• Journal of Powder Materials
• /
• v.22 no.6
• /
• pp.391-395
• /
• 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.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.330-332
• /
• 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 Vacuum Society Conference
• /
• 2004.08a
• /
• pp.116-116
• /
• 2004

• Journal of the Korean Vacuum Society
• /
• v.20 no.3
• /
• pp.211-216
• /
• 2011

In this study, the effects of growth temperature on structural and optical properties of hydrothermally grown ZnO nanorod arrays have been investigated. Zinc nitrate ($Zn(NO_3)_2$) and hexamethylenetetramine were used as precursors. The ZnO buffered Si(100) with a thickness of 40 nm was used as the substrates. The ZnO nanorods were grown on these substrates with the temperature ranging from 55 to $115^{\circ}C$. The results were characterized by scanning electron microscope, X-ray diffraction and room temperature photoluminescence measurements. Well-aligned ZnO nanorods arrays were obtained from all samples. The tips of nanorods were flat when the temperature was less than $95^{\circ}C$, and the sharp-tip nanoneedle-like morphologies were obtained with the temperature of $115^{\circ}C$. In addition, some bundles were on the nanorods arrays with $115^{\circ}C$ due to the non-equilibrium growth. The growth temperature could affect the crystal and optical properties of ZnO. For the effects on crystal properties, the intensity of (002) peak was increased as the temperature was increased to $75^{\circ}C$, then decreased as the temperature was further increased to $115^{\circ}C$. As for the effects on optical properties, the intensity ratio of UV peak to visible peak is increased with the temperature increasing and the strongest UV peak intensity was obtained with the growth temperature of $95^{\circ}C$.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.02a
• /
• pp.226-226
• /
• 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.

• Journal of the Korean Vacuum Society
• /
• v.18 no.1
• /
• pp.73-78
• /
• 2009

Zinc Oxide (ZnO) nanorods arrays were deposited on ZnO buffered p-Si(100) substrates by hydrothermal method. The ZnO buffer layer with a thickness of 30 nm was deposited by metal oxide chemical vapor deposition at $500^{\circ}C$. The structural and optical properties of ZnO nanorods arrays controlled by precursor concentrations from 0.06 to 0.5 M were studied by FE-SEM(field emission scanning electron microscopy), XRD(X-ray diffraction), and PL(photoluminescence), respectively. It was found that the structural and optical properties of ZnO nanorods arrays are changed significantly with increase of precursor concentration. The sizes of diameter and length of nanorods were increased as the concentration increase, and good optical property was shown with the concentration of 0.3 M.

• Transactions on Electrical and Electronic Materials
• /
• v.4 no.3
• /
• pp.15-18
• /
• 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.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.23 no.3
• /
• pp.222-227
• /
• 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.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2009.05a
• /
• pp.28.1-28.1
• /
• 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.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2013.08a
• /
• pp.252.2-252.2
• /
• 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.