착하고, 증착된 박막에 고에너지 전자선 처리에 대한 효과를 조사하였다. XPS와 Raman 결과를 분석해보면, 전자선 처리 전후 박막내부의 탄소 결합 변화에는 매우 제한적인 영향만 미치는 것으로 보인다. 전자선 처리 전후의 [N]/[C+N] 값은 각각 18.4%와 16.7%로 박막 내부의 질소의 함량은 감소한다. 두개의 탄소와 결합한 형태(Nd, =N) 와 질소 주위로 3개의 탄소와 결합한 형태(Nt, –N<)의 변화는 [Nt]/[Nd + Nt]의 값의 변화로 나타낼수 있으며, 전자선 처리 후에 이 값은 15.6%에서 8.2%의 값으로 감소한다. 이러한 결과들을 종합해보면, 전자선 처리 후 비정질 질화 탄소 박막은 질소와 탄소 사이의 결합에 주요하게 영향을 미치는 것으로판단이 된다. 즉 고에너지의 전자선이 비정질 질화 탄소 박막에 입사하여 탄소와 질소 사이의 Nt 결합을Nd 결합으로 변환시키며, 이 과정에서 일부 질소 성분은 N2 가스 형태로 박막으로부터 방출되는 것으로보인다. 이러한 변화가 박막의 광학적 특성과 광발광/흡수 특성에 주요한 영향을 미치는 것으로 사료된다.

탄소 나노튜브 위에 붕소 및 탄소 질화 박막이 코팅된 이종접합 구조 미세팁의 전자방출 특성

노영록(Young-Rok Noh),김종필(Jong-Pil Kim),박진석(Jin-Seok Park) 대한전기학회 2010 전기학회논문지 Vol.59 No.4

Boron nitride (BN) and carbon nitride (CN) films, which have relatively low work functions and commonly exhibit negative electron affinity behaviors, were coated on carbon nanotubes (CNTs) by magnetron sputtering. The CNTs were directly grown on metal-tip (tungsten, approximately 500nm in diameter at the summit part) substrates by inductively coupled plasma-chemical vapor deposition (ICP-CVD). The variations in the morphology and microstructure of CNTs due to coating of the BN and CN films were analyzed by field-emission scanning electron microscopy (FE-SEM). The energy dispersive x-ray (EDX) spectroscopy and Raman spectroscopy were used to identify the existence of the coated layers (CN and BN) on CNTs. The electron-emission properties of the BN-coated and CN-coated CNT-emitters were characterized using a high-vacuum field emission measurement system, in terms of their maximum emission currents (Imax) at 1kV and turn-on voltage (Von) for approaching 1μA. The results showed that the Imax current was significantly increased and the Von voltage were remarkably reduced by the coating of CN or BN films. The measured values of Imax-Von were as follows; 176μA-500V for the 5nm CN-coated emitter and 289μA-540V for the 2nm BN-coated emitter, respectively, while the Imax-Von of the as-grown (i.e., uncoated) emitter was 134μA-620V. In addition, the CNT emitters coated with thin CN or BN films also showed much better long-term (up to 25h) stability behaviors in electron emission, as compared with the conventional CNT emitter.

PECVD로 제조된 비정질 질화탄소 박막의 특성에 미치는 증착변수의 영향

문형모,김상섭,Moon, Hyung-Mo,Kim, Sang-Sub 한국재료학회 2003 한국재료학회지 Vol.13 No.3

Amorphous carbon nitride films were deposited on Si(001) substrates by a plasma enhanced chemical vapor deposition technique (PECVD) using $CH_4$and $N_2$as reaction gases. The growth and film properties were investigated while the gas ratio and the working pressure were changed systematically. At 1 Torr working pressure, an increase in the $N_2$partial pressure results in a significant increase of the deposition rate as well as an apparent presence of C ≡N bonding, while little affecting the microstructure and amorphus nature of the films. In the case of changing the working pressure at a fixed $N_2$partial pressure of 98%, a film grown at a medium pressure of $1${\times}$10^{-2}$ Torr shows the most prominent C=N bonding nature and photoluminescent property.

PECVD로 제조된 비정질 질화탄소 박막의 물성에 미치는 열처리 효과

문형모,김상섭,Moon, Hyung-Mo,Kim, Sang-Sub 한국재료학회 2003 한국재료학회지 Vol.13 No.5

Amorphous carbon nitride films deposited on Si(001) substrates by a plasma enhanced chemical vapor deposition (PECVD) technique using CH$_4$and $N_2$as reaction gases were thermally annealed at various temperatures under$ N_2$atmosphere, then their physical properties were investigated particularly as a function of annealing temperature. Above $600^{\circ}C$ a small amount of crystalline $\beta$-$C_3$$N_4$ phase evolves, while the film surface becomes very rough due to agglomeration of fine grains on the surface. As the annealing temperature increases, both the hardness and the $sp^3$ bonding nature are enhanced. In contrast to our expectation, higher annealing temperature results in a relatively higher friction mainly due to big increase in roughness at that temperature.

질화탄소 표면층 및 열처리가 탄소 나노튜브 미세팁의 전계방출 및 장시간 안정성에 미치는 영향

노영록,김종필,박진석,Noh, Young-Rok,Kim, Jong-Pil,Park, Jin-Seok 한국반도체디스플레이기술학회 2010 반도체디스플레이기술학회지 Vol.9 No.1

The effects of thermal treatment on CNTs, which were coated with a-$CN_x$ thin film, were investigated and related to variations of chemical bonding and morphologies of CNTs and also properties of field emission induced by thermal treatment. CNTs were directly grown on nano-sized conical-type tungsten tips via the inductively coupled plasma-chemical vapor deposition (ICP-CVD) system, and a-$CN_x$ films were coated on the CNTs using an RF magnetron sputtering system. Thermal treatment on a-$CN_x$ coated CNT-emitters was performed using a rapid thermal annealing (RTA) system by varying temperature ($300-700^{\circ}C$). Morphologies and microstructures of a-$CN_x$/CNTs hetero-structured emitters were analyzed by FESEM and HRTEM. Chemical composition and atomic bonding structures were analyzed by EDX, Raman spectroscopy, and XPS. The field emission properties of the a-$CN_x$/CNTs hetero-structured emitters were measured using a high vacuum (below $10^{-7}$ Torr) field-emission measurement system. For characterization of emission stability, the fluctuation and degradation of the emission current were monitored in terms of operation time. The results were compared with a-$CN_x$ coated CNT-emitters that were not thermally heated as well as with the conventional non-coated CNT-emitters.

대향 타겟 스퍼터링 방법으로 제작한 비정질 질화 탄소 박막에서의 광발광

김홍탁,이형락,이성엽 한국물리학회 2021 새물리 Vol.71 No.5

In this study, amorphous carbon nitride (a-C:N) thin films were deposited on glass substrates by using a facing target sputtering technique, and the effects of growth temperature were investigated. The deposition rate of the films gradually increased from 1.6 nm/min to 5 nm/min with increasing growth temperature. Emission peaks in the PL spectra of a-C:N films were found at 2.6 eV (green), 3.0 eV (blue), and 3.2 eV (UV). The blue and the UV emissions exhibited an inverse relationship with increasing growth temperature. The ratio of [N]/[C+N] increased from 11% to 15% with increasing to growth temperatures, and this implied an increase of C-N bonding in the films. As the growth temperature was increased, double-bonded nitrogen (Nd, =N-) and triple-bonded nitrogen (Nt, -N<) showed an inverse relationship, and the ratio of [Nt]/[Nd + Nt] increased from 80% to 93%. This tendency was similar to the relationship between the blue and the UV emissions according to growth temperature. Thus, the ratio of Nt and the intensity of UV emission are thought to be closely related, and these changes are thought to play a major role in determining the optoelectronic properties of the films. 본 연구에서는 대향 타겟 스퍼터링 (facing target sputtering) 방법을 사용하여 비정질 질화 탄소(a-C:N) 박막을 증착하고, 증착 온도 변화에 따른 물성을 조사하였다. 그리고 He-Cd 레이저 (파장 : 325 nm, 파워 : 4 mW) 를 여기 광원으로 이용하여 광발광 특성을 분석하였다. 온도의 증가에 따라박막의 증착율은 1.6 nm/min에서 5 nm/min으로 증가한다. 녹색 (2.6 eV), 청색 (3.0 eV), 자외선(3.2 eV) 영역에서 광발광이 관측되고, 성막 온도 증가에 따라서 청색 발광이 감소하고, 자외선 발광이증가하는 경향을 보인다. 온도의 증가에 따라 C-N 결합비를 나타내는 질소함량비 ([N]/[C+N])는 11% 에서 15%로 증가한다. 또한, 온도의 변화에 따라서 질소 삼중결합 Nt (-N<) 과 이중결합 Nd (-N=) 은 반비례 관계를 나타내며, Nt 의 결합비 ([Nt]/[Nt+Nd]) 는 80%에서 93%로 증가한다. 광발광의결과와 비교하였을 때, a-C:N 박막 내부에서의 Nt 의 비와 자외선 발광 세기는 밀접한 관계가 있다고 유추할 수 있으며, 이러한 변화가 박막의 광학적 특성과 광발광 특성에 주요한 영향을 미치는 것으로 사료된다.

Materials (Organic, Inorganic, Electronic, Thin Films), Polymer, Fluidization, Particle Technology : Formation of nanodots and nanostripes of carbon nitride on silicon by Plasma and thermal treatments

( Sang Hoon Kim ),( Ju Hyung Hong ),( Yoon Bong Hahn ) 한국화학공학회 2006 Korean Journal of Chemical Engineering Vol.23 No.2

TRIBOLOGICAL PROPERTIES OF NANO METER SCALE HARD COATINGS

Umehara, N.,Kato, K. ENGINEERING TRIBOLOGY RESEARCH INSTITUTE KYUNGPOOK 1998 INTERNATIONAL SYMPOSIUM ON HIGH PERFORMANCE OF TRI Vol.1998 No.-

By using ion beam assisted deposition (IBAD), carbon nitride coatings whose thickness were less than 100nm were coated on Si substrate, Friction and wear properties against SiC pin were investigated with a pin-on-disk tester. Experimental results show that wear of CNx coatings and SiC pin were dramatically reduced by Cnx coating, even if coating thickness was less than 100nm. Thicker CNx coating provided better wear resistant at high sliding speed.

비대칭 마그네트론 스퍼터링법에 의한 비정질 질화탄소 박막의 합성 및 윤활 특성

박용섭,조형준,최원석,홍병유,Park, Yong-Seob,Cho, Hyung-Jun,Choi, Won-Seok,Hong, Byung-You 한국전기전자재료학회 2007 전기전자재료학회논문지 Vol.20 No.8

The incorporation of N in a-C film is able to improve the friction coefficient and the adhesion to various substrates. In this study, a-C:N films were deposited on Si and steel substrates by closed-field unbalanced magnetron (CFUBM) sputtering system in $Ar/N_2$ plasma. The lubricant characteristics was investigated for a-C:N deposited with total working pressure from 4 to 7 mTorr. We obtained high hardness up to 24GPa, friction coefficient lower than 0.1 and the smooth surface of having the extremely low roughness (0.16 nm). The physcial properties of a-C:N thin film are related to the increase of cross-linked $sp^2$ bonding clusters in the film. However, the decrease of hardness, elastic modulus and the increase of surface roughness, friction coefficient with the increase of $N_2$ partial pressrue might be due to the effect of energetic ions as a result of the increase of ion bombardment with the increase of ion density in the plasma.