Vibrational Raman spectra of CdSx Se1‐x magic‐size nanocrystals

Resonant Raman scattering spectra of ultrasmall (<2 nm) magic‐size nanocrystals (NCs) are reported. The spectra of CdS and CdS_x Se_1‐x NCs, resonantly excited with 325 nm and 442 nm laser lines, correspondingly, reveal broad features in the range of bulk optical phonons. The relatively large width, ～50 cm^‐1, and downward shift, ～20 cm^‐1, of the Raman bands with respect to the longitudinal optical phonon in bulk crystals and large NCs are discussed based on the breaking of the translational symmetry and bond distortion in these ultrasmall NCs. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low‐temperature photoluminescence studies of In‐rich InAlN nanocolumns

High‐quality In_x Al_1–xN (0.71 ≤ x_In ≤ 1.00) nanocolumns (NCs) have been grown on Si(111) substrates by rf‐plasma‐assisted molecular‐beam epitaxy (rf‐MBE). Low‐temperature photoluminescence (LT‐PL) spectra of various In‐rich InAlN NCs were measured at 4 K and single peak PL emissions were observed in the wavelength region from 0.89 µm to 1.79 µm. Temperature‐dependent PL spectra of In_0.92Al_0.08N NCs were studied and the so‐called “S‐shape” (decrease–increase–decrease) PL peak energy shift was observed with increasing temperature. This shift indicates the carrier localization induced by the In segregation effect and is different from the anomalous blue shift frequently observed in InN films and nanowires with high residual carrier concentra‐ tions. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low‐temperature synthesis and Raman scattering of Mn‐doped ZnO nanopowders

Nanocrystalline Mn‐doped zinc oxides Zn_1−xMn_xO (x = 0–0.10) were synthesized by the sol–gel technique at low temperature. The calcination temperature of the as‐prepared powder was found at 350 °C using differential thermal analysis. A thermogravimetric analysis showed that there is a mass loss in the as‐prepared powder till 350 °C and an almost constant mass till 800 °C. The X‐ray diffraction patterns of investigated nanopowders calcined at 350 °C correspond to the hexagonal ZnO structure without any foreign impurities. The average grain size of the nanocrystal that was observed around ∼25–40 nm from transmission electron microscopy matched well with the crystallite size calculated from the line shape of X‐ray diffraction. The chemical bonding structure in Zn_1−xMn_xO nanopowders was examined using X‐ray photoelectron spectroscopy techniques, which indicate substitution of Mn²⁺ ions into Zn²⁺ sites in ZnO lattice. Micro Raman spectroscopy confirmed the insertion of Mn ions in the ZnO host matrix, and similar wurtzite structure of Zn_1−xMn_xO (x < 10%) nanocrystals. Temperature‐dependent Raman spectra of the nanocrystals displayed suppression of luminescence and enhancement in full width at half maximum in pure ZnO nanocrystals with increase in temperature, which suggests an enhancement in particle size at elevated temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

miXAFS: a program for X‐ray absorption fine‐structure data analysis

A new program called miXAFS for the analysis of X‐ray absorption fine‐structure (XAFS) data is presented. miXAFS can analyze the XAFS functions simultaneously for all measured X‐ray absorption edges of the constituent elements in a sample under the constraints for the structural parameters over the edges. The program provides a surface plot of the R‐factor as a function of two structural parameters, which is useful to validate the optimized structural parameters. The structural parameters can be obtained from the XAFS data in a few steps using the setting file and batch process. The program, which is coded in MATLAB and freely available, runs on Macintosh and Windows operating systems. It has a graphical user interface and loads experimental data and XAFS functions in a variety of ASCII data formats.     

Analysis of oxygen shell splitting in hydrothermally grown single crystal ThO2(200)

Single crystals of ThO₂ have been synthesized using hydrothermal growth and studied using the X‐ray absorption fine structure (XAFS) technique. The extended X‐ray absorption fine structure (EXAFS) has been extracted from the XAFS and analyzed using a novel, computational Latin hypercube sampling method. The methodology not only confirms the expected space group and crystal structure, it also identifies the origin of a previously reported split O shell. Since EXAFS is a local order analysis technique, the O shell splitting is identified as an O atom occupying an interstitial site. This result is significant for examining O^2– transport in a ThO₂ matrix and corroborating research indicating partial Th 5f occupancy that is similar to hyper‐stoichiometric UO_2+x compounds. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Electro-Optic Coefficient Measurements for Zn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript> Te Single Crystals at 1550 nm Wavelength

Nonlinear optical materials of the type Zn _x Cd_1-x Te single crystals, where x = 0.0, 0.2, 0.4, 0.6, 0.7, 0.8, and 1.0, have been grown by the Bridgman method, using a vertical furnace. We have investigated the electro-optic (E-O) coefficient and refractive index of Zn _x Cd_1-x Te single crystals at optical communication wavelength (1550 nm). In the case of CdTe crystal, the E-O coefficient was 15.5 × 10^-12 m/V, which is the biggest among the E-O coefficients of Zn _x Cd_1-x Te crystals. The E-O modulation signal was very big in low frequency range (DC-100kHz), but the signal amplitude became smaller as we increased frequency above 100 kHz. We also found the acousto-optic modulation at CdTe single crystals.     

Development of a two‐dimensional imaging system of X‐ray absorption fine structure

A two‐dimensional imaging system of X‐ray absorption fine structure (XAFS) has been developed at beamline BL‐4 of the Synchrotron Radiation Center of Ritsumeikan University. The system mainly consists of an ionization chamber for I₀ measurement, a sample stage, and a two‐dimensional complementary metal oxide semiconductor (CMOS) image sensor for measuring the transmitted X‐ray intensity. The X‐ray energy shift in the vertical direction, which originates from the vertical divergence of the X‐ray beam on the monochromator surface, is corrected by considering the geometrical configuration of the monochromator. This energy correction improves the energy resolution of the XAFS spectrum because each pixel in the CMOS detector has a very small vertical acceptance of ～0.5 µrad. A data analysis system has also been developed to automatically determine the energy of the absorption edge. This allows the chemical species to be mapped based on the XANES feature over a wide area of 4.8 mm (H) × 3.6 mm (V) with a resolution of 10 µm × 10 µm. The system has been applied to the chemical state mapping of the Mn species in a LiMn₂O₄ cathode. The heterogeneous distribution of the Mn oxidation state is demonstrated and is considered to relate to the slow delocalization of Li⁺‐defect sites in the spinel crystal structure. The two‐dimensional‐imaging XAFS system is expected to be a powerful tool for analyzing the spatial distributions of chemical species in many heterogeneous materials such as battery electrodes.     

Temperature‐dependent Raman scattering in ferroelectric Bi4−xNdxTi3O12(x = 0, 0.5, 0.85) single crystals

The temperature‐dependent Raman spectra of ferroelectric Bi_4−xNd_xTi₃O₁₂(x = 0, 0.5, 0.85) single crystals were recorded from 100 to 800 K. It was found that there is a critical Nd content x₀ between 0.5 and 0.85. The Nd³⁺ ions prefer to replace Bi³⁺ ions in pseudo‐perovskite layers when x < x₀, while they might begin to incorporate into (Bi₂O₂)²⁺ layers when x ≥ x₀. Nd substitution leads to a decrease in the ferroelectric–paraelectric transition temperature (T_c). A monoclinic distortion of orthorhombic structure occurs in Bi₄Ti₃O₁₂ crystals at temperatures below 200 K. Copyright © 2009 John Wiley & Sons, Ltd.     

X‐ray fluorescence analysis of Co,Ni, Pd,Ag, and Au in the scrapped printed‐circuit‐board ash

A method for the quantitative analysis of Co, Ni, Pd, Ag, and Au in the scrapped printed‐circuit‐board ash by X‐ray fluorescence (XRF) spectrometry using loose powder was developed. The printed‐circuit‐board samples were converted to ash pyrolytically in porcelain crucibles by sequential heating using a gas burner and electric furnace, and then were ground with a ball mill. The calibrating standards were prepared by adding the appropriate amounts of NiO powder and aqueous standard solutions containing Co, Pd, Ag, and Au to the base mixtures of Al₂O₃ (5.0 mass%), SiO₂ (49 mass%), CaCO₃ (11 mass%), Fe₂O₃ (3.3 mass%), and CuO (30 mass%) as a matrix. Then, 10 g of the resulting mixtures were dried and homogenized for 90 min with a V‐type mixing machine. Specimens for XRF analysis were prepared from the so‐called loose‐powder method in which powder samples were compacted into a hole (12.0‐mm diameter and 5.0‐mm height) in an acrylic plate and covered with a 6‐µm thickness of polypropylene film. Matrix effects were corrected using the intensity value of Compton scattering for PdKα, AgKα, and AuLβ₂, and that of background scattering at 35.8° (2θ) for CoKα and NiKα. The detection limits corresponding to three times the standard deviation of the blank intensity were 2.5–45 µg g^?1. The proposed method was validated against the pressed‐powder‐pellet method by comparing the calibration curves. Moreover, the concentrations of Co, Ni, Pd, and Ag determined using the proposed XRF method were approximately the same as those resulting from an atomic‐absorption‐spectrometric analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of α‐Willemite Nanoparticles by Post‐calcination of Flame‐made Zinc Oxide/Silica Composites

Composite ZnO/SiO₂ nanoparticles were made by flame spray pyrolysis (FSP). Characteristics of the product powder and its crystallization behavior on post‐calcination were evaluated. Polyhedral aggregates of nano‐sized primary particles consisting of ZnO nano‐crystals 1–3 nm in size and amorphous SiO₂ were obtained by FSP. A short residence time in the flame can result in the co‐existence of the ZnO and SiO₂ clusters without substitution or reaction hindering each other's grain growth. There was almost no change in the XRD pattern by calcination at 600 °C for 2 h, suggesting a high thermal stability of the ZnO nano‐crystals in the composite particles. A pure α‐willemite phase was obtained at 900 °C. At this calcination temperature, d_C and d_BET of the powder were 63 and 44 nm, respectively. The nano‐composite structure of the FSP‐made particles can suppress crystalline growth of ZnO during calcination to maintain a high reactivity of ZnO with SiO₂, obtaining pure α‐willemite with high specific surface area at low calcination temperatures.     

Composition dependent self‐regenerative property of perovskite‐type oxides

The self‐regenerative property of LaCo_{1–x –y}Pd_x Zn_y O_3±δ and LaFe_{1–x –y}Pd_x Zn_y O_3±δ solid solutions with monometallic Pd or bimetallic Pd/Zn substituents for Co or Fe is studied under a redox cycle by high angular annular dark‐field scanning transmission electron microscopy (STEM‐HAADF) and energy dispersive X‐ray spectroscopy (EDX) and X‐ray diffraction (XRD). These results reveal that the composition of perovskites determines the self‐regenerative property that occurs largely in LaCo_{1–x –y}Pd_x Zn_y O_3±δ but is limited greatly in LaFe_{1–x –y}Pd_x Zn_y O_3±δ. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of irradiation on ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate: an ESR study

Ethyl 2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophene‐3‐carboxylate [C₁₁H₁₅NO₂S] was synthesized by the Gewald method. Its single crystals were grown from an alcohol/ethyl acetate solution at 15 °C and characterized using IR and ¹H‐NMR. These single crystals were irradiated for 72 h at 298 K by a ⁶⁰Co gamma source with a dose speed of 0.864 kGy/h. After irradiation, electron spin resonance (ESR) measurements were carried out to study radiation‐induced radicals in the temperature range from 120 to 450 K. Additionally, for the single crystal, ESR angular dependencies were measured in the xy, xz and yz planes of the substance. This irradiated single crystal was analyzed based on the ESR spectra. Analysis of the spectra revealed that the radical was formed by a C–H bond fission at the carbon end of the substance. It was also observed that the color of the sample changed after irradiation. The hyperfine and g parameters were determined from the experimental spectra. It was inferred from these results that the hyperfine parameters and g value exhibited anisotropic behavior. The average values of these parameters were calculated as follows: g = 2.0088, A_H1=H2 = 20.70 G, A_H3=H4 = 10.80 G, A_Ha = 4.59 G, A_Hb = 3.24 G and, A_N = 6.10 G. Copyright © 2011 John Wiley & Sons, Ltd.     

Standard‐free composition measurements of Alx In1–xN by low‐loss electron energy loss spectroscopy

We demonstrate a standard‐free method to retrieve compositional information in Al_x In_1–xN thin films by measuring the bulk plasmon energy (E_p), employing electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Two series of samples were grown by magnetron sputter epitaxy (MSE) and metal organic vapor phase epitaxy (MOVPE), which together cover the full com‐ positional range 0 ≤ x ≤ 1. Complementary compositional measurements were obtained using Rutherford backscattering spectroscopy (RBS) and the lattice parameters were obtained by X‐ray diffraction (XRD). It is shown that E_p follows a linear relation with respect to composition and lattice parameter between the alloying elements from AlN to InN allowing for straightforward compositional analysis. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Measurement of the X‐ray mass attenuation coefficients of silver in the 5–20 keV range

The X‐ray mass attenuation coefficients of silver were measured in the energy range 5–20 keV with an accuracy of 0.01–0.2% on a relative scale down to 5.3 keV, and of 0.09–1.22% on an absolute scale to 5.0 keV. This analysis confirms that with careful choice of foil thickness and careful correction for systematics, especially including harmonic contents at lower energies, the X‐ray attenuation of high‐Z elements can be measured with high accuracy even at low X‐ray energies (<6 keV). This is the first high‐accuracy measurement of X‐ray mass attenuation coefficients of silver in the low energy range, indicating the possibility of obtaining high‐accuracy X‐ray absorption fine structure down to the L₁ edge (3.8 keV) of silver. Comparison of results reported here with an earlier data set optimized for higher energies confirms accuracy to within one standard error of each data set collected and analysed using the principles of the X‐ray extended‐range technique (XERT). Comparison with theory shows a slow divergence towards lower energies in this region away from absorption edges. The methodology developed can be used for the XAFS analysis of compounds and solutions to investigate structural features, bonding and coordination chemistry.     

AgInS2–ZnS nanocrystals: Evidence of bistable states using light‐induced electron paramagnetic resonance and photoluminescence

The precursor (AgIn)_x Zn_2(1–x)(S₂CN(C₂H₅)₂)₄ was used to prepared AgInS₂–ZnS nanocrystals with different compositions (x = 0.4 and x = 0.7) and with different time of reaction (10 min and 75 min). The photoluminescence features of the nanocrystals were addressed by combining steady‐state spectroscopy and light‐induced electron paramagnetic resonance. Both techniques showed the contribution of at least two components for the emission, previously assigned to surface and intrinsic states. Light‐induced electron paramagnetic resonance allowed detection of the photocreation both of irreversible paramagnetic species that are likely responsible for the nano‐crystals degradation assigned to surface states and of reversible paramagnetic species assigned to intrinsic states. Moreover, reversible bistable paramagnetic states were observed. This Letter provides a scheme that might be useful in addressing the well‐known problem of aging of the nanocrystals. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Simple solar cells of 3.5% efficiency with antimony sulfide‐selenide thin films

Thin films of antimony sulfide‐selenide solid solutions (Sb₂S_x Se_3–x) were prepared by chemical bath deposition and thermal evaporation to constitute solar cells of a transparent conductive oxide (FTO)/CdS/Sb₂S_x Se_3–x/C–Ag. The cell parameters vary depending on the sulfide‐selenide composition in the films. The best solar cell efficiency of 3.6% was obtained with a solid solution Sb₂S_1.5Se_1.5 prepared by thermal evaporation of the precipitate for which the open circuit voltage is 0.52 V and short circuit current density, 15.7 mA/cm²under AM 1.5G (1000 W/m²) solar radiation. For all‐chemically deposited solar cells of Sb₂S_1.1Se_1.9 absorber, these values are: 2.7%, 0.44 V, and 15.8 mA/cm², and for Sb₂S_0.8Se_2.2, they are: 2.5%, 0.38 V and 18 mA/cm². (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Mg‐doped Al0.85Ga0.15N layers grown by hot‐wall MOCVD with low resistivity at room temperature

We report on the hot‐wall MOCVD growth of Mg‐doped Al_x Ga_1–xN layers with an Al content as high as x ～ 0.85. After subjecting the layers to post‐growth in‐situ annealing in nitrogen in the growth reactor, a room temperature resistivity of 7 kΩ cm was obtained indicating an enhanced p‐type conductivity compared to published data for Al_x Ga_1–xN layers with a lower Al content of x ～ 0.70 and a room temperature resistivity of about 10 kΩ cm. It is believed that the enhanced p‐type conductivity is a result of reduced compensation by native defects through growth conditions enabled by the distinct hot‐wall MOCVD system. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray fluorescence induced by standing waves in the grazing‐incidence and grazing‐exit modes: study of the Mg–Co–Zr system

The characterization of Mg–Co–Zr tri‐layer stacks using X‐ray fluorescence induced by X‐ray standing waves, in both the grazing‐incidence (GI) and the grazing‐exit (GE) modes, is presented. The introduction of a slit in the direction of the detector improves the angular resolution by a factor of two and significantly improves the sensitivity of the technique for the chemical characterization of the buried interfaces. By observing the intensity variations of the Mg Kα and Co Lα characteristic emissions as a function of the incident (GI mode) or detection (GE mode) angle, it is shown that the interfaces of the Si/[Mg/Co/Zr]_×30 multilayer are abrupt, whereas in the Si/[Mg/Zr/Co]_×30 multilayer a strong intermixing occurs at the Co‐on‐Zr interfaces. An explanation of this opposite behavior of the Co‐on‐Zr and Zr‐on‐Co interfaces is given by the calculation of the mixing enthalpies of the Co–Mg, Co–Zr and Mg–Zr systems, which shows that the Co–Zr system presents a negative value and the other two systems present positive values. Together with the difference of the surface free energies of Zr and Co, this leads to the Mg/Zr/Co system being considered as a Mg/Co_xZr_y bi‐layer stack, with x/y estimated around 3.5.     

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles for strained‐silicon surface enhanced Raman spectroscopy

Poly(vinylpyrrolidone)‐stabilized silver nanoparticles deposited onto strained‐silicon layers grown on graded Si_1−xGe_x virtual substrates are utilized for selective amplification of the Si–Si vibration mode of strained silicon via surface‐enhanced Raman scattering spectroscopy. This solution‐based technique allows rapid, highly sensitive and accurate characterization of strained silicon whose Raman signal would usually be overshadowed by the underlying bulk SiGe Raman spectra. The analysis was performed on strained silicon samples of thickness 9, 17.5 and 42 nm using a 488 nm Ar⁺ micro‐Raman excitation source. The quantitative determination of strained‐silicon enhancement factors was also made. Copyright © 2011 John Wiley & Sons, Ltd.