• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.839-844
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• 2014

The gas-phase radical-radical reaction $O(^3P)$ + $C_2H_5$ (ethyl) ${\rightarrow}$ $H(^2S)$ + $CH_3CHO$(acetaldehyde) was investigated by applying a combination of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration and ab initio calculations. The two radical reactants $O(^3P)$ and $C_2H_5$ were respectively produced by photolysis of $NO_2$ and supersonic flash pyrolysis of the synthesized precursor azoethane. Doppler profile analysis of the nascent H-atom products in the Lyman-${\alpha}$ region revealed that the average translational energy of the products and the average fraction of the total available energy released as translational energy were $5.01{\pm}0.72kcalmol^{-1}$ and 6.1%, respectively. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title exchange reaction is a major channel and proceeds via an addition-elimination mechanism through the formation of a short-lived, dynamical addition complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed small kinetic energy release can be explained in terms of the loose transition state with a product-like geometry and a small reverse activation barrier along the reaction coordinate.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.02a
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• pp.183-184
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• 2013

Two main MBE growth techniques have been used: plasma-assisted MBE (PA-MBE), which utilizes a rf plasma to supply active nitrogen, and ammonia MBE, in which nitrogen is supplied by pyrolysis of NH3 on the sample surface during growth. PA-MBE is typically performed under metal-rich growth conditions, which results in the formation of gallium droplets on the sample surface and a narrow range of conditions for optimal growth. In contrast, high-quality GaN films can be grown by ammonia MBE under an excess nitrogen flux, which in principle should result in improved device uniformity due to the elimination of droplets and wider range of stable growth conditions. A drawback of ammonia MBE, on the other hand, is a serious memory effect of NH3 condensed on the cryo-panels and the vicinity of heaters, which ruins the control of critical growth stages, i.e. the native oxide desorption and the surface reconstruction, and the accurate control of V/III ratio, especially in the initial stage of seed layer growth. In this paper, we demonstrate that the reliable and reproducible growth of GaN on Si (110) substrates is successfully achieved by combining two MBE growth technologies using rf plasma and ammonia and setting a proper growth protocol. Samples were grown in a MBE system equipped with both a nitrogen rf plasma source (SVT) and an ammonia source. The ammonia gas purity was ＞99.9999% and further purified by using a getter filter. The custom-made injector designed to focus the ammonia flux onto the substrate was used for the gas delivery, while aluminum and gallium were provided via conventional effusion cells. The growth sequence to minimize the residual ammonia and subsequent memory effects is the following: (1) Native oxides are desorbed at $750^{\circ}C$ (Fig. (a) for [$1^-10$] and [001] azimuth) (2) 40 nm thick AlN is first grown using nitrogen rf plasma source at $900^{\circ}C$ nder the optimized condition to maintain the layer by layer growth of AlN buffer layer and slightly Al-rich condition. (Fig. (b)) (3) After switching to ammonia source, GaN growth is initiated with different V/III ratio and temperature conditions. A streaky RHEED pattern with an appearance of a weak ($2{\times}2$) reconstruction characteristic of Ga-polarity is observed all along the growth of subsequent GaN layer under optimized conditions. (Fig. (c)) The structural properties as well as dislocation densities as a function of growth conditions have been investigated using symmetrical and asymmetrical x-ray rocking curves. The electrical characteristics as a function of buffer and GaN layer growth conditions as well as the growth sequence will be also discussed. Figure: (a) RHEED pattern after oxide desorption (b) after 40 nm thick AlN growth using nitrogen rf plasma source and (c) after 600 nm thick GaN growth using ammonia source for (upper) [110] and (lower) [001] azimuth.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2010.06a
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• pp.375-375
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• 2010

CdTe as an absorber material is widely used in thin film solar cells with the heterostructure due to its almost ideal band gap energy of 1.45 eV, high photovoltaic conversion efficiency, low cost and stable performance. The deposition methods and preparation conditions for the fabrication of CdTe are very important for the achievement of high solar cell conversion efficiency. There are some rearranged reports about the deposition methods available for the preparation of CdTe thin films such as close spaced sublimation (CSS), physical vapor deposition (PVD), vacuum evaporation, vapor transport deposition (VTD), closed space vapor transport, electrodeposition, screen printing, spray pyrolysis, metalorganic chemical vapor deposition (MOCVD), and RF sputtering. The RF sputtering method for the preparation of CdTe thin films has important advantages in that the thin films can be prepared at low growth temperatures with large-area deposition suitable for mass-production. The authors reported that the optical and electrical properties of CdTe thin film were closely connected by the thickness-uniformity of the film in the previous study [1], which means that the better optical absorbance and the higher carrier concentration could be obtained in the better condition of thickness-uniformity for CdTe thin film. The thickness-uniformity could be controlled and improved by the some process parameters such as vacuum level and RF power in the sputtering process of CdTe thin films. However, there is a limitation to improve the thickness-uniformity only in the preparation process [1]. So it is necessary to introduce the external or additional method for improving the thickness-uniformity of CdTe thin film because the cell size of thin film solar cell will be enlarged. Therefore, the authors firstly applied the chemical mechanical polishing (CMP) process to improving the thickness-uniformity of CdTe thin films with a G&P POLI-450 CMP polisher [2]. CMP process is the most important process in semiconductor manufacturing processes in order to planarize the surface of the wafer even over 300 mm and to form the copper interconnects with damascene process. Some important CMP characteristics for CdTe were obtained including removal rate (RR), WIWNU%, RMS roughness, and peak-to-valley roughness [2]. With these important results, the CMP process for CdTe thin films was performed to improve the thickness-uniformity of the sputtering-deposited CdTe thin film which had the worst two thickness-uniformities of them. Some optical properties including optical transmittance and absorbance of the CdTe thin films were measured by using a UV-Visible spectrophotometer (Varian Techtron, Cary500scan) in the range of 400 - 800 nm. After CMP process, the thickness-uniformities became better than that of the best condition in the previous sputtering process of CdTe thin films. Consequently, the optical properties were directly affected by the thickness-uniformity of CdTe thin film. The absorbance of CdTe thin films was improved although the thickness of CdTe thin film was not changed.