Chi-Liang Chen

Heterojunction of Zinc Blende/Wurtzite in Zn1-xCdxS Solid Solution for Efficient Solar Hydrogen Generation: X-ray Absorption/Diffraction Approaches.

In the past decade, inorganic semiconductors have been successfully demonstrated as light absorbers in efficient solar water splitting to generate chemical fuels. Pseudobinary semiconductors Zn1-xCdxS (0≤x≤1) have exhibited a superior photocatalytic reactivity of H2 production from splitting of water by artificial solar irradiation without any metal catalysts. However, most studies had revealed that the extremely high efficiency with an optimal content of Zn1-xCdxS solid solution was determined as a result of elevating the conduction band minimum (CBM) and the width of bandgap. In addition to corresponding band structure and bandgap, the local crystal structure should be taken into account as well to determine its photocatalytic performance. Herein, we demonstrated the correlations between the photocatalytic activity and structural properties that were first studied through synchrotron X-ray diffraction and X-ray absorption spectroscopy. The crystal structure transformed from zinc blende to coexisted phases of major zinc blende and minor wurtzite phases at a critical point. The heterojunction formed by coexistence of zinc blende and wurtzite phases in the Zn1-xCdxS solid solution can significantly improve the separation and migration of photoinduced electron-hole pairs. Besides, X-ray absorption spectra and UV-vis spectra revealed that the bandgap of the Zn0.45Cd0.55S sample extended into the region of visible light because of the incorporation of Cd element in the sample. These results provided a significant progress toward the realization of the photoelectrochemical mechanism in heterojunction between zinc blende and wurtzite phases, which can effectively separate the charge-carriers and further suppress their recombination to enhance the photocatalytic reactivity.

Towards understanding the electronic structure of Fe-doped CeO2 nanoparticles with X-ray spectroscopy

This study reports on the electronic structure of Fe-doped CeO2 nanoparticles (NPs), determined by coupled X-ray absorption spectroscopy and X-ray emission spectroscopy. A comparison of the local electronic structure around the Ce site with that around the Fe site indicates that the Fe substitutes for the Ce. The oxygen K-edge spectra that originated from the hybridization between cerium 4f and oxygen 2p states are sensitive to the oxidation state and depend strongly on the concentration of Fe doping. The Ce M(4,5)-edges and the Fe L(2,3)-edges reveal the variations of the charge states of Ce and Fe upon doping, respectively. The band gap is further obtained from the combined absorption-emission spectrum and decreased upon Fe doping, implying Fe doping introduces vacancies. The oxygen vacancies are induced by Fe doping and the spectrum reveals the charge transfer between Fe and Ce. Fe(3+) doping has two major effects on the formation of ferromagnetism in CeO2 nanoparticles. The first, at an Fe content of below 5%, is that the formation of Fe(3+)-Vo-Ce(3+) introduces oxygen deficiencies favoring ferromagnetism. The other, at an Fe content of over 5%, is the formation of Fe(3+)-Vo-Fe(3+), which favors antiferromagnetism, reducing the Ms. The defect structures Fe(3+)-Vo-Ce(3+) and Fe(3+)-Vo-Fe(3+) are crucial to the magnetism in these NPs and the change in Ms can be described as the effect of competitive interactions of magnetic polarons and paired ions.

Controlled placement and electrical contact properties of individual multiwalled carbon nanotubes on patterned silicon chips

A scheme that allows on-chip growth of multiwalled carbon nanotubes at designed locations is demonstrated. The nanotubes were grown by thermal chemical vapor deposition and were contacted to nanoscaled Cr electrodes fabricated by standard e-beam lithography techniques. The contacts were found to be Ohmic with resistance values on the order of 103 Ω at room temperature. Remarkably, the contacts showed weak temperature dependence down to 40 mK and were insensitive to the magnetic field up to 5 T.

Local geometric and electronic structures of gasochromic VOx films

VOx films were deposited by radio-frequency reactive magnetron sputtering from a vanadium target at room temperature. Local atomic and electronic structures of the films were then modified by thermal annealing. The oxidation state and structural and gasochromic properties of the films were elucidated by X-ray absorption spectroscopy. Analytical results indicate that the as-deposited VOx films were amorphous with mixed V(4+) and V(5+) valences. The amorphous VOx had a disordered and expanded lamellar structure resembling that of polymer-intercalated V2O5 gels. VOx films were crystallized into orthorhombic V2O5 at 300 °C, and the lamellar structure was eliminated at 400 °C. Additionally, the gasochromic reaction reduced the vanadium valence via intervalence transitions between V(5+) and V(3+). Moreover, removing the lamellar structure reduced the gasochromic rate, and the gasochromic reaction transformed the V2O5 crystalline phase irreversibly into an H1.43V2O5 phase. Based on the results of this study, amorphous VOx with a lamellar structure is recommended for use in H2 gas sensors.

Mechanism of light emission and electronic properties of a Eu3+-doped Bi2SrTa2O9 system determined by coupled X-ray absorption and emission spectroscopy

The origin of light emission from newly discovered orange-red UV light emitting diodes, and their electronic properties are critical issues yet to be understood. In this study, X-ray absorption spectroscopy (XAS) and emission spectroscopy (XES) are utilized to examine the electronic structure of the Eu3+-doped Bi2SrTa2O9 system. While no significant change in the electronic structure is observed around the Bi and Ta sites, variation around the Eu and Sr atoms is observed, along with even more significant changes in the O 2p states in the conduction band. Upon UV irradiation, Eu-induced states within the conduction band are observed and found to shift to the conduction band minimum upon substitution of Sr with Eu. This phenomenon is the result of the creation by Eu of an excitable state and the fact that Eu is more electronegative than Sr, such that the substitution lowers the Eu 4f5d–O 2p hybridized states. Consequently, the substitution reduces the energy of electron recombination between the valence and conduction bands, which is consistent with the red shift in the photoluminescence spectra. The presence of the newly formed hole states distributed over the O 2p states in the conduction band is strongly correlated with the emission intensity. The results and analyses demonstrate that Eu can be introduced to tailor the Eu–O hybridized states within the conduction band and change the route of recombination, suggesting that Eu is critically involved in light emission in these UV-induced orange-red emitting LED materials.

Mechanism of Electrochemical Deposition and Coloration of Electrochromic V2O5 Nano Thin Films: an In Situ X-Ray Spectroscopy Study.

Electrochromic switching devices have elicited considerable attention because these thin films are among the most promising materials for energy-saving applications. The vanadium oxide system is simple and inexpensive because only a single-layer film of this material is sufficient for coloration. Vanadium dioxide thin films are fabricated by electrochemical deposition and cyclic voltammetry. Chronoamperometric analyses have indicated that the thin V2O5 film demonstrates faster intercalation and deintercalation of lithium ions than those of the thick V2O5 film, benefiting the coloration rate. Despite substantial research on the synthesis of vanadium oxides, the monitoring of electronic and atomic structures during growth and coloration of such material has not been thoroughly examined. In the present study, in situ X-ray absorption spectroscopy (XAS) is employed to determine the electronic and atomic structures of V2O5 thin films during electrochemical growth and then electrochromic coloration. In situ XAS results demonstrate the growth mechanism of the electrodeposited V2O5 thin film and suggest that its electrochromic performance strongly depends on the local atomic structure. This study improves our understanding of the electronic and atomic properties of the vanadium oxide system grown by electrochemical deposition and enhances the design of electrochromic materials for potential energy-saving applications.

Enhancement of thermoelectric figure of merit in β-Zn4Sb3 by indium doping control

We demonstrate the control of phase composition in Bridgman-grown β-Zn4Sb3 crystals by indium doping, an effective way to overcome the difficulty of growing very pure β-Zn4Sb3 thermoelectric material. The crystal structures are characterized by Rietveld refinement with synchrotron X-ray diffraction data. The results show an anisotropic lattice expansion in In-doped β-Zn4Sb3 wherein the zinc atoms are partially substituted by indium ones at 36f site of R-3c symmetry. Through the elimination of ZnSb phase, all the three individual thermoelectric properties are simultaneously improved, i.e., increasing electrical conductivity and Seebeck coefficient while reducing thermal conductivity. Under an optimal In concentration (x = 0.05), pure phase β-Zn4Sb3 crystal can be obtained, which possesses a high figure of merit (ZT) of 1.4 at 700 K.

Atomic and electronic aspects of the coloration mechanism of gasochromic Pt/Mo-modified V2O5 smart films: an in situ X-ray spectroscopic study

In this work, gasochromic pristine and Mo-modified V2O5 thin films were prepared by the sol-gel spin coating method. Both films exhibit excellent gasochromic coloration. Synchrotron grazing incidence X-ray diffraction reveals that the Mo-modified V2O5 thin film is more amorphous than the pristine V2O5 thin film. X-ray absorption spectroscopy (XAS) was utilized to elucidate the modifications of the local electronic and atomic structures that are caused by Mo. In situ soft-XAS and in situ hard-XAS were performed to monitor the effect of the adsorption of dihydrogen on the charge state of vanadium and local atomic rearrangement in the gasochromic thin films. The gasochromic V2O5 film has a significantly pyramid-like oxygen-coordinated environment. However, the Mo-modified film exhibits mixed pyramid- and octahedral-like structures. Analytic results indicate that upon gasochromic coloration, adsorption of hydrogen adds electrons to the V 3d t2g orbital, lowering the charge state of vanadium. The films undergo structural modification before the valence is changed. The Mo-modified V2O5 film exhibits faster coloration because the apical V-O bond differs from that in the pristine V2O5 film. This in situ XAS allows real-time monitoring of changes in the element-specific local atomic structure during the gasochromic reaction and enables the elucidation of the gasochromic mechanism.

Understanding and tuning electronic structure in modified ceria nanocrystals by defect engineering.

This study investigates the effect of Fe(3+) on the electronic structure of nanocrystalline ceria. Systematic synchrotron X-ray absorption spectroscopy coupled with scanning transmission electron microscopy/electron energy loss spectroscopy was utilized. The oxygen vacancies can be engineered and their number varied with the degree of iron doping. Comparing the local electronic structure around Ce sites with that around Fe sites reveals two stages of defect engineering. The concentration of Ce(3+) and the distribution of defects differ between lower and higher degrees of doping. Charge is transferred between Ce and Fe when the doping level is less than 5%, but this effect is not significant at a doping level of over 5%. This transfer of charge is verified by energy loss spectroscopy. These Fe-modified ceria nanoparticles exhibit core-shell-like structures at low doping levels and this finding is consistent with the results of scanning transmission electron microscopy/electron energy loss spectroscopy. More Fe is distributed at the surface for doping levels less than 5%, whereas the homogeneity of Fe in the system increases for doping levels higher than 5%. X-ray magnetic circular dichroism spectroscopy reveals that Ce, rather than Fe, is responsible for the ferromagnetism. Interestingly, Ce(3+) is not essential for producing the ferromagnetism. The oxygen vacancies and the defect structure are suggested to be the main causes of the ferromagnetism. The charge transfer and defect structure Fe(3+)-Vo-Ce(3+) and Fe(3+)-Vo-Fe(3+) are critical for the magnetism, and the change in saturated magnetization can be understood as being caused by the competition between interactions that originate from magnetic polarons and from paired ions.

Transport dynamics with alternate Cooper-pair and quasiparticle tunnelings in one-dimensional charge Josephson arrays

For a single weak-coupled Josephson junction, stochastic Cooper-pair tunnelings drive the superconducting current on low voltage biases, while quasiparticle tunnelings stimulate the normal current on high biases above the superconducting gap voltage. Considering these interactive dynamics simultaneously in one-dimensional weak-coupled Josephson arrays in electrodynamic environments, the theoretical work by rate equations is structured herein, and the charge transport associated with short-range (Cooper pair and quasiparticle) and long-range (Cooper-pair soliton and quasiparticle soliton) behaviors is analyzed.