• Corrosion Science and Technology
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• v.18 no.5
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• pp.206-211
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• 2019

Silicon carbide (SiC) thin films become superhard when they have microstructures of nanocolumnar crystalline grains (NCCG) with an intergranular amorphous SiC matrix. We investigated the role of ion bombardment and deposition temperature in forming the NCCG in SiC thin films. A direct-current (DC) unbalanced magnetron sputtering method was used with pure Ar as sputtering gas to deposit the SiC thin films at fixed target power of 200 W and chamber pressure of 0.4 Pa. The Ar ion bombardment of the deposited films was conducted by applying a negative DC bias voltage 0-100 V to the substrate during deposition. The deposition temperature was varied between room temperature and $450^{\circ}C$. Above a critical bias voltage of -80 V, the NCCG formed, whereas, below it, the SiC films were amorphous. Additionally, a minimum thermal energy (corresponding to a deposition temperature of $450^{\circ}C$ in this study) was required for the NCCG formation. Transmission electron microscopy, Raman spectroscopy, and glancing angle X-ray diffraction analysis (GAXRD) were conducted to probe the samples' structural characteristics. Of those methods, Raman spectroscopy was a particularly efficient non-destructive tool to analyze the formation of the SiC NCCG in the film, whereas GAXRD was insufficiently sensitive.

• Journal of the Korean institute of surface engineering
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• v.38 no.2
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• pp.65-68
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• 2005

The effect of crystal orientation and microstructure on the mechanical properties of $TaN_x$ was investigated. $TaN_x$ films were grown on $SiO_2$ substrates by ultrahigh vacuum unbalanced magnetron sputter deposition in mixed $Ar/N_2$ discharges at 20 mTorr (2.67 Pa) and at $350^{\circ}C$. Unlike the Ti-N system, in which TiN is the terminal phase, a large number of N-rich phases in the Ta-N system could lead to layers which had nano-sized lamella structure of coherent cubic and hexagonal phases, with a correct choice of nitrogen fraction in the sputtering mixture and ion irradiation energy during growth. The preferred orientations and the micro-structure of $TaN_x$ layers were controlled by varing incident ion energy $E_i\;(=30eV\~50eV)$ and nitrogen fractions $f_{N2}\;(=0.1\~0.15)$. $TaN_x$ layers were grown on (0002)-Ti underlayer as a crystallographic template in order to relieve the stress on the films. The structure of the $TaN_x$ film transformed from Bl-NaCl $\delta-TaN_x$ to lamellar structured Bl-NaCl $\delta-TaN_x$ + hexagonal $\varepsilon-TaN_x$ or Bl-NaCl $\delta-TaN_x$ + hexagonal $\gamma-TaN_x$ with increasing the ion energy at the same nitrogen fraction $f_{N2}$. The hardness of the films also increased by the structural change. At the nitrogen fraction of $0.1\~0.125$, the structure of the $TaN_x$ films was changed from $\delta-TaN_x\;+\;\varepsilon-TaN_x\;to\;\delta-TaN_x\;+\;\gamma-TaN_x$ with increasing the ion energy. However, at the nitrogen fraction of 0.15 the film structure did not change from $\delta-TaN_x\;+\;\varepsilon-TaN_x$ over the whole range of the applied ion energy. The hardness increased significantly from 21.1 GPa to 45.5 GPa with increasing the ion energy.

• Journal of the Korean institute of surface engineering
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• v.38 no.4
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• pp.137-143
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• 2005

CrSiN coatings of stepwise changing Si concentration were deposited on stainless steel by closed field unbalanced magnetron sputtering (CFUBM) system. Microstructure of the films due to the Si concentration is measured by XRD. The corrosion behavior of CrSiN coatings in deaerated $3.5\%$ NaCl solution was investigated by potentiodynamic test, electrochemical impedance spectroscopy (EIS) and surface analyses. The microstructure of CrSiN film depends on the Si concentration. When Si/(Cr+si) was under $11.7\%$, preferred orientation is defined at CrN(220), CrN(311) and $Cr_2N(111).$ The results of potentiodynamic polarization tests showed that the corrosion current density and porosity decreased with increasing Si/(Cr+si) ratio. EIS measurements showed that the corrosion resistance of Si-bearing CrN was improved by phase transformation of the film, which leads to increase of pore resistance and charge transfer resistance. At the Si(Cr+si) ratio of 20, the Si-bearing CrN possesses the best corrosion resistance due to the highest pore resistance and charge transfer resistance.

• Journal of the Korean institute of surface engineering
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• v.45 no.6
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• pp.257-263
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• 2012

CrN/AlN multilayer coatings with various bilayer periods in the range of 1.8 to 7.4 nm were synthesized using a closed-field unbalanced magnetron sputtering method. Their crystalline structure, chemical compositions and mechanical properties have been investigated with Auger electron spectroscopy, X-ray diffractometry, atomic force microscopy, nanoindentation, scratch tests. The properties of the multilayer coatings varied strongly depending upon the magnitude of the bilayer period. The multilayer coating with a bilayer period of 1.8 nm showed the maximum hardness and an elastic modulus of approximately 37.6 and 417 GPa, respectively, which was 1.54 times higher than the hardness predicted by the rule of mixture from the CrN and AlN coatings. The hardness of the multilayer coating increased as the bilayer period decreased, i.e. as the rotation speed increased. The Hall-Petch type relationship, hardness being related to (1/periodicity)$^{-1/2}$, suggested by Lehoczky was confirmed for the CrN/AlN multilayer coatings with bilayer period close to the 5-10 nm range. With decreasing bilayer period, the surface morphology of the films became rougher and the critical load of films for adhesion strength gradually decreased.

• Journal of the Korean institute of surface engineering
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• v.50 no.6
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• pp.473-479
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• 2017

CrN coatings have been used as protective coatings for cutting tools, forming tools, and various tribological machining applications because these coatings have high hardness. Cr-Al-N coatings have been investigated to improve the properties of CrN coatings. Cr-Al-N coatings were fabricated by a hybrid physical vapor deposition method consisting of unbalanced magnetron sputtering and arc ion plating with different working pressure and substrate bias voltage. The phase analysis of the composition was performed using XRD (x-ray diffraction). Cr-Al-N coatings were grown with textured CrN phase and (111), (200), and (220) planes. The adhesion strength of the coatings tested by scratch test increased. The friction coefficient and removal rate of the coatings were measured by a ball-on-disk test. The friction coefficient and removal rate of the coatings decreased from 0.46. to 0.22, and from $2.00{\times}10^{-12}m^2/N$ to $1.31{\times}10^{-13}m^2/N$, respectively, with increasing bias voltage. The tribological properties of the coatings increased with increasing substrate bias voltage.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.237-237
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• 2010

에너지소비와 엔진 부품의 마모문제를 해결하기 위해, soft-phase를 doping한 hard상의 coating에 대한 실험이 최근 중요한 연구 테마로서 진행 중이다. 특히 MoN-Cu coating은 미국 Argon 연구소의 Erdemer박사 등에 의해, 고온 및 상온 윤활성이 우수한 코팅층으로 보고된 이후 많은 연구가 진행되고 있다. 그러나 기존 연구는 Mo와 Cu의 원소타겟을 이용한 연구가 주력이 되었다. 높은 경도와 저온 고온에서의 낮은 나노 혼합물 코팅 종류는 일반적으로 Mo와 Cu와 같은 원소 합금을 이용한 다수 타겟을 이용한 공정에 의해 진행되어왔다. 이러한 복수의 타겟에 의해 증착 동안에는, 정확한 조성, 큰 크기의 시편들의 균일 증착을 조절하기가 쉽지 않다. 또한, 코팅층에 3번째 성분을 추가하기가 어렵다는 문제점이 있다. 본 연구에서는, 최상의 마찰계수와 표면경도를 보이는 MoN-Cu층을 형성시키기 위하여 합금으로 단일 타겟을 제조하였다. 이를 위한 최적 조성을 결정하기 위하여 Mo, Cu 단일 타겟을 이용한 Unbalanced Magnetron sputtering 법으로 다양한 Cu 함량의 MoN+Cu 합금을 제조하였으며, 이에 대한 경도 및 마찰계수 측정을 통해 최적의 Cu 함량을 결정하였다. 이러한 최적 조성의 Cu 타겟제조를 기계적 합금화와 Spark plasma sintering 기술을 이용하여 제작하였으며, 복수의 합금 타겟과 단일 합금 타겟으로 제조된 코팅층의 물성 비교를 통해 합금 타겟의 우수성 여부를 확인하고자 하였다. 증착된 두 조건의 물성을 비교 단일 타겟은 두가지 타겟으로 증착한 것보다 비슷한 조성에서 경도가 높았으며 경도가 비슷한 조성에서는 마찰계수가 낮았다. 또 입자는 10 at.% Cu 조성에 대해 단일타겟이 50nm 결정립을 갖는 반해 단일타겟은 측정이 불가능할 정도의 미세한 결정립을 가졌다. Erdemir의 연구 결과에 의하면, Cu 함량이 증가함에 따라 columnar 형태의 코팅층구조가 나노 구조로 변한다고 하였는데, 본 연구에서 복수의 원소 타겟에서는 확인이 안되었으며, 단일 합금 타겟에서 완벽한 featurless 형태의 코팅층 구조와 우수한 조도의 박막층을 얻을 수 있었다. 이렇게 제조된 다양한 코팅층에 대한 마찰계수 측정이 진행중이다.

• Journal of the Korean institute of surface engineering
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• v.40 no.2
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• pp.91-97
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• 2007

In this study we investigated the oxygen effect on the nucleation and its residual stress during unbalanced magnetron sputtering. Up to 0.5% in oxygen flow rate, cubic phase (c-BN) was dominated with extremely small fraction of Hexagonal phase (h-BN) of increasing trend with oxygen concentration, whereas hexagonal phase is dominated beyond 0.75% flow rate. Interestingly, the residual stress in cubic-phase-dominated films was substantially reduced with small amount of oxygen (${\sim}0.5%$) down to a low value comparable to the h-BN case. This may be because oxygen atoms break B-N $sp^3$ bonds and make B-O bonds more favorably, increasing $sp^2$ bonds preference, as revealed by FTIR and NEXAFS. It was confirmed by experimental facts that the threshold bias voltage for nucleation and growth of cubic phase were increased from -55 V to -70 V and from -50 V to -60 V respectively. The reduction of residual stress in O-added c-BN films is seemingly resulting from the microstructure of the films. The oxygen tends to increase slightly the amount of h-BN phase in the grain boundary of c-BN and the soft h-BN phase of 3D network including surrounding nano grains of cubic phase may relax the residual stress of cubic phase.

• Journal of the Korean institute of surface engineering
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• v.47 no.6
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• pp.330-334
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• 2014

In this study, the Zn-Mg alloy coatings with various Mg contents were deposited using an unbalanced magnetron sputtering process. Their surface microstructure, chemical composition, phase, and corrosion property were investigated. The microstructure of the Zn-Mg coatings changed from porous microstructure to dense one with increasing Mg contents in the coatings. As Mg contents in coatings increased, intermetallic phases such as $Mg_2Zn_{11}$ and $MgZn_2$ were detected from X-ray diffraction (XRD) results. The corrosion resistance of the Zn-Mg alloy coatings was investigated quantitatively using electrochemical impedance spectroscopy (EIS) measurement with 3.5% NaCl solution. The results of EIS measurement showed that the charge transfer resistance and the phase angle of the Zn-Mg alloy coatings were increased from $162.1{\Omega}{\cdot}cm^2$ to $558.8{\Omega}{\cdot}cm^2$ and from about $40^{\circ}$ to $60^{\circ}$ with increasing Mg contents from 5.1 wt.% to 15.5 wt.% in the coatings. These results demonstrate that the Zn-Mg coatings with increasing Mg contents showed an enhanced corrosion resistance.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2012.05a
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• pp.167-168
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• 2012

Films of CrN, $Cr_{40}Zr_9N$, and $Cr_{31}Zr_{16}N$ were deposited on a steel substrate by closed field unbalanced magnetron sputtering, and their oxidation behaviors at $700^{\circ}C$ and $800^{\circ}C$ for up to 60h in air were investigated. All the deposited films were composed of the CrN phase. Zirconium atoms in $Cr_{40}Zr_9N$ and $Cr_{31}Zr_{16}N$ films partially dissolved in the CrN phase. They advantageously refined the columnar structure, reduced the surface roughness, and increased the microhardness. The CrN film displayed relatively good oxidation resistance, owing to the formation of the highly protective $Cr_2O_3$ on its surface. The $Cr_{40}Zr_9N$ and $Cr_{31}Zr_{16}N$ films oxidized to $Cr_2O_3$ as the major phase and ${\alpha}-ZrO_2$ as the minor one. They oxidized primarily by the inward transport of oxygen. The addition of Zr could not increase the oxidation resistance of the CrN film, because the formed $ZrO_2$ that was intermixed in the $Cr_2O_3$-rich oxide layer was oxygen permeable, and developed the compressive stress in the oxide scale owing to the volume expansion during its formation.