• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.330-332
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• 2013

소 분위기에서 플라즈마 표면 처리의 경우 기판 표면에 존재하는 수소와 탄소 유기물들이 산소와 반응하여 $H_2O$와 $CO_2$ 등으로 제거되며 표면에 오존 결합을 유도하여 표면 에너지를 증가시키는 것으로 알려져 있다. ZnO 나노구조물을 성장시키는 방법으로는 MOCVD (Metal-Organic Chemical Vapor Deposited), PLD (Pulsed Laser Deposition), VLS (Vapor-Liquid-Solid), Sputtering, 습식화학합성법(Wet Chemical Method) 방법 등이 있다. 그중에서도 습식화학합성법은 쉽게 구성요소를 제어할 수 있고, 저비용 공정과 낮은 온도에서 성장 가능하며 플렉서블 소자에도 적용이 가능하다. 그러므로 본 연구에서는 플라즈마 표면처리에 따라 표면에너지를 변화하여 습식화학합성법으로 성장시킨 ZnO nanorods의 밀도를 제어하고 photolithography 공정 없이 패터닝 가능성을 유 무를 판단하는 연구를 진행하였다. 기판은 Si wafer (100)를 사용하였으며 세척 후 표면에너지 증가를 위한 플라즈마 표면처리를 실시하였다. 분위기 가스는 Ar/$O_2$를 사용하였으며 입력전압 400 W에서 0, 5, 10, 15, 60초 동안 각각 실시하였다. ZnO nanorods의 seed layer를 도포하기 위하여 Zinc acetate dehydrate [Zn $(CH_3COO)_2{\cdot}2H_2O$, 0.03 M]를 ethanol 50 ml에 용해시킨 후 스핀코팅기를 이용하여 850 RPM, 15초로 5회 실시하였으며 $80^{\circ}C$에서 5분간 건조하였다. ZnO rods의 성장은 Zinc nitrate hexahydrate [$Zn(NO_3)_2{\cdot}6H_2O$, 0.025M], HMT [$C6H_{12}N_4$, 0.025M]를 deionized water 250 ml에 용해시켜 hotplate에 올리고 $300^{\circ}C$에서 녹인 후 $200^{\circ}C$에서 3시간 성장시켰다. ZnO nanorods의 성장 공정은(Fig. 1)과 같다. 먼저 플라즈마 처리한 시편의 표면에너지 측정을 위해 접촉각 측정 장치[KRUSS, DSA100]를 이용하였다. 그 결과 0, 5, 10, 15, 60 초로 플라즈마 표면 처리했던 시편이 각각 Fig. l, 2와 같이 $79^{\circ}$, $43^{\circ}$, $11^{\circ}$, $6^{\circ}$, $7.8^{\circ}$로 측정되었으며 이것을 각각 습식화학합성법으로 ZnO nanorods를 성장 시켰을 때 Fig. 3과 같이 밀도 차이를 확인할 수 있었다. 이러한 결과를 바탕으로 기판의 표면에너지를 제어하여 Fig. 4와 같이 나타나며 photolithography 공정없이 ZnO nanorods를 패터닝을 할 수 있었다. 본 연구에서는 플라즈마 표면 처리를 통하여 표면에너지의 변화를 제어함으로써 ZnO nanorods 성장의 밀도 차이를 나타냈었다. 이러한 저비용, 저온 공정으로 $O_2$, CO, $H_2$, $H_2O$와 같은 다양한 화학종에 반응하는 ZnO를 이용한 플렉시블 화학센서에 응용 및 사용될 수 있고, 플렉시블 디스플레이 및 3D 디스플레이 소자에 활용 가능하다.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2001.06a
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• pp.8-8
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• 2001

초고속 증착은 짧은 시간에 박막 형성을 가능하게 하므로 window glass 코팅등의 대면적 코팅에 있어서 비용을 절감 시키고, 대량생산을 가능하게 만들기 때문에 관심이 집중되고 있다. 고속증착 공정으로는 high current arc, laser arc, hollow cathode discharge ion plating 그리고 마그네트론 스퍼터링법 등이 있다. 특별히 마그네트론 스퍼터링법은 3m이상의 넓이에 코팅을 할때 두께가 매우 균일하며, 증착율은 evaporation 공정에 비해 경제적, 기능적인 면에서 효율적이다. 그리고 증착된 박막은 매우 조밀하고 좋은 밀착력을 갖고 있으며, 고융점 금속을 포함하여 금속 합금 및 혼합물의 비율을 조정 및 금속 산화물, 질화물, 탄화물 등과 같은 금속의 증착도 stoichiometry를 조정하여 박막을 합성 시키는데 있어서 효과적이다. 이러한 초고속 증착을 만들기 위한 마그네트론 스퍼터링법의 요건은 마그네트론 원이 높은 타켓 power density를 가져야 하며, 타켓에서 효율적으로 플라즈마를 구속하여 스퍼터 되는 이온의 양을 최대화 시킬 수 있어 한다. 따라서 본 실험에서는 초고속 증착을 위해서 직경 50mm 타켓의 UBM magnetron원을 설계 제작하였다. 고밀도의 플라즈마를 형성시키기 위해서, Poisson simulation c code를 이용하여 자기장의 방향, 세기 및 밀도를 측정 하였고, 자기장 측정기(Gauss meter)를 이용하여 실제 자장을 측정 비교 분석하였다. 상기의 data를 바탕으로 여러 형상의 마그네트론원을 설계, 제작하였고. 마그네트론 원의 특성 분석을 위해 I-V 방전 특성을 평가하였고 substrate ion current density와 박막의 증착율을 측정하였다.duty-on 시간의 증가에 따라 $Cr_2N$ 상의 형성이 점점 많아져 80% duty-on 시간 경우에는 거의 CrN과 $Cr_2N$ 상이 공존하는 것으로 나타났다. 또한 duty-on 시간이 증가할수록 회절피크의 세기가 증가하여 결정화가 더 많이 진행되어짐을 알 수 있었다. 마찬가지로 바이어스 펄스이 주파수에 다른 결정성의 변화도 펄스의 주파수가 증가할수록 박막이 결정성이 좋아지고 $Cr_2N$ 상이 쉽게 형성되었다. 증착 진공도에 따른 결정성은 상대적으로 질소의 농도가 높은 낮은 진공도에서는 CrN 상이 주로 형성되었으며, 반대로 높은 진공도에서는 $Cr_2N$ 상이 많이 만들어졌다. 즉 $1.3{\times}10^{-2}Torr$의 증착 진공도에서는 CrN 상만이 보이는 반면 $9.0{\tiems}1-^{-2}Torr$ 진공도에서부터 $Cr_2N$ 상이 형성되기 시작하여 $5.0{\tiems}10^{-2}Torr$ 진공도에서는 두개의 상이 혼재되어 있음을 알 수 있었다. 박막의 내마모성을 조사한 결과 CrN 박막의 마찰 계수는 초기에 급격하게 증가한 후 0.5에서 0.6 사이의 값으로 큰 변화를 보이지 않았으며, $Cr_2N$ 박막도 비슷한 거동을 보였다.차 이, 목적의 차이, 그리고 환경의 의미의 차이에 따라 경관의 미학적 평가가 달라진 것으로 나타났다.corner$적 의도에 의한 경관구성의 일면을 확인할수 있지만 엄밀히 생각하여 보면 이러한 예의 경우도 최락의 총체적인 외형은 마찬가지로 $\ulcorner$순응$\lrcorner$

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.20-20
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• 2008

최근 LEDs가 동일 효율의 전구에 비해 에너지 절감 효과 크며 신뢰성이 뛰어나다기 때문에 기존 광원을 빠르게 대체해 나가고 있다. 특히 자외선 파장을 가지는 LEDs는 발열이 낮아 냉각장치가 필요 없으며, 수명이 길어 기존 UV lamp에 비해 많은 장점을 가지고 있기 때문에 많은 관심을 밭고 있다. 그럼에도 불구하고 자외선 LEDs는 제조 단가가 높고 power가 낮아 소요량이 많은 등 아직 해결해야 할 부분이 많기 때문에 이를 해결하기 위해 여러가지 재료와 다양한 구조가 고려되고 있다. 그 중 ZnO는 II-VI족 화합물 반도체로써 UV영역의 넓은 밴드갭(3.37eV)을 가지는 투명한 재료이다. 특히 ZnO는 60meV의 큰 엑시톤 결합에너지를 가지며, 가시광 영역에서 높은 투과율을 가지고, 상온에서 물리적, 화학적으로 안정하기 때문에 UV sensor, UV laser, UV converter, UV LEDs 등 광소자 분야에서 연구가 활발히 진행되고 있다. ZnO가 광소자의 발광재료로써 높은 효율을 얻기 위해서는 결정성을 높여 내부 결함을 감소시키며, 발광 면적을 높일 수 있는 구조가 요구된다. 특히 MOCVD 법으로 성장한 나노막대는 에피성장되어 높은 결정성을 기대할 수 있으며, 성장 조건을 조절함으로써 나노막대의 aspect ratio와 밀도 제어할 수 있기 때문에 표면적을 효과적으로 넓혀 높은 발광효율을 얻을 수 있다. 본 실험에서는 MOCVD 법으로 실리콘과 사파이어 기판 위에 다양한 성장 온도를 가진 나노구조를 성장 시키고 온도에 따른 형상 변화와 특성을 평가하였다. ZnO 의 성장온도가 약 $360^{\circ}C$ 일 때, 밀도가 조밀하고 기판에 수직 배열한 균일한 나노막대가 성장되었으며 우수한 결정성, 광학적 특성이 나타남을 SEM, TEM, PL, XRD를 사용하여 확인하였다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.41-41
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• 2007

For use in spintronic materials, dilute magnetic semiconductors (DMS) are under consideration as spin injectors for spintronic devices[l]. $TiO_2$-based DMS doped by a cobalt, iron, and manganese et al. was recently reported to show ferromagnetic properties, even at temperatures above 300K and the magnetic ordering was explained in terms of carrier-induced ferromagnetism, as observed for a III-V based DMS. An anomalous Hall effect (AHE) and co-occurance of superparamagnetism in reduced Co-doped rutile $TiO_{2-\delta}$ films have also been reported[2]. Metal segregation in the reduced metal-doped rutile $TiO_2-\delta$ films still remains as problems to solve the intrinsic DMS properties. Superlattice films have been proposed to get dilute magnetic semiconductor (DMS) with intrinsicroom-temperature ferromagnetism. For a $TiO_2$-based DMS superlattice structure, each layer was alternately doped by two different transition metals (Fe and Mn) and deposited to a thickness of approximately $2.7\;{\AA}$ on r-$Al_2O_3$(1102) substrates by pulsed laser deposition. The r-$Al_2O_3$(1102) substrates with atomic steps and terrace surface were obtained by thermal annealing. Samples of $Ti_{0.94}Fe_{0.06}O_2$(TiFeO), $Ti_{0.94}Mn_{0.06}O_2$(TiMnO), and $Ti_{0.94}(Fe_{0.03}Mn_{0.03})O_2$ show a low remanent magnetization and coercive field, as well as superparamagnetic features at room temperature. On the other hand, superlattice films (TiFeO/TiMnO) show a high remanent magnetization and coercive field. An anomalous Hall effect in superlattice films exhibits hysisteresis loops with coercivities corresponding to those in the ferromagnetic Hysteresis loops. The superlattice films composed of alternating layers of $Ti_{0.94}Fe_{0.06}O_2$ and $Ti_{0.94}Mn_{0.06}O_2$ exhibit intrinsic ferromagnetic properties for dilute magnetic semiconductor applications.

• Journal of the Korean Vacuum Society
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• v.9 no.3
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• pp.227-232
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• 2000

$MgTiO_3$thin films have been grown on various substrates by pulsed laser deposition (PLD) to investigate the application for microwave dielectrics and optical devices. Epitaxial $MgTiO_3$thin films were obtained on sapphire (c-plane$A1_2O_3$$MgTiO_3$thin films deposited on $SiO_2/Si$ and platinized silicon ($Pt/Ti/SiO_2/Si$) substrates were highly oriented. $MgTiO_3$thin films grown on sapphire were transparent in the visible and had a sharp absorption edge about 290 nm. These $MgTiO_3$thin films had extremely fine feature of surface morphology, i.e., rms roughness of 0.87 nm, which was examined by AFM. We have investigated the dielectric properties of the $MgTiO_3$thin films in $MIM(Pt/MgTiO_3/Pt)$ capacitors. Dielectric constant and loss of $MgTiO_3$thin films deposited by PLD were about 24 and 1.5% at 1 MHz, respectively. These $MgTiO_3$thin films also exhibited little dielectric dispersion.

• The Journal of the Korea institute of electronic communication sciences
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• v.18 no.5
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• pp.797-802
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• 2023

We prepared GZO (Ga₂O₃ : 5 wt %, ZnO : 95 wt %) thin film on glass substrate according to the substrate temperature using the pulsed laser deposition method and investigated electrical and optical properties of the thin film. Through the XRD measurements, their were confirmed that all GZO thin films grew preferentially in c-axis and the GZO thin film deposited at 300℃ showed the best crystallinity with a FWHM of 0.38°. As the substrate temperature increased from 150 to 300℃, the resistivity of GZO thin film tend to decrease, while the average transmittance in the visible light region was not significantly affected. The figure of merit of the GZO thin film deposited at 300℃ was 2.05×10⁴ Ω^-1·cm^-1, which was the best value, the resistivity and the average transmittance in the visible light region were 3.72 × 10^-4 Ω·cm and 87.71 %, respectively. In this study, it was found that GZO thin film is very promising material for transparent conducting thin film.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.08a
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• pp.174-175
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• 2012

(In, Ga) N-based III-nitride semiconductor materials have been viewed as the most promising materials for the applications of blue and green light emitting devices such as light-emitting diodes (LEDs) and laser diodes. Although the InGaN alloy can have wide range of visible wavelength by changing the In composition, it is very hard to grow high quality epilayers of In-rich InGaN because of the thermal instability as well as the large lattice and thermal mismatches. In order to avoid phase separation of InGaN, various kinds of structures of InGaN have been studied. If high-quality In-rich InGaN/GaN multiple quantum well (MQW) structures are available, it is expected to achieve highly efficient phosphor-free white LEDs. In this study, we proposed a novel InGaN double hetero-structure grown on GaN nano-pyramids to generate broad-band red-color emission with high quantum efficiency. In this work, we systematically studied the optical properties of the InGaN pyramid structures. The nano-sized hexagonal pyramid structures were grown on the n-type GaN template by metalorganic chemical vapor deposition. SiNx mask was formed on the n-type GaN template with uniformly patterned circle pattern by laser holography. GaN pyramid structures were selectively grown on the opening area of mask by lateral over-growth followed by growth of InGaN/GaN double hetero-structure. The bird's eye-view scanning electron microscope (SEM) image shows that uniform hexagonal pyramid structures are well arranged. We showed that the pyramid structures have high crystal quality and the thickness of InGaN is varied along the height of pyramids via transmission electron microscope. Because the InGaN/GaN double hetero-structure was grown on the nano-pyramid GaN and on the planar GaN, simultaneously, we investigated the comparative study of the optical properties. Photoluminescence (PL) spectra of nano-pyramid sample and planar sample measured at 10 K. Although the growth condition were exactly the same for two samples, the nano-pyramid sample have much lower energy emission centered at 615 nm, compared to 438 nm for planar sample. Moreover, nano-pyramid sample shows broad-band spectrum, which is originate from structural properties of nano-pyramid structure. To study thermal activation energy and potential fluctuation, we measured PL with changing temperature from 10 K to 300 K. We also measured PL with changing the excitation power from 48 ${\mu}W$ to 48 mW. We can discriminate the origin of the broad-band spectra from the defect-related yellow luminescence of GaN by carrying out PL excitation experiments. The nano-pyramid structure provided highly efficient broad-band red-color emission for the future applications of phosphor-free white LEDs.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.31-31
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• 2010

The growth of the high-quality GaN epilayers is of significant technological importance because of their commercializedoptoelectronic applications as high-brightness light-emitting diodes (LEDs) and laser diodes (LDs) in the visible and ultraviolet spectral range. The GaN-based heterostructural epilayers have the polar c-axis of the hexagonal structure perpendicular to the interfaces of the active layers. The Ga and N atoms in the c-GaN are alternatively stacked along the polar [0001] crystallographic direction, which leads to spontaneous polarization. In addition, in the InGaN/GaN MQWs, the stress applied along the same axis contributes topiezoelectric polarization, and thus the total polarization is determined as the sum of spontaneous and piezoelectric polarizations. The total polarization in the c-GaN heterolayers, which can generate internal fields and spatial separation of the electron and hole wave functions and consequently a decrease of efficiency and peak shift. One of the possible solutions to eliminate these undesirable effects is to grow GaN-based epilayers in nonpolar orientations. The polarization effects in the GaN are eliminated by growing the films along the nonpolar [$11\bar{2}0$] ($\alpha$-GaN) or [$1\bar{1}00$] (m-GaN) orientation. Although the use of the nonpolar epilayers in wurtzite structure clearly removes the polarization matters, however, it induces another problem related to the formation of a high density of planar defects. The large lattice mismatch between sapphiresubstrates and GaN layers leads to a high density of defects (dislocations and stacking faults). The dominant defects observed in the GaN epilayers with wurtzite structure are one-dimensional (1D) dislocations and two-dimensional (2D) stacking faults. In particular, the 1D threading dislocations in the c-GaN are generated from the film/substrate interface due to their large lattice and thermal coefficient mismatch. However, because the c-GaN epilayers were grown along the normal direction to the basal slip planes, the generation of basal stacking faults (BSFs) is localized on the c-plane and the generated BSFs did not propagate into the surface during the growth. Thus, the primary defects in the c-GaN epilayers are 1D threading dislocations. Occasionally, the particular planar defects such as prismatic stacking faults (PSFs) and inversion domain boundaries are observed. However, since the basal slip planes in the $\alpha$-GaN are parallel to the growth direction unlike c-GaN, the BSFs with lower formation energy can be easily formed along the growth direction, where the BSFs propagate straightly into the surface. Consequently, the lattice mismatch between film and substrate in $\alpha$-GaN epilayers is mainly relaxed through the formation of BSFs. These 2D planar defects are placed along only one direction in the cross-sectional view. Thus, the nonpolar $\alpha$-GaN films have different atomic arrangements along the two orthogonal directions ($[0001]_{GaN}$ and $[\bar{1}100]_{GaN}$ axes) on the $\alpha$-plane, which are expected to induce anisotropic biaxial strain. In this study, the anisotropic strain relaxation behaviors in the nonpolar $\alpha$-GaN epilayers grown on ($1\bar{1}02$) r-plane sapphire substrates by metalorganic chemical vapor deposition (MOCVO) were investigated, and the formation mechanism of the abnormal zigzag shape PSFs was discussed using high-resolution transmission electron microscope (HRTEM).

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.46 no.7
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• pp.7-14
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• 2009

In this paper, the effects of annealing conditions on the structural ((002) intensity, FWHM, d-spacing, grain size, (002) peak position), optical (UV peak, UV peak position) and electrical properties (carrier concentrations, resistivity, mobility) of ZnO films were investigated. ZnO films were deposited onto SiO$_2$/si substrates by RF magnetron sputtering from a ZnO target. The substrate was not heated during deposition. ZnO films were annealed in temperature ranges of $500\sim650^{\circ}C$ in the O$_2$ flow for 5$\sim$20 min. The film average thicknesses were in the range of 291 nm. The surface morphologies and structures of the samples were characterize by SEM and XRD, respectively. The optical properties were evaluated by photoluminescence (PL) measurement at room temperature (RT) using a He-Cd 325 nm laser. As the annealing temperature and time vary, the following relations were also observed: (1) proportional relationships among UV intensity (002) intensity, and grain size exist, (2) UV intensity is inversely proportional to FWHM, (3) there is no special relationship between UV intensity and electron carrier concentrations, (4) d-spacing is inversely proportional to (002) peak position, (5) UV peak position in the range of 3.20$\sim$3.24 eV means that ZnO films have a n-type conductivity which was consistent with that obtained from the electrical property, (6) the optimal conditions for the best optical and structural characteristics were found to be oxygen fraction, (O$_2$/(O$_2$+Ar)) of 0.2, RF power of 240W, substrate temperature of RT, annealing condition of 600$^{\circ}C$ for 20 min, and sputtering pressure of 20 mTorr.