• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.70-70
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• 2013

As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

• Proceedings of the Korean Magnestics Society Conference
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• 2011.06a
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• pp.7-8
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• 2011

Basically, the lattice mismatch between film and substrate can make those BiFeO3(BFO) films distorted with strain structure. BFO phase can be stabilized on LaAlO3(LAO) represents the example of a multiferroic with giant axial ratio. Its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion and related to the rotation of the oxygen octahedra. In this study, we show that phases with a tetragonal-like epitaxial BFO films can indeed be ferroelectric and also can be stabilized via epitaxial growth onto LAO. Recent reports on epitaxial BFO films show that the crystal structure changes from nearly rhombohedral ("R-like") to nearly tetragonal("T-like") at strains exceeding approximately -4.5%, with the "T-like" structure being characterized by a highly enhanced c/a ratio. While both the "R-like" and the "T-like" phases are monoclinic, our detailed x-ray diffraction results reveal asymmetry change from MA and MC type, respectively. By applying additional strain or by modifying the unit cell volume of the film by substituting Ba for Bi, the monoclinic distortion in the "T-like" MC phase is reduced, i.e. the system approaches a true tetragonal symmetry. There are two different M-H loops for $Bi_{1-x}Ba_xFeO_{3-{\delta}}$(BBFO) and BFO films on SrTiO3(STO) & LAO substrates. Along with the ferroelectric characterization, these magnetic data indicate that the BFO phase stabilized on LAO represents the first example of a multiferroic with giant axial ratio. However, there is a significant difference between this phase and other predicted ferroelectrics with a giant axial ratio: its crystal structure is not strictly tetragonal, but tetragonal with a slight monoclinic distortion. Therefore, in going from bulk to highly-strained films, a phase sequence of rhombohedral(R)-to-monoclinic ["R-like" MA-to-monoclinic, "T-like" MC-to-tetragonal (T)] is observed. This sequence is otherwise seen only near morphotropic phase boundaries in lead-based solid-solution perovskites (i.e. near a compositionally induced phase instability), where it can be controlled by electric field, temperature, or composition. Our results show that this evolution can occur in a lead-free, stoichiometric material and can be induced by stress alone. Those major results are summarized as follows ; 1) Ba-doping increases the unit cell volume, 2) BBFO on LAO can be fully strained up to x=0.08 as a strain limit (Fig. 1), 3) P(E) & M(H) properties can be tuned by the variation of composition, strain, and film thickness.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.08a
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• pp.173-173
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• 2010

$Bi_4Ti_3O_{12}$ ($B_4T_3$) is a unique ferroelectric material that has a relatively high dielectric constant, high Curie temperature, high breakdown strength, and large spontaneous polarization. As a result this material has been widely studied for many applications, including nonvolatile ferroelectric random memories, microelectronic mechanical systems, and nonlinear-optical devices. Several reports have appeared on the use of Mn dopants to improve the electrical properties of $B_4T_3$ thin films. Mn ions have frequently been used for this purpose in thin films and multilayer capacitors in situations where intrinsic oxygen vacancies are the major defects. However, no systematic study of the optical properties of $B_4T_3$ films has appeared to date. Here, we report optical data for these films, determined by spectroscopic ellipsometry (SE). We also report the effects of thermal annealing and Mn doping on the optical properties. The SE data were analyzed using a multilayer model that is consistent with the original sample structure, specifically surface roughness/$B_4T_3$ film/Pt/Ti/$SiO_2$/c-Si). The data are well described by the Tauc-Lorentz dispersion function, which can therefore be used to model the optical properties of these materials. Parameters for reconstructing the dielectric functions of these films are also reported. The SE data show that thermal annealing crystallizes $B_4T_3$ films, as confirmed by the appearance of $B_4T_3$ peaks in X-ray diffraction patterns. The bandgap of $B_4T_3$ red-shifts with increasing Mn concentration. We interpret this as evidence of the existence deep levels generated by the Mn transition-metal d states. These results will be useful in a number of contexts, including more detailed studies of the optical properties of these materials for engineering high-speed devices.