• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1205-1211
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• 2013

The structural and optical properties of the ZnO, Al-doped ZnO, Ga-doped ZnO, and In-doped ZnO nanorods were investigated using field-emission scanning electron microscopy, X-ray diffraction, photoluminescence (PL) and ultraviolet-visible spectroscopy. All the nanorods grew with good alignment on the ZnO seed layers and the ZnO nanorod dimensions could be controlled by the addition of the various dopants. For instance, the diameter of the nanorods decreased with increasing atomic number of the dopants. The ratio between the near-band-edge emission (NBE) and the deep-level emission (DLE) intensities ($I_{NBE}/I_{DLE}$) obtained by PL gradually decreased because the DLE intensity from the nanorods gradually increased with increase in the atomic number of the dopants. We found that the dopants affected the structural and optical properties of the ZnO nanorods including their dimensions, lattice constants, residual stresses, bond lengths, PL properties, transmittance values, optical band gaps, and Urbach energies.

• Korean Journal of Materials Research
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• v.31 no.9
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• pp.481-487
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• 2021

ZnO particles are successfully synthesized at 150 ℃ for 30 min using zinc acetate as the Zn source and 1,4-butanediol as solvent using a relatively facile and convenient glycol process. The effect of ammonium hydroxide amounts on the growth behavior and the morphological evolution of ZnO particles are investigated. The prepared ZnO nanoparticle with hexagonal structure exhibits a quasi-spherical shape with an average crystallite size of approximately 30 nm. It is also demonstrated that the morphology of ZnO particles can be controlled by 1,4-butanediol with an additive of ammonium hydroxide. The morphologies of ZnO particles are changed sequentially from a quasi-spherical shape to a rod-like shape and a hexagonal rod shape with a truncated pyramidal tip, exhibiting preferential growth along the [001] direction with increasing ammonium hydroxide amounts. It is demonstrated that much higher OH^- amounts can produce a nano-tip shape grown along the [001] direction at the corners and center of the (001) top polar plane, and a flat hexagonal symmetry shape of the bottom polar plane on ZnO hexagonal prisms. The results indicate that the presence of NH⁴⁺ and OH^- ions in the solution greatly affects the growth behaviors of ZnO particles. A sharp near-band-edge (NBE) emission peak centered at 383 nm in the UV region and a weak broad peak in the visible region between 450 nm and 700 nm are shown in the PL spectra of the ZnO synthesized using the glycol process, regardless of adding ammonium hydroxide. Although the broad peak of the deep-level-emission (DLE) increases with the addition of ammonium hydroxide, it is suggested that the prominent NBE emission peaks indicate that ZnO nanoparticles with good crystallization are obtained under these conditions.

• Journal of the Korean Vacuum Society
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• v.19 no.4
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• pp.293-299
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• 2010

Vertically aligned ZnO nanorods on Si (111) substrate were prepared by hydrothermal method. The ZnO nanorods on spin-coated seed layer were synthesized at $140^{\circ}C$ for 6 hours in autoclave and were thermally annealed in argon atmosphere for 20 minutes at temperature of 300, 500, $700^{\circ}C$. The effects of the thermal annealing on the structural and optical properties of the grown on ZnO nanorods were investigated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), photoluminescence (PL). All the ZnO nanorods show a strong ZnO (002) and weak (004) diffraction peak, indicating c-axis preferred orientation. The residual stress of the ZnO nanorods is changed from compressive to tensile by increasing annealing temperature. The hexagonal shaped ZnO nanorods are observed. The PL spectra of the ZnO nanorods show a sharp near-band-edge emission (NBE) at 3.2 eV, which is generated by the free-exciton recombination and a broad deep-level emission (DLE) at about 2.12~1.96 eV, which is caused by the defects in the ZnO nanorods. The intensity of the NBE peak is decreased and the DLE peak is red-shifted due to oxygen-related defects by thermal annealing.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2009.06a
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• pp.9-9
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• 2009

1 wt % Ga-dope ZnO (ZnO:Ga) thin films with n-type semiconducting behavior were grown on c-sapphire substrates by radio frequency magnetron sputtering at various growth temperatures. The room temperature grown ZnO:Ga film showed the faint preferred orientation behavior along the c-axis with small domain size and high density of stacking faults, despite limited surface diffusion of the deposited atoms. The increase in the growth temperature in the range between $300\sim550^{\circ}C$ led to the granular shape of epitaxial ZnO:Ga films due to not enough thermal energy and large lattice mismatch. The growth temperature above $550^{\circ}C$ induced the quite flat surface and the simultaneous improvement of electrical carrier concentration and carrier mobility, $6.3\;\times\;10^{18}/cm^3$ and $27\;cm^2/Vs$, respectively. In addition, the increase in the grain size and the decrease in the dislocation density were observed in the high temperature grown films. The low-temperature photoluminescence of the ZnO:Ga films grown below $450^{\circ}C$ showed the redshift of deep-level emission, which was due to the transition from $Zn_j$ to $O_i$ level.

• Transactions on Electrical and Electronic Materials
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• v.12 no.2
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• pp.51-55
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• 2011

We investigated the etching characteristics of zinc oxide (ZnO) thin films deposited by the atomic layer deposition method. The gases of the inductively coupled plasma chemistry consisted of $Cl_2$, Ar, and $O_2$. The maximum etch rate was 40.3 nm/min at a gas flow ratio of $Cl_2$/Ar=15:5 sccm, radio-frequency power of 600 W, bias power of 200 W, and process pressure of 2 Pa. We also investigated the plasma induced damage in the etched ZnO thin films using X-ray diffraction (XRD), atomic force microscopy and photoluminescence (PL). A highly oriented (100) peak was present in the XRD spectroscopy of the ZnO samples. The full width at half maximum value of the ZnO sample etched using the $O_2/Cl_2$/Ar chemistry was higher than that of the as-deposited sample. The roughness of the ZnO thin films increased from 1.91 nm to 2.45 nm after etching in the $O_2/Cl_2$/Ar plasma chemistry. Also, we obtained a strong band edge emission at 380 nm. The intensities of the peaks in the PL spectra from the samples etched in all of the chemistries were increased. However, there was no deep level emission.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.290.2-290.2
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• 2014

본 연구에서는 스핀코팅방법으로 증착된 ZnO 박막의 Zn-seed 층 열처리에 따른 구조적 광학적 특성에 관한 연구를 수행하였다. ZnO 박막을 증착하기 전, Quartz 기판에 열증착법으로 Zn-seed층을 증착하였고, furnace에서 300, 350, 400, $450^{\circ}C$의 온도로 1시간 동안 열처리하였다. ZnO 박막은 스핀코팅방법으로 5층을 증착한 후, $600^{\circ}C$에서 1시간 동안 후열처리를 하였다. X-ray diffractometer, UV-visible spectrometer, Photoluminescence를 이용하여 ZnO 박막의 구조적, 광학적 특성을 분석하였다. 모든 ZnO 박막 시료에서 c-축 배향성을 나타내는 강한 ZnO(002)피크와 ZnO(100), ZnO(101) 회절피크가 나타났고, wurtzite 형태의 ZnO 박막이 관찰되었다. Zn-seed층을 $350^{\circ}C$에서 열처리함에 따라 deep-level emission 피크에 대한 near-band-edge emission 피크의 발광세기 비율이 증가하였으나, 온도가 증가함에 따라 점점 감소하였다. 또한, Zn-seed층을 $350^{\circ}C$에서 열처리 하였을 때 가장 높은 광 투과도를 나타내었다.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.78-78
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• 2011

수열합성법을 이용하여 Si(111) 기판에 ZnO 박막을 성장하였다. ZnO 박막의 성장을 위한 씨앗층은 plasma-assisted molecular beam epitaxy (PA-MBE)를 이용하였다. 씨앗층의 표면 거칠기(root-mean-square roughness)는 2.5 nm이고, 씨앗층 위에 성장된 ZnO 박막은 다양한 크기의 입자들로 이루어져 있었으며 두께는 약 $1.8{\mu}m$로 매우 일정하였다. 배향성을 알아보기 위하여 texture coefficient (TC)를 계산해 보았다. TC(100)과 TC(200)은 a-축 배향성을, TC(002)는 c-축 배향성을 나타내는데, c-축으로 더 우세한 배향성(99.5%)을 보였다. TC 비율(TCa-axis/TCc-axis)은 열처리 온도를 $700^{\circ}C$까지 올렸을 때, 점차적으로 증가하였고, 그 이상의 열처리 온도(< $900^{\circ}C$)에서는 급격히 감소하였다. 잔류응력과 Zn와 O의 bond length도 유사한 경향을 보였다. $700^{\circ}C$까지 열처리 온도가 증가함에 따라, 잔류응력은 증가하였고 bond length는 감소하였다. Near-band-edge emission (NBE)의 피크 강도는 열처리 온도가 $700^{\circ}C$까지 증가함에 따라 점차적으로 증가하였다. 열처리 온도가 $800^{\circ}C$ 이상 증가함에 따라 deep-level emission (DLE)가 적색편이(red-shift)하였다. $700^{\circ}C$로 열처리를 한 ZnO 박막이 가장 우세한 (002)방향의 배향성을 보였을 뿐만 아니라 가장 큰 발광효율 증가를 보였다.

• Korean Journal of Materials Research
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• v.8 no.6
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• pp.526-531
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• 1998

A hydride vapor phase epitaxy (HVPE) method was performed to grow the $10~240\mu{m}$ thick GaN films on (111) spinel $MgAl_2O_4$ substrate. The GaN films on $MgAl_2O_4$ substrate revealed a photoluminescence (PL) characteristics of the impurity doped GaN by the out-diffusion and auto-doping of Mg from $MgAl_2O_4$ substrate during GaN growth. The PL spectrum measured at 10K consists of free and bound excitons related recombination transitions and impurity-related donor-acceptor pair recombination and its phonon replicas. However, the deep-level related yellow band emission was not observed. The peak energy of neutral donor bound excitonic emission and the frequency of Raman $E_2$ mode were exponentially decreased with increasing the GaN thicknesses. and the frequency of E, Raman mode was shifted with the relation of $\Delta$$\omega$=3.93$\sigma$($cm^{-1}$/GPa), where l1 (GPa) is the residual strain in the GaN epilayers.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.95-98
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• 2013

The photoluminescence (PT) properties of Al-doped ZnO thin films grown by the sol-gel dip-coating method have been investigated. At 12 K, nine distinct PL peaks were observed at 2.037, 2.592, 2.832, 3.027, 3.177, 3.216, 3.260, 3.303, and 3.354 eV. The deep-level emissions (2.037, 2.592, 2.832, and 3.027 eV) were attributed to native defects. The near-band-edge (NBE) emission peaks at 3.354, 3.303, 3.260, 3.216, and 3.177 eV were attributed to the emission of the neutral-donor-bound excitons ($D^0X$), two-electron satellite (TES), free-to-neutral-acceptors (e,$A^0$), donor-acceptor pairs (DAP), and second-order longitudinal optical (2LO) phonon replicas of the TES (TES-2LO), respectively. According to Haynes' empirical rule, we calculated the energy of a free exciton (FX) to be 3.374 eV. The thermal activation energy for $D^0X$ in the nanocrystalline ZnO thin film was found to be ~25 meV, corresponding to the thermal dissociation energy required for $D^0X$ transitions.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.05a
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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.