• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1195-1201
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• 2014

Atomic layer deposition (ALD) of $TiO_2$ thin film from $TiCl_4$ and $H_2O$ has been intensively studied since the invention of ALD method to grow thin films via chemical adsorptions of two precursors. However the role of HCl which is a gaseous byproduct in ALD chemistry for $TiO_2$ growth is still intriguing in terms of the growth mechanism. In order to investigate the role of HCl in $TiO_2$ ALD, HCl pulse and its purging steps are inserted in a typical sequence of $TiCl_4$ pulse-purge-$H_2O$ pulse-purge. When they are inserted after the first-half reaction (chemisorption of $TiCl_4$), the grown thickness of $TiO_2$ becomes thinner or thicker at lower or higher growth temperatures than $300^{\circ}C$, respectively. However the insertion after the second-half reaction (chemisorption of $H_2O$) results in severely reduced thicknesses in all growth temperatures. By using the result, we explain the growth mechanism and the role of HCl in $TiO_2$ ALD.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.519-523
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• 2013

When atomic layer deposition (ALD) is performed on a porous material by using an organometallic precursor, minimum exposure time of the precursor for complete coverage becomes much longer since the ALD is limited by Knudsen diffusion in the pores. In the previous report by Min et al. (Ref. 23), shrinking core model (SCM) was proposed to predict the minimum exposure time of diethylzinc for ZnO ALD on a porous cylindrical alumina monolith. According to the SCM, the minimum exposure time of the precursor is influenced by volumetric density of adsorption sites, effective diffusion coefficient, precursor concentration in gas phase and size of the porous monolith. Here we modify the SCM in order to consider undesirable adsorption of byproduct molecules. $TiO_2$ ALD was performed on the cylindrical alumina monolith by using titanium tetrachloride ($TiCl_4$) and water. We observed that the byproduct (i.e., HCl) of $TiO_2$ ALD can chemically adsorb on adsorption sites, unlike the behavior of the byproduct (i.e., ethane) of ZnO ALD. Consequently, the minimum exposure time of $TiCl_4$ (~16 min) was significantly much shorter than that (~71 min) of DEZ. The predicted minimum exposure time by the modified SCM well agrees with the observed time. In addition, the modified SCM gives an effective diffusion coefficient of $TiCl_4$ of ${\sim}1.78{\times}10^{-2}\;cm^2/s$ in the porous alumina monolith.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.3
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• pp.164-168
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• 2017

This study experimentally determined the effect of calcium ion ($Ca^{2+}$) (0-0.55 mM) and intial pH (4.0-10.0) on phosphorus (P) removal in synthetic wastewater (2 mg P/L) using titanium tetrachloride ($TiCl_4$) (0.12-0.18 mM). At TiCl4 concentration ([$TiCl_4$]) = 0.12 mM, the P removal efficiency was the highest (95.1%) at pH 7 but the efficiency decreased to 51.4% at pH 8. The P removal efficiency was 55.6% at $Ca^{2+}$ concentration ([$Ca^{2+}$]) = 0 mM but the efficiency increased to 90.5% at [$Ca^{2+}$] = 0.045 mM at [$TiCl_4$] = 0.12 mM. On the other hand, the P removal efficiency difference was not large (96.5-99.5%) with [$Ca^{2+}$] at [$TiCl_4$] = 0.15-0.18 mM. Within the design boundaries of $0.00{\leq}[Ca^{2+}]{\leq}0.18mM$ and $7.0{\leq}initial$ $pH{\leq}9.0$ at [$TiCl_4$] = 0.12 mM, the 90% P removal efficiency could be achieved at $[Ca2+]{\geq}0.10mM$ with pH 8.0 and $[Ca2+]{\geq}0.12mM$ with pH 9.0.

• Applied Chemistry for Engineering
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• v.1 no.1
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• pp.35-43
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• 1990

A series of $TiO_2-SiO_2$catalysts were prepared by coprecipitation from the mixed solution of titanium tetrachloride and sodium silicate. Some of the samples were treated with 1N $H_2SO_4$ and used as modified catalysts. The catalytic activities of modified catalysts were higher than those of unmodified catalysts, and the effect of modification on the catalytic activity was higher for 2 - propanol dehydration than for cumene dealkylation. The catalytic activity of unmodified catalysts was correlated with their acid amount for the above two reactions. As $TiO_2-SiO_2$ catalysts had relatively large amount of weak acid sites and small amount of strong acid sites, the catalytic activity for 2 - propanol dehydration was higher than that for cumene dealkylation. The effect of modification on catalytic activity increased with increasing $TiO_2$content of the catalysts. Actually, $92-TiO_2-SiO_2/SO_4{^2}$had the highest increment in catalytic activity and $10-TiO_2-SiO_2/SO_4{^2}$had the lowest increment for the 2 - propanol dehydration.

• Applied Chemistry for Engineering
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• v.19 no.3
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• pp.270-276
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• 2008

$N_2$ doped $TiO_2$ nano-sized powder was prepared using a DC arc plasma jet and investigated with XRD, BET, SEM, TEM, and photo-catalytic decomposition. Recently the research interest about the nano-sized $TiO_2$ powder has been increased to improve its photo-catalytic activity for the removal of environmental pollutants. Nitrogen gas, reacting gas, and titanium tetrachloride ($TiCl_4$) were used as the raw materials and injected into the plasma reactor to synthesize the $N_2$ doped $TiO_2$ power. The particle size and XRD peaks of the synthesized powder were analyzed as a function of the flow rate of the nitrogen gas. Also, the characteristics of the photo-catalytic decomposition using the prepared powder were studied. For comparing the photo-catalytic decomposition performance of $TiO_2$ powder with that of $TiO_2$ coating, $TiO_2$ thin films were prepared by the spin coating and the pulsed laser deposition. For the results of the acetaldehyde decomposition, the photo-catalytic activity of $TiO_{2-x}N_x$ powder was higher than that of the pure $TiO_2$ powder in the visible light region. For the methylene blue decomposition, the decomposition efficiency of $TiO_2$ powder was also higher than that of $TiO_2$ film.