• 한국분말재료학회지
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• 제22권6호
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• pp.391-395
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• 2015

We report on the successful fabrication of ZnO nanorod (NR)/polystyrene (PS) nanosphere hybrid nanostructure by combining drop coating and hydrothermal methods. Especially, by adopting an atomic layer deposition method for seed layer formation, very uniform ZnO NR structure is grown on the complicated PS surfaces. By using zinc nitrate hexahydrate $[Zn(NO_3)_2{\cdot}6H_2O]$ and hexamine $[(CH_2)_6N_4]$ as sources for Zn and O in hydrothermal process, hexagonal shaped single crystal ZnO NRs are synthesized without dissolution of PS in hydrothermal solution. X-ray diffraction results show that the ZnO NRs are grown along c-axis with single crystalline structure and there is no trace of impurities or unintentionally formed intermetallic compounds. Photoluminescence spectrum measured at room temperature for the ZnO NRs on flat Si and PS show typical two emission bands, which are corresponding to the band-edge and deep level emissions in ZnO crystal. Based on these structural and optical investigations, we confirm that the ZnO NRs can be grown well even on the complicated PS surface morphology to form the chestnut-shaped hybrid nanostructures for the energy generation and storage applications.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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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.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2004년도 제27회 학술발표회 초록집
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• pp.116-116
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• 2004

• 한국진공학회지
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• 제20권3호
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• pp.211-216
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• 2011

본 연구에서는 수열합성법으로 성장시킨 정렬된 산화아연 나노로드의 성장온도에 따른 구조적, 광학적 특성이 조사되었다. Zinc nitrate ($Zn(NO_3)_2$)와 hexamethylenetetramine가 전구체로 사용되었으며 40 nm 두께의 산화아연 버퍼막이 증착된 실리콘 (100) 기판이 사용되었다. 산화아연 나노로드는 $55^{\circ}C$에서 $115^{\circ}C$까지의 성장 온도에서 40 nm 산화아연 버퍼레이어 위에 성장되었다. 결과 분석을 위하여 FE-SEM, XRD, PL 방법 등이 사용되었다. 분석 결과, 잘 정렬된 산화아연 나노로드가 모든 샘플에서 관찰되었다. $95^{\circ}C$ 이하의 증착 온도에서 성장된 산화아연 나노로드의 끝부분은 평평하였으며, $115^{\circ}C$의 증착 온도에서 성장된 산화아연 나노로드의 끝부분은 날카로운 바늘모양의 형태를 나타내었다. 또한 $115^{\circ}C$의 증착 온도에서 비평형 성장때문에 엉킨 나노 구조물이 부분적으로 생성되었다. 성장 온도는 산화아연의 구조적, 광학적 특성에 영향을 미칠 수 있다. 구조적 특성의 경우 성장 온도가 $75^{\circ}C$까지 증가함에 따라 XRD (002) 피크 세기가 증가했고, 성장온도가 $115^{\circ}C$까지 계속적으로 증가함에 따라 피크의 크기는 다시 감소하였다. 광학적 특성에서는, 성장 온도가 증가함에 따라 가시광선 영역 피크 세기에 대한 UV 피크 세기 비율이 증가하였고, $95^{\circ}C$의 성장온도에서는 가장 큰 UV 피크의 세기를 얻을 수 있었다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.226-226
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• 2013

Si is a dominant solar material, which is the second most abundant element in the earth giving a benefit in the aspect in cost with low toxicity. However, the inherent limit of Si has an indirect band gap of 1.1 eV resulting in the limited optical absorption. Therefore, a critical issue has been raised to increase the utilization of the incident light into the Si absorber. The enhancement of light absorption is a crucial to improve the performances and thus relieves the cost burden of Si photovoltaics. For the optical aspect, an efficient design of a front surface, where the incident light comes in, has been intensively investigated to improve the performance of photon absorption. Lambertian light trapping can be attained when the light active surface is ideally rough to increase the optical length by about 50 compared to a planar substrate. This suggests that an efficient design may reduce thickness of the Si absorber from the conventional 100~300 ${\mu}m$ to less than 3 ${\mu}m$. Theoretically, a hole-array structure satisfies an equivalent efficiency of c-Si with only one-twelfth mass and one-sixth thickness. Various approaches have been applied to improve the incident light utilization in a Si absorber using textured structures, periodic gratings, photonic crystals, and nanorod arrays. We have designed hole and pillar structured Si absorbers. Four-different Si absorbers have been simultaneously fabricated on an identical Si wafer with hole arrays or pillar arrays at a fixed depth of 2 ${\mu}m$. We have found that the significant enhanced solar cell performances both for the hole arrayed and pillar arrayed Si absorbers compared to that of a planar Si wafer resulting from the effective improvement in the quantum efficiencies.

• 한국진공학회지
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• 제18권1호
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• pp.73-78
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• 2009

본 연구에서는 metal oxide chemical vapor deposition (MOCVD)을 이용하여 p형 실리콘(100) 기판 위에 30 nm 두께의 산화 아연 완충층을 $500^{\circ}C$ 에서 증착 시킨 후, 그 위에 산화 아연 나노로드를 수열합성법을 이용하여 성장시켰다. 그리고 산화아연 나노로드 성장 시 0.02몰${\sim}$0.5몰의 다양한 농도의 전구체를 사용함으로써 그에 따라 변화되는 산화 아연 나노로드의 배열상태, 구조적, 그리고 광학적 특성 평가를 실시하였다. 특성 평가는 FE-SEM(field emission scanning electron microscopy), XRD(X-ray diffraction), 그리고 PL(photoluminescence) 등의 분석 방법들을 통해 이루어졌다 본 연구를 통하여 전구체의 농도가 증가할수록 나노로드의 직경과 길이가 길어지며 0.3몰의 농도에서 뛰어난 광학 특성이 나타나는 것을 발견할 수 있었다.

• Transactions on Electrical and Electronic Materials
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• 제4권3호
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• pp.15-18
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• 2003

Aluminum oxide ($Al_2O_3$) materials were coated conformally on ZnO nanorods by atomic layer deposition (ALD). The ZnO nanorods were first synthesized on a Si(100) substrate from ball-milled ZnO powders by a thermal evaporation procedure. $Al_2O_3$ films were then deposited on these ZnO nanorods by ALD at a substrate temperature of $300^{\circ}C$ using trimethylaluminum (TMA) and distilled water ($H_2O$). Transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) images of the deposited ZnO nanorods revealed that amorphous $Al_2O_3$ cylindrical shells surround the ZnO nanorods. These TEM images illustrate that ALD has an excellent capability to coat any shape of nanorods conformally.

• 한국전기전자재료학회논문지
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• 제23권3호
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• pp.222-227
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• 2010

ZnO nanorods array have been grown on the seed crystal coated Si(100) substrate by hydrothermal method. The growth, structural and optical properties of ZnO nanorods array were investigated with a variation of precursor concentration from 0.01 M to 0.04 M. The array density of grown ZnO nanorods per same area was increased with increasing the concentration of precursor solution. Vertically aligned ZnO nanorods with hexagonal wurtzite structure have highly preferred c-axis orientation along (002) lattice plane. Especially, ZnO nanorods array developed from 0.04 M precursor solution showed a diameter of about 85 nm and length of 1.2 {\mu}m$ without any crystallographic defects. The photoluminescence spectra of ZnO nanorods from heavier precursor concentration exhibited stronger UV emission around 380 nm corresponding with near-band-edge emission.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2009년도 춘계학술발표대회
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• pp.28.1-28.1
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• 2009

The superior properties of ZnO such as high exciton binding energy, high thermal and chemical stability, low growth temperature and possibility of wet etching process in ZnO have great interest for applications ranging from optoelectronics to chemical sensor. Particularly, vertically well-aligned ZnO nanorods on large areas with good optical and structural properties are of special interest for the fabrication of electronic and optical nanodevices. Currently, low-dimensional ZnO is synthesized by metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), thermal evaporation, and sol.gel growth. Recently, our group has been reported about achievement the growth of Ga-doped ZnO nanorods using ZnO seed layer on p-type Si substrate by RF magnetron sputtering system at high rf power and high growth temperature. However, the crystallinity of nanorods deteriorates due to lattice mismatch between nanorods and Si substrate. Also, in the growth of oxide using sputtering, the oxygen flow ratio relative to argon gas flow is an important growth parameter and significantly affects the structural properties. In this study, Phosphorus (P) doped ZnO nanorods were grown on c-sapphire substrates without seed layer by radio frequency magnetron sputtering with various argon/oxygen gas ratios. The layer change films into nanorods with decreasing oxygen partial pressure. The diameter and length of vertically well-aligned on the c-sapphire substrate are in the range of 51-103 nm and about 725 nm, respectively. The photoluminescence spectra of the nanorods are dominated by intense near band-edge emission with weak deep-level emission.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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• pp.252.2-252.2
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• 2013

ZnO nanostructures have a lot of interest for decades due to its varied applications such as light-emitting devices, power generators, solar cells, and sensing devices etc. To get the high performance of these devices, the factors of nanostructure geometry, spacing, and alignment are important. So, Patterning of vertically- aligned ZnO nanowires are currently attractive. However, many of ZnO nanowire or nanorod fabrication methods are needs high temperature, such vapor phase transport process, metal-organic chemical vapor deposition (MOCVD), metal-organic vapor phase epitaxy, thermal evaporation, pulse laser deposition and thermal chemical vapor deposition. While hydrothermal process has great advantages-low temperature (less than $100^{\circ}C$), simple steps, short time consuming, without catalyst, and relatively ease to control than as mentioned various methods. In this work, we investigate the dependence of ZnO nanowire alignment and morphology on si substrate using of nanosphere template with various precursor concentration and components via hydrothermal process. The brief experimental scheme is as follow. First synthesized ZnO seed solution was spun coated on to cleaned Si substrate, and then annealed $350^{\circ}C$ for 1h in the furnace. Second, 200nm sized close-packed nanospheres were formed on the seed layer-coated substrate by using of gas-liquid-solid interfacial self-assembly method and drying in vaccum desicator for about a day to enhance the adhesion between seed layer and nanospheres. After that, zinc oxide nanowires were synthesized using a low temperature hydrothermal method based on alkali solution. The specimens were immersed upside down in the autoclave bath to prevent some precipitates which formed and covered on the surface. The hydrothermal conditions such as growth temperature, growth time, solution concentration, and additives are variously performed to optimize the morphologies of nanowire. To characterize the crystal structure of seed layer and nanowires, morphology, and optical properties, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy, and photoluminescence (PL) studies were investigated.