John S. McCloy

Combined Charge Carrier Transport and Photoelectrochemical Characterization of BiVO4 Single Crystals: Intrinsic Behavior of a Complex Metal Oxide

Bismuth vanadate (BiVO4) is a promising photoelectrode material for the oxidation of water, but fundamental studies of this material are lacking. To address this, we report electrical and photoelectrochemical (PEC) properties of BiVO4 single crystals (undoped, 0.6% Mo, and 0.3% W:BiVO4) grown using the floating zone technique. We demonstrate that a small polaron hopping conduction mechanism dominates from 250 to 400 K, undergoing a transition to a variable-range hopping mechanism at lower temperatures. An anisotropy ratio of ~3 was observed along the c axis, attributed to the layered structure of BiVO4. Measurements of the ac field Hall effect yielded an electron mobility of ~0.2 cm(2) V(-1) s(-1) for Mo and W:BiVO4 at 300 K. By application of the Gärtner model, a hole diffusion length of ~100 nm was estimated. As a result of low carrier mobility, attempts to measure the dc Hall effect were unsuccessful. Analyses of the Raman spectra showed that Mo and W substituted for V and acted as donor impurities. Mott-Schottky analysis of electrodes with the (001) face exposed yielded a flat band potential of 0.03-0.08 V versus the reversible H2 electrode, while incident photon conversion efficiency tests showed that the dark coloration of the doped single crystals did not result in additional photocurrent. Comparison of these intrinsic properties to those of other metal oxides for PEC applications gives valuable insight into this material as a photoanode.

Rhenium Solubility in Borosilicate Nuclear Waste Glass: Implications for the Processing and Immobilization of Technetium-99

The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.

Structural model of homogeneous As–S glasses derived from Raman spectroscopy and high-resolution XPS

The structure of homogeneous bulk As x S100− x (25 ≤ x ≤ 42) glasses, prepared by the conventional rocking–melting–quenching method, was investigated using high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. It is shown that the main building blocks of their glass networks are regular AsS3/2 pyramids and sulfur chains. In the S-rich domain, the existence of quasi-tetrahedral (QT) S = As(S1/2)3 units is deduced from XPS data, but with a concentration not exceeding ∼3–5% of total atomic sites. Therefore, QT units do not appear as primary building blocks of the glass backbone in these materials, and an optimally-constrained network may not be an appropriate description for glasses when x < 40. It is shown that, in contrast to Se-based glasses, the ‘chain-crossing’ model is only partially applicable to sulfide glasses.

Photoluminescence in Chemical Vapor Deposited ZnS: insight into electronic defects

Photoluminescence spectra taken from chemical vapor deposited (CVD) ZnS are shown to exhibit sub-band-gap emission bands characteristic of isoelectronic oxygen defects. The emission spectra vary spatially with position and orientation with respect to the major axis of CVD growth. These data suggest that a complex set of defects exist in the band gap of CVD ZnS whose structural nature is highly dependent upon local deposition and growth conditions, contributing to inherent heterogeneity in optical behavior throughout the material.

Ion irradiation of Fe-Fe oxide core-shell nanocluster films: Effect of interface on stability of magnetic properties

A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NCs) of Fe core-Fe3O4 shell or fully oxidized Fe3O4. Films of these NC on Si(100) or MgO(100)/Fe3O4(100) were irradiated to 1016 Si2+/cm2 near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. In all cases, the particle sizes increased due to ion irradiation, and when a core of Fe is present, irradiation reduces the oxide shells to lower valent Fe species. These results show that ion irradiated behavior of the NC films depends strongly on the initial nanostructure and chemistry, but in general saturation magnetization decreases slightly.

Anisotropy in Structural and Optical Properties of Chemical Vapor Deposited ZnS

Significant anisotropy in as-deposited CVD ZnS at several length scales has been demonstrated through investigation of structural and optical properties. Compressive strength of cylinders of CVD ZnS oriented in the growth direction is ~50% higher than cylinders taken perpendicular to the growth direction. Lattice parameter measurements of mandrel side (first-to-grow) material is ~0.4% smaller than growth side (last-to-grow) material in a cored sample representing ~500 hours of CVD growth, indicating significant strain along the growth direction. X-ray diffraction also shows evidence of preferred orientations for hexagonality which differ depending on position in the growth history. In crosssection, the cored sample shows several large bands which are correlated with different degrees of infrared absorption and BTDF scattering. However, no universal trend is found that applies to the whole length from the mandrel to the growth side regarding optical properties. The extinction in the visible and infrared is lower for measurements perpendicular to the growth axis than parallel to it, possibly due to scattering from the growth bands.

Magnetic hardening from the suppression of domain walls by nonmagnetic particles

Magnetic domain switching and hysteresis loops in a single crystal α-iron with and without nonmagnetic particles were simulated based on the Landau-Lifshitz-Gilbert equation of magnetization dynamics. Both the nonmagnetic particle and the 360° domain wall are nucleation sites of an antidirection domain during domain switching; however, the 360° Bloch domain wall is the easiest nucleation site. The nucleation occurs by splitting the 360° Bloch domain wall into two 180° Bloch domain walls. The existence of nonmagnetic particles could prevent the formation of 360° Bloch domain walls and cause magnetic hardening. Simulations demonstrate the impact of nonmagnetic particle sizes on magnetic domain switching and coercive field.

Regenerative feedback resonant circuit to detect transient changes in electromagnetic properties of semi-insulating materials

A prototype regenerative feedback resonant circuit has been developed for measuring the transient spectral response due to perturbations in properties of various electromagnetic materials. The circuit can accommodate a variety of cavity resonators, shown here in the 8 GHz range, with passive quality factors (Qstat) as high as 7000 depending upon material loading. The positive feedback enhanced dynamic quality factors (Qdyn) of resonator∕material combinations in the regenerative circuit are on the order of 10(7)-10(8). The theory, design, and implementation of the circuit is discussed along with real-time monitored example measurements of effects due to photon-induced charge carriers in high-resistivity silicon wafers and magnetic-field induced perturbations of yttrium-iron garnet.

Millimeter-wave dielectric properties of single-crystal ferroelectric and dielectric materials

Transmittance measurements on various single crystal ferroelectric and dielectric materials, BaTiO3, SrTiO3, LiNbO3, LiTaO3, (PbMg1/3Nb2/3O3)0.73-(PbTiO3)0.27, LaAlO3, and Bi4Ge3O12,, over a broad millimeter-wave (MMW) frequency range have been performed. Frequency dependence of the complex dielectric permittivity has been measured in the MMW region using high-power sources for the first time, using a free-space, quasi-optical MMW spectrometer equipped with high-power backward wave oscillators (BWOs) as sources of coherent radiation, tunable in the range from 30 to 120 and 180 to 260 GHz. These results are compared with MMW permittivity of these materials obtained by other methods as well as to RF, microwave, and optical frequency permittivities for all the materials tested. The effects of both crystallographic orientation and quality of the surface polishing of the crystals have been examined. Uncertainties and possible sources of instrumentation and measurement errors related to the freespace MMW technique are discussed. This work demonstrates that precise MMW permittivity data can be obtained even on relatively small and thin crystals of different surface conditions and orientations using the high-power BWO-based quasioptical approach.

Infrared-transmitting glass-ceramics: a review

A large body of literature was reviewed with the aim of identifying binary and ternary systems for producing long-wave infrared transmitting glass-ceramics for window applications. Known optical and physical property data was summarized for many ternary sulfides as well as their constituent binary sulfides. Some phosphide and arsenide chalcopyrite structures were reviewed as well. Where available, data on the transmission range, energy gap, refractive index, and hardness were tabulated. Several glass-forming systems were identified containing Ga2S3, GeS2, or As2S3.