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We tested a new soft‐x‐ray transmission spectromiscropy technique on the Aladdin storage ring at the Wisconsin Synchrotron Radiation Center. Transmitted x rays were converted with a photocathode into photoelectrons, which were subsequently electron‐optically processed by an x‐ray secondary electron‐emission microscope producing submicron‐resolution images. Test images demonstrated the excellent contrast due to the chemical differences between silicon features and a silicon nitride substrate. We also obtained x‐ray transmission versus photon energy curves for microscopic specimen areas.

Ferromagnetic Co-doped rutile TiO2 single crystals were synthesized by high-temperature ion implantation and characterized by a variety of techniques. Co is uniformly distributed to a depth of ∼300 nm with an average concentration of ∼2 at. %, except in the near-surface region, where the concentration is ∼3 at. %. Ferromagnetic behavior is exhibited at room temperature with an effective saturation magnetization of ∼0.6 μB/Co atom. The Co is in a formal oxidation state of +2 throughout the implanted region, and no Co(O) is detected.

We have grown epitaxial Fe-doped TiO2 rutile films on rutile TiO2(110) substrates, and have explored the resulting compositional, structural, morphological and magnetic properties. Clusters of mixed TiO2 rutile and Fe3O4 form on the surface of a continuous rutile epitaxial film during growth. Room-temperature ferromagnetism is observed, and is associated with the formation of secondary phase Fe3O4 rather than a true diluted magnetic oxide semiconductor.

We have used x-ray photoelectron spectroscopy with high energy resolution to determine band discontinuities at the two buried interfaces of the epitaxial TiO2 (anatase)/SrTiO3/Si(001) system. The valence band offsets are −2.1±0.1 eV and +0.2±0.1 eV at the SrTiO3/Si and TiO2/SrTiO3 heterojunctions, respectively. Assuming bulk band gaps for the SrTiO3 and TiO2 epitaxial films, the associated conduction band offsets are +0.1±0.1 eV and +0.1±0.1 eV. Si at the interface is in a flatband state, indicating a very low density of electronic states. These results suggest that spin-polarized electron injection from ferromagnetic Co-doped TiO2 anatase into Si should be facile.

We show that under certain conditions, highly Co-enriched TiO2 anatase clusters nucleate on epitaxial TiO2 anatase grown on LaAlO3(001) by oxygen plasma assisted molecular beam epitaxy. In the most extreme cases, virtually all incident Co segregates to the clusters, yielding a nanoscale ferromagnetic phase that is not ferromagnetic in homogeneous films of the same Co concentration. The nucleation of this phase simultaneous with continuous epitaxial film growth must be carefully monitored in order to avoid drawing false conclusions about the film structure.

The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

Thin films of CsBr and KBr were deposited on Cu(100) to investigate photoemission properties of these potential photocathode materials. After prolonged laser ultraviolet irradiation photoemission, quantum efficiency increases by factors of 26 and 77 for KBr/Cu(100) and CsBr/Cu(100) photocathodes, respectively. Immediately following thin film deposition, a decrease in work function is observed, compared to bare Cu, in both cases. Quantum efficiency enhancements are attributed to the decrease in photocathode work function, and photo-induced processes that introduce defect states into the alkali halide bandgap. Our results suggest that KBr, a relatively stable alkali-halide, also has potential for photocathode applications.

Growth of Ga-doped ZnO by pulsed laser deposition at 200 °C in an ambient of Ar and H2 produces a resistivity of 1.5 × 10−4 Ω-cm, stable to 500 °C. The resistivity can be further reduced to 1.2 × 10−4 Ω-cm by annealing on Zn foil, which reduces the compensating Zn-vacancy acceptor concentration NA to 5 × 1019 cm−3, only 3% of the Ga-donor concentration ND of 1.6 × 1021 cm−3, with ND and NA determined from a degenerate mobility theory. The plasmon-resonance wavelength is only 1060 nm, further bridging the gap between metals and semiconductors.

Band alignments were measured by x-ray photoelectron spectroscopy for thin films of ZnO on polycrystalline Sn:In2O3 (ITO) and single crystal CdTe. Hybrid density functional theory calculations of epitaxial zinc blende ZnO(001) on CdTe(001) were performed to compare with experiment. A conduction band (CB) offset of −0.6 eV was measured for ZnO/ITO, which is larger than desired for efficient electron injection. For ZnO/CdTe, the experimental conduction band offset of 0.25 eV is smaller than the calculated value of 0.67 eV, possibly due to the TeOx layer at the ZnO/CdTe interface. The measured conduction band offset for ZnO/CdTe is favorable for photovoltaic devices.

Little is currently known about the effects of gamma-ray irradiation on oxide magnet materials. In particular, the effect of particle size on radiationsusceptibility was investigated. Two commercial powders of BaFe12O19 were thoroughly characterized, then exposed to 1 MGy of gamma radiation from a 60Co source. ACsusceptibility and DC magnetometry and Mossbauer spectroscopy were performed after irradiation and compared to pre-irradiated measurements. DC magnetization and ACsusceptibility decreased for both samples with the relative change of DC magnetization being larger for the micrometer-sized particles and the relative change of the ACsusceptibility being larger for the nanometer-sized particles. Mossbauer spectroscopy indicated a decrease in both the hyperfine fields and in their distribution for each Fe site, particularly in the larger particle sample. Decreases in susceptibility are believed to be due to radiation-induced amorphization at the particle surfaces as well as amorphization and nucleation of new crystallites at internal crystallite boundaries, resulting in overall reduction in the particle magnetic moment. This radiation damage mechanism is different than that seen in previous studies of neutron and heavy ion irradiation of BaFe12O19.

Inequivalent angular distributions have been found for La and Al in the ablation plume from LaAlO3 single crystal targets using a KrF laser during pulsed laser deposition. Angular distributions and stoichiometries in the condensate were measured and reveal decidedly nonstoichiometric transfer from target to substrate over most of the angular range. Composition varied dramatically for plume angles parallel to the long axis of the laser spot with the on-axis position exhibiting a peak in the La/Al atom ratio at ∼1.5. The distributions were more diffuse in the perpendicular direction. Stoichiometric LaAlO3 was found in the condensate only at an extreme off-axis position.

The electrical resistivity values for a series of pure and doped (Co, Mn, Al) ZnO epitaxial films grown by pulsed laser deposition were measured with equipment designed for determining the direct current resistivity of high resistance samples. Room-temperature resistances ranging from 7 x 10(1) to 4 x 10(8) Omega/sq were measured on vacuum-reduced cobalt-doped ZnO, (Al,Co) co-doped ZnO, pure cobalt-doped ZnO, Mn-doped ZnO, and undoped ZnO. Using a four-point collinear geometry with gold spring-loaded contacts, resistivities were measured from 295 to 5 K for resistances of < approximately 10(12) Omega/sq. In addition, magnetoresistance and Hall effect were measured as a function of temperature for select samples. Throughout the investigation, samples were also measured on commercially available instrumentation with good agreement. The challenges of transport measurements on high resistivity samples are discussed, along with some offered solutions to those challenges.

We examine the crystal structure and electrical and optical properties of ZnO epitaxial films grown by pulsed laser deposition in a H2 or D2 ambient. n-type electrical conductivity is enhanced by three orders of magnitude as a result of growing in H2 (D2) compared to ZnO films grown in O2. Hall effect measurements reveal very small carrier activation energies and carrier concentrations in the mid-1018 cm−3 range. Optical absorption measurements show that the enhanced conductivity is not a result of ZnO reduction and interstitial Zn formation. Photoluminescence spectra suggest excitonic emission associated with exciton-hydrogen donor complex formation and show no evidence for midgap emission resulting from defects. We have modeled the transport properties of H (D) doped ZnO films using variable range hopping and surface layer conductivity models, but our data do not fit well with these models. Rather, it appears that growth in H2 (D2) promotes the formation of an exceedingly shallow donor state not seen in...

ZnO epitaxial films grown by pulsed laser deposition in an ambient of H2 or D2 exhibit qualitatively different electronic properties compared to films grown in vacuum or O2 or bulk single crystals annealed in H2. These include temperature-independent resistivities of ∼0.1Ωcm, carrier (electron) concentrations in the 1018cm−3 range, mobilities of 20–40cm2∕Vs, and negligible (a few meV) activation energies for conduction. These transport properties are consistent with H (D) forming an ultrashallow donor or conduction band states not achievable by postgrowth annealing in H2.

Co-doped rutile TiO2 was synthesized by injecting Co ions into single crystal rutile TiO2 using high energy ion implantation. Microstructures of the implanted specimens were studied in detail using high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray spectroscopy, electron diffraction, and HRTEM image simulations. The spatial distribution and conglomeration behavior of the implanted Co ions, as well as the point defect distributions induced by ion implantation, show strong dependences on implantation conditions. Uniform distribution of Co ions in the rutile TiO2 lattice was obtained by implanting at 1075K with a Co ion fluence of 1.25×1016Co∕cm2. Implanting at 875K leads to the formation of Co metal clusters. The precipitated Co metal clusters and surrounding TiO2 matrix exhibit the orientation relationships Co⟨110⟩‖TiO2[001] and Co{111}‖TiO2(110). A structural model representing the interface between Co metal clusters and TiO2 is developed based on HRTEM imaging and image sim...

Cobalt-doped titanium dioxide, or CTO, has emerged in the past 2 years as a semiconducting, transparent, room-temperature ferromagnet. Very recently it has been shown that the magnetism in CTO often originates in surface nanoparticles or Co-rich regions that have a much-enhanced substitutional Co content up to 40% of Ti sites, so that magnetic CTO is not a true dilute magnetic semiconductor (DMS), but rather a fairly high-density spin system. In this work we describe a computational study of Co-rich CTO using the generalized gradient approximation to the density functional theory within the supercell model. Our total energy calculations show a strong tendency for Co-atom clustering or segregation on Ti sites. There is also a strong tendency for the oxygen vacancies to form complexes with the Co atoms. In addition, we find that the oxygen stoichiometry plays an essential role in determining the system’s magnetic order. The largest ordered moments require at least enough oxygen vacancies to put all of the C...

Pure anatase TiO2 and CoxTi1−xO2(0.01

Epitaxial ferromagnetic films of Cr-doped TiO2 anatase (CrxTi1−xO2−x∕2) were grown on LaAlO3(001) using oxygen-plasma-assisted molecular-beam epitaxy. CrK-shell x-ray absorption near-edge spectroscopy shows that the formal oxidation state of Cr is +3 throughout the films, with no evidence for either elemental Cr or half-metallic CrO2. Cr is found to substitute for Ti in the lattice, with uniform distribution throughout the doped region of the film. The Cr-doped anatase films exhibit room-temperature ferromagnetism aligned in-plane, with a saturation magnetization of ∼0.6μB/Cr atom.