2009. "Antibody recognition force microscopy shows that outer membrane cytochromes OmcA and MtrC are expressed on the exterior surface of Shewanella oneidensis MR-1." Applied and Environmental Microbiology 75(9):2931-2935. Abstract Antibody-recognition force microscopy showed that OmcA and MtrC are expressed on the exterior surface of living Shewanella oneidensis MR-1 cells during anaerobic growth, when Fe(III) served as the terminal electron acceptor. OmcA was localized to the interface with hematite, while MtrC was more uniformly displayed on the bacterium’s exterior cell surface. Both cytochromes were also found associated with extracellular material.
2009. "X-ray absorption fine structure and magnetization characterization of the metallic Co component in Co-doped ZnO thin films ." Physical Review. B, Condensed Matter 79(7):Art. No. 075202. Abstract X-ray absorption fine structure (XAFS) measurements have been used to characterize a series of Co doped ZnO films grown on sapphire substrates by pulsed laser deposition. The emphasis is on characterization of the fate of the Co dopant: metallic particles or substitutional Co2+. It is shown that analysis of both the near edge and extended fine structure can provide a measurement of the fraction of metallic Co. Any quantitative understanding of magnetism in this system needs to take account of both types of Co. Results are reported for two types of films from two different groups that show distinctly different behavior. Films grown with high concentrations of Co show varying amounts of metallic Co that could be identified as hcp or fcc Co. Another set of films were annealed in Zn vapor to induce magnetism. These also showed significant metallic Co, but of a different type similar to the CoZn intermetallic. The bulk forms of both metals are magnetic and should contribute to the magnetism. Using bulk magnetic values, there are some discrepancies with room temperature magnetic measurements. The 2 magnetic properties of the small metal particles are likely changed by their surroundings and by superparamagnetism. Low temperature magnetic measurements for one of the samples confirmed this with an estimated blocking temperature of 50K.
2009. "Cation dopant distributions in nanostructures of transition-metal doped ZnO:Monte Carlo simulations." Physical Review. B, Condensed Matter and Materials Physics 79(7):Art. No. 075324. Abstract The path from trace doping to solid solution formation involves an intermediate regime in which the doping level is a few to several atomic percent. In this regime, dopant-dopant interactions, which are driven by the spatial arrangement of dopants, are critical factors in determining the resulting properties. Conventional wisdom counts on simple probabilistic methods for predicting dopant distributions. Here, we use Monte Carlo simulations to show that widely used, straightforward statistical models, such as that of Behringer1, are accurate only in the limit of infinitesimally small surface–to-volume ratio. For epitaxial films and nanoparticles, where much of the current interest resides, dopant distributions depend strongly on the surface-to-volume ratio. We present empirical expressions that accurately predict dopant bonding configurations as a function of film or particle size, shape and dopant concentration for doped ZnO, a material of particular interest in semiconductor spintronics.
2008. "Electronic properties of H and D doped ZnO epitaxial films." Applied Physics Letters 92(15):Art. No. 152105. Abstract 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 ~0.1 -cm, carrier (electron) concentrations in the 1018 cm-3 range, mobilities of 20-40 cm2/V-sec, and negligible (a few meV) activation energies for conduction. These transport properties are consistent with H (D) forming an ultra-shallow donor or conduction band states not achievable by post-growth annealing in H2.
2008. "A Study of H and D doped ZnO epitaxial films grown by pulsed laser deposition." Journal of Applied Physics 104(5):Article no. 053711. doi:10.1063/1.2975219 Abstract We examine the crystal structure, electrical and optical properties of ZnO epitaxial films grown by pulsed laser deposition in a H2 or D2 ambient. We compared with pure ZnO films grown in O2 and vacuum. N-type electrical conductivity is enhanced by two to three orders of magnitude as a result of growing in H2 or D2. Temperature dependent Hall effect measurements reveal small (a few meV) carrier activation energies, along with carrier concentrations of 2-7 x 1018 cm-3, and mobilities of 20-40 cm2/Vs in ZnO films doped with H or D in the 1018 cm-3 range. We have modeled the low-temperature electrical properties of H- and 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 or D2 promotes the formation of an exceedingly shallow or conduction-band degenerate donor state, possibly associated with H or D substitution at O sites in the lattice.
2008. "Lack of ferromagnetism in n-type cobalt-doped ZnO epitaxial thin films." New Journal of Physics 10:Art. No. 055010. doi:10.1088/1367-2630/10/5/055010 Abstract Epitaxial thin films of cobalt-doped ZnO (Co:ZnO) were deposited by pulsed laser deposition (PLD) on both c-plane and r-plane sapphire (Al2O3). The films exhibited high structural quality with narrow x-ray diffraction (XRD) rocking curve peak widths. X-ray absorption spectroscopy (XANES and EXAFS) confirmed well-ordered Co substitution for Zn in ZnO without the formation of secondary phases. A wide range of n-type conductivities (10-4 – 105 -cm) was achieved by controlling the deposition conditions, post-annealing in vacuum, and/or addition of Al during deposition. Despite the high structural quality of the Co:ZnO thin films, no significant room temperature ferromagnetism was observed under any processing or treatment conditions. The lack of ferromagnetism indicates that itinerant conduction band electrons alone are not sufficient to induce ferromagnetism in Co:ZnO, even when the carrier concentration is a significant fraction of the magnetic dopant concentration. The implications of this observation are discussed.
2008. "Hidden Ferromagnetic Secondary Phases in Cobalt-doped ZnO Epitaxial Thin Films." Physical Review. B, Condensed Matter 77(20):201303. doi:10.1103/PhysRevB.77.201303 Abstract The quest to discover a dilute magnetic semiconductor which is ferromagnetic at room temperature has led to extensive research on doped semiconducting oxides. However, the wide range of reported properties has raised doubts regarding the presence of intrinsic ferromagnetism in these materials. Here we explore the origin of ferromagnetism in epitaxial Co:ZnO thin films, which are paramagnetic but become weakly ferromagnetic (~0.05 μB/Co) after annealing in Zn vapor to introduce interstitial Zn. Conventional bulk materials characterization techniques indicate no phase segregation or Co reduction has occurred. However, x-ray photoelectron spectroscopy sputter depth profiling clearly indicates the presence of Co(0) in the Zn-treated films; x-ray absorption spectroscopy is utilized to identify the secondary phase as ferromagnetic CoZn (1.5 μB/Co, TC ~ 400 – 450 K). This work demonstrates that the potential for ferromagnetic secondary phases in doped oxides must be thoroughly discounted, through painstaking materials characterization, before claims of intrinsic ferromagnetism can be made.
2008. "Binding and Direct Electrochemistry of OmcA, an Outer-Membrane Cytochrome from an Iron Reducing Bacterium, with Oxide Electrodes: A Candidate Biofuel Cell System." Inorganica Chimica Acta 361(3):769-777. doi:10.1016/j.ica.2007.07.015 Abstract Dissimilatory iron-reducing bacteria transfer electrons to solid ferric respiratory electron acceptors. Outer-membrane cytochromes expressed by these organisms are of interest in both microbial fuel cells and biofuel cells. We use optical waveguide lightmode spectroscopy (OWLS) to show that OmcA, an 85 kDa decaheme outer-membrane c-type cytochrome from Shewanella oneidensis MR-1, adsorbs to isostructural Al2O3 and Fe2O3 in similar amounts. Adsorption is ionic-strength and pH dependent (peak adsorption at pH 6.5–7.0). The thickness of the OmcA layer on Al2O3 at pH 7.0 [5.8 ± 1.1 (2r) nm] from OWLS is similar, within error, to that observed using atomic force microscopy (4.8 ± 2 nm). The highest adsorption density observed was 334 ng cm 2 (2.4 · 1012 molecules cm 2), corresponding to a monolayer or 9.9 nm diameter spheres or submonolayer coverage by smaller molecules. Direct electrochemistry of OmcA on Fe2O3 electrodes was observed using cyclic voltammetry, with cathodic peak potentials of 380 to 320 mV versus Ag/AgCl. Variations in the cathodic peak positions are speculatively attributed to redox-linked conformation change or changes in molecular orientation. OmcA can exchange electrons with ITO electrodes at higher current densities than with Fe2O3. Overall, OmcA can bind to and exchange electrons with several oxides, and thus its utility in fuel cells is not restricted to Fe2O3.
2007. "Photoemission Electron Microscopy of TiO2 Anatase Films Embedded with Rutile Nanocrystals." Advanced Functional Materials 17(13):2133-2138. doi:10.1002/adfm.200700146 Abstract Photoemission electron microscopy (PEEM) excited by x-ray and UV sources is used to investigate epitaxial anatase thin films embedded with rutile nanocrystals, a model system for the study of heterocatalysis on mixed-phase TiO2. Both excitation sources show distinct contrast between the two TiO2 phases, however, the contrast is reversed. Rutile nanocrystals appear darker than the anatase film in X-ray PEEM images but brighter in UV-PEEM images. Topography-induced contrast is dominant X-ray PEEM imaging, whereas work function contrast, dominates for UV-PEEM. Work function contrast results from the differences in work function and surface defect state densities between the two phases near the Fermi level. This assertion is confirmed by UPS data that shows the rutile work function to be 0.2 eV lower and a greater occupied valence band density-of-states in rutile (100) than in anatase (001). Since the boundaries between rutile nanocrystals and the anatase film are clearly resolved, these results indicate that PEEM studies of excited state dynamics and heterocatalysis are possible at chemically intriguing mixed-phase TiO2 interfaces and grain boundaries.
2007. "Growth and structure of MBE grown TiO2 anatase films with rutile nano-crystallites ." Surface Science 601(6):1582-1589. doi:10.1016/j.susc.2007.01.039 Abstract We have grown TiO2 anatase films with rutile nanocrystalline inclusions using molecular beam epitaxy under different growth conditions. This model system is important for investigating the role of rutile/anatase interfaces in heterogeneous photocatalysis. To control the film structure, we grew a pure anatase (001) layer at a slow rate and then increased the growth rate to drive the nucleation of rutile particles. Structure analysis indicates that the rutile phase has four preferred orientations in the anatase film.
2007. "Specific Bonds between an Iron Oxide Surface and Outer Membrane Cytochromes MtrC and OmcA from Shewanella oneidensis MR-1." Journal of Bacteriology 189(13):4944-4952. doi:10.1128/JB.01518-06 Abstract Shewanella oneidensis MR-1 is purported to express outer membrane cytochromes (e.g., MtrC and OmcA) that transfer electrons directly to Fe(III) in a mineral during anaerobic respiration. A prerequisite for this type of reaction would be the formation of a stable bond between a cytochrome and an iron oxide surface. Atomic force microscopy (AFM) was used to detect whether a specific bond forms between a hematite (Fe2O3) thin film, created with oxygen plasma assisted molecular beam epitaxy (MBE), and recombinant MtrC or OmcA molecules coupled to gold substrates. Force spectra displayed a unique force signature indicative of a specific bond between each cytochrome and the hematite surface. The strength of the OmcA-hematite bond was approximately twice as strong as the MtrC-hematite bond, but direct binding to hematite was twice as favorable for MtrC. Reversible folding/unfolding reactions were observed for mechanically denatured MtrC molecules bound to hematite. The force measurements for the hematite-cytochrome pairs were compared to spectra collected between an iron oxide and S. oneidensis under anaerobic conditions. There is a strong correlation between the whole cell and pure protein force spectra suggesting that the unique binding attributes of each cytochrome complement one another and allow both MtrC and OmcA to play a prominent role in the transfer of electrons to Fe(III) in minerals. Finally, by comparing the magnitude of binding force for the whole cell vs. pure protein data, we were able to estimate that a single bacterium of S. oneidensis (2 x 0.5 μm) expresses ~104 cytochromes on its outer surface.
2007. "Structure, Magnetism and Conductivity in Epitaxial Ti-doped -Fe2O3 Hematite: Experiment and density functional theory calculations." Physical Review. B, Condensed Matter and Materials Physics 75(10):, doi:10.1103/PhysRevB.75.104412 Abstract We explore the feasibility of growing epitaxial Ti-doped -Fe2O3 in which Ti(IV) substitutes for Fe(III) preferentially in one magnetic sublattice, but not the other. Such a structure has been predicted by first-principles theory to be energetically likely, and is expected to yield interesting and useful magnetic and electronic properties. However, we find that a majority of Ti dopants disperse and occupy random cation sites in both magnetic sublattices. Density functional theory predicts that the magnetically ordered and magnetically random structures are nearly isoenergetic.
2007. "Study of Martensitic Phase transformation in a NiTiCu Thin Film Shape Memory Alloy Using Photoelectron Emission Microscopy." Advanced Functional Materials 17(1):161-167. doi:10.1002/adfm.200600611 Abstract The thermally-induced martensitic phase transformation in a polycrystalline NiTiCu thin film shape memory alloy was probed by photoelectron emission microscopy (PEEM). In situ PEEM images reveal distinct changes in microstructure and photoemission intensity at the phase transition temperatures. In particular, images of the low temperature, martensite phase are brighter than that of the high temperature, austenite phase, due to the relatively lower work function of the martensite. Ultra-violet photoelectron spectroscopy shows that the effective work function changes by about 0.16 eV during thermal cycling. In situ PEEM images also show that the network of trenches observed on the room temperature film disappear suddenly during heating and reappear suddenly during subsequent cooling. These trenches are also characterized by atomic force microscopy at selected temperatures. We describe implications of these observations with respect to the spatial distribution of phases during thermal cycling in this thin film shape memory alloy.
2007. "An In Situ Study of the Martensitic Transformation in Shape Memory Alloys Using Photoemission Electron Microscopy." Journal of Nuclear Materials 361(2-3):306-312. doi:10.1016/j.jnucmat.2006.12.008 Abstract Thermally-induced martensitic phase transformations in polycrystalline CuZnAl and thin-film NiTiCu shape memory alloys were probed using photoemission electron microscopy (PEEM). Ultra-violet photoelectron spectroscopy shows a reversible change in the apparent work function during transformation, presumably due to the contrasting surface electronic structures of the martensite and austenite phases. In situ PEEM images provide information on the spatial distribution of these phases and the evolution of the surface microstructure during transformation. PEEM offers considerable potential for improving our understanding of martensitic transformations in shape memory alloys in real time.
2006. "Synthesis of Room-Temperature Ferromagnetic Cr-doped TiO₂(110) Rutile Single Crystals using Ion Implantation." Nuclear Instruments and Methods in Physics Research. Section B, Beam Interactions with Materials and Atoms 242(1-2):198-200. doi:10.1016/j.nimb.2005.08.149 Abstract Ferromagnetic Cr-doped rutile TiO₂ single crystals were synthesized by high-temperature ion implantation. The associated structural, compositional and magnetic properties were studied by x-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, proton induced x-ray emission, x-ray diffraction, Cr K- and L-shell near-edge x-ray absorption spectroscopy, and vibrating sample magnetometry. Cr was distributed uniformly to the depth of about 300 nm with an average concentration of ~1 at. %. The samples are semiconducting and ferromagnetic as implanted, with a saturation magnetization of 0.29B/Cr atom at room temperature. Cr is in a formal oxidation state of +3 throughout the implanted region, and no CrO₂ is detected.
2006. "Quantification of Dopant Concentrations in Diluted Magnetic Semiconductors using Ion Beam Techniques." Nuclear Instruments and Methods in Physics Research. Section B, Beam Interactions with Materials and Atoms 249(1-2):402-405. doi:10.1016/j.nimb.2006.04.038 Abstract It has recently been demonstrated that magnetically doped TiO2 and SnO2 show ferromagnetism at room-temperature and Curie temperatures above room temperature. However, accurate knowledge of dopant concentrations is necessary to quantify magnetic moments in these materials. Rutherford Backscattering spectrometry (RBS) is one of the powerful techniques to quantify magnetic transition metal dopant concentrations in these materials. However, in some cases, the interference of RBS signals for different dopants and substrate elements in these materials makes analysis difficult. In this work, we demonstrate that particle induced x-ray emission (PIXE) can be successfully used to quantify the magnetic transition element dopants in several room temperature ferromagnetic materials synthesized using three different synthesis methods: oxygen plasma assisted molecular beam epitaxy, ion implantation and wet chemical methods.
2006. "Magnetic properties of epitaxial Co-doped anatase TiO2 thin films with excellent structural quality." Journal of Vacuum Science and Technology B--Microelectronics and Nanometer Structures 24(4):2012-2017. doi:10.1116/1.2216723 Abstract The heteroepitaxy of Co-doped anatase TiO2 on LaAlO3(001) has been refined with the goal of determining the relationship between structural quality and magnetic ordering. By significantly reducing the deposition rate and substrate temperature, well-ordered Co:TiO2 films with unprecedented crystalline quality were obtained by oxygen-plasma-assisted molecular beam epitaxy, as characterized by x-ray diffraction. These films exhibit uniform Co doping, with no evidence of Co segregation or secondary phases throughout the film depth or on the surface. Despite the improvement in crystalline quality and Co distribution, the films exhibit negligible ferromagnetism, with saturation moments of only ~0.1 B/Co. This loss of ferromagnetism is in stark contrast to faster-grown Co:TiO2 films, where a higher growth rate and substrate temperature typically result in lower crystalline quality, a highly non-uniform Co distribution, and average saturation moments of ~1.2 B/Co. The presence of ferromagnetism in faster-grown Co:TiO2 does not appear to arise from intrinsic point defects present in the bulk material, such as charge-compensating oxygen vacancies, but is instead attributed to the presence of extended structural defects.
2006. "Ferromagnetism and structure of epitaxial Cr-doped anatase TiO2 thin films." Physical Review. B, Condensed Matter and Materials Physics 73(15):155327 (12 p.). doi:10.1103/PhysRevB.73.155327 Abstract The materials and magnetic properties of Cr-doped anatase TiO2 thin films deposited on LaAlO3(001) and SrTiO3(001) substrates by oxygen-plasma-assisted molecular beam epitaxy have been studied in detail to elucidate the origin of ferromagnetic ordering. Cr substitution for Ti in the anatase lattice, with no evidence of Cr interstitials, segregation, or secondary phases, was independently confirmed by transmission electron microscopy (TEM) with energy dispersive x-ray (EDX) spectroscopy, extended x-ray absorption fine structure (EXAFS), and Rutherford backscattering spectrometry (RBS) in the channeling geometry. Epitaxial films deposited at ~0.1 Å/s were found to have a highly defected crystalline structure, as quantified by high resolution x-ray diffraction (XRD). These films were also ferromagnetic at room temperature with a moment of ~0.5 B/Cr, Curie temperatures in the range of 400 – 700°C, and exhibited shape and in-plane magnetocrystalline anisotropy. However, no free carrier spin polarization was observed by Hall effect measurements, raising questions about the mechanism of magnetism. Films deposited slowly (~0.015 Å/s) possessed a nearly perfect crystalline structure as characterized by XRD. Contrary to expectations, these films exhibited negligible ferromagnetism at all Cr concentrations. Annealing in vacuum to generate additional oxygen defects and free carrier electrons did not significantly increase the ferromagnetic ordering in either fast- or slow-grown films. These results contradict both oxygen-vacancy-derived free-carrier-mediated exchange and F-center-mediated bound magnetic polaron exchange mechanisms, and instead indicate the primary role of extended structural defects in mediating the ferromagnetic ordering in doped anatase films.
2006. "Ferromagnetism in Oxide Semiconductors ." Materials Today 9(11):28-35. Abstract In order to become a practical technology, semiconductor spintronics requires the discovery and utilization of ferromagnetic semiconductors which exhibit spin polarization in the majority carrier band at and above room temperature. Intrinsic remanent magnetization would allow spin polarized currents to be propagated in such materials without the need for a continuous magnetic field. However, the discovery and understanding of such materials is proving to be a grand challenge in solid-state science. Indeed, one of the 125 critical unanswered scientific questions recently posed in Science magazine asks, “Is it possible to create magnetic semiconductors that work at room temperature?”
2005. "Epitaxial Growth and Properties of Magnetically Doped TiO₂." Chapter 7 in Thin Films and Heterostructures for Oxide Electronics, ed. Satishchandra B. Ogale, pp. 219-247. Springer, New York, NY. Abstract Spin electronics and photonics represent exciting frontiers in which new paradigms are envisioned for signal processing and computing.1-4 Using quantum mechanical spin states associated with charged particles to propagate information offers potential advantages over the use of charge alone, as in present-day technology. These advantages include the ability to combine logic and memory on the same chip, lower power consumption, decrease switching times in device architectures similar to those used today, and incorporate entirely new functionalities.
2005. "Microstructure of Co-doped TiO₂ (110) Rutile by Ion Implantation." Journal of Applied Physics 97(7):99-104. Abstract 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 (EDS), 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 1075 K with a Co ion fluence of 1.25x10¹⁶ Co/cm². Implanting at 875 K 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 simulations.
2005. "Topography of Anatase TiO₂ Film Synthesized on LaAlO₃(001) ." Nanotechnology 16(3):S18–S21. Abstract The surface of an anatase titanium dioxide (TiO₂) film grown on LaAlO₃ was observed by noncontact atomic force microscopy (NC-AFM). After cleaning with a cycle of argon ion sputtering and annealing, (1x4) and (1x5) reconstructed terraces appeared. In addition to the terraces, the sputter-annealed surface included many agglomerations. X-ray photoelectron spectroscopy analysis showed the presence of Tiⁿ⁺ (n≤3). The low diffusivity of the Tiⁿ⁺(n≤3) species generated by argon ion sputtering is responsible for the generation of the agglomerations.
2005. "Growth of Cr-doped TiO₂ Films in the Rutile and Anatase Structures by Oxygen Plasma Assisted Molecular Beam Epitaxy ." Thin Solid Films 484(1-2):289-298. Abstract As part of a search for new spintronic materials, highly ordered films of CrxTi₁-xO₂ in both rutile and anatase structure and for several Cr concentrations ranging from x=0.02 to 0.16 were grown by oxygen-plasma assisted molecular beam epitaxy. X-ray photoelectron diffraction data of the Cr 2p level exhibit the same patterns and the same modulation amplitudes as those observed for Ti 2p, providing a strong indication that a large fraction of the Cr atoms occupy substitutional lattice sites in both structures. The Cr 2p core-level spectra as well as a Cr 3d related dopant signal above the valence band of TiO₂ are characteristic of Cr³⁺ ions. At room temperature, Cr-doped anatase films exhibit ferromagnetic order with a saturation magnetization of ~0.6 µB per Cr atom and strong in-lane anisotropy.
2005. "Negligible Magnetism in Excellent Structural Quality CrxTi₁-xO₂ Anatase: Contrast with High-Tc Ferromagnetism in Structurally Defective CrxTi₁-xO₂." Physical Review Letters 95:217203. doi:10.1103/PhysRevLett.95.217203 Abstract The mechanism of ferromagnetism in doped oxides is under active debate. We reexamine doped TiO₂ anatase, using epitaxial Cr:TiO₂ with excellent structural quality as a model system. In contrast to highly oriented but defective Cr:TiO₂ (~0.5 µB/Cr), these structurally superior single crystal films exhibit negligible ferromagnetism. We show for the first time that charge compensating oxygen vacancies alone, as predicted by F-center mediated exchange, are not sufficient to activate ferromagnetism. Instead, the onset of ferromagnetism correlates with the presence of structural defects.
2005. "Co-doped Anatase TiO₂ Heteroepitaxy on Si(001)." Journal of Applied Physics 97(7):073511-073511-10. doi:10.1063/1.1868854 Abstract Pure anatase TiO₂ and CoxTi₁-x O₂ (0.01 < x < 0.04) epitaxial thin films were deposited by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE) on Si(001) for evaluation as a potential dilute magnetic semiconductor material suitable for Si-based spintronic devices. Epitaxial growth on Si(001) was facilitated by the deposition of ¼or ½ ML Sr metal on the clean Si(001) surface to form an oxidation resistant silicide layer, followed by deposition of a thin SrTiO₃ buffer layer. Using ½ ML Sr metal to form the silicide allowed the deposition of 10 ML SrTiO₃ without oxidation of the Si interface. Epitaxial anatase could be grown on this heterostructure, although use of the oxygen plasma during deposition resulted in significant SiO₂ formation. Pure anatase films consisted of epitaxial anatase surface particles on a continuous anatase film. For Co-doped films, Co segregation to surface particles of epitaxial anatase was observed by Auger electron spectroscopy and transmission electron microscopy (TEM); faceting of the particles was observed for low Co doping concentrations. Although no secondary phases containing Co were observed in Co-doped anatase films by x-ray diffraction or TEM, x-ray absorption near edge spectroscopy indicated Co was present in the films as a mixture of Co(0), Co(II), and Co(III). All samples were ferromagnetic at room temperature; for lower Co concentrations, the ferromagnetic remanence (9%) and coercive field (100 Oe) were similar to phase-pure Co:TiO₂ / LaAlO₃. However, the presence of Co(0) under strongly oxidizing growth conditions known to oxidize the Si interface implies that under no deposition conditions can Co metal be eliminated while simultaneously protecting the Si interface from oxidation.
2005. "XAFS study of CoxTi₁-xO₂-x-anatase." Physica Scripta T115:597-599. doi:10.1238/Physica.Topical.115a00597 Abstract Co doped TiO₂ anatase is a promising candidate dilute magnetic semiconductor (DMS). DMS materials have potential applications in spintronics devices. These utilize the spin of carriers, and offer the promise of new devices with enhanced functionality. The application of DMS materials to spintronics is as spin injectors. These materials can have spin-polarized states in their valence or conduction bands. At interfaces with nonmagnetic semiconductors they can then be used for spin polarized carrier injection, allowing for the fabrication of novel devices utilizing spin. Theory and measurements indicate that they can be much more efficient spin injectors than ferromagnetic metals. This report describes some recent XAFS studies of these materials using the PNC-CAT beamlines at the APS.
2005. "Cr-doped TiO₂ Anatase- A Ferromagnetic Insulator ." Journal of Applied Physics 97:046103. Abstract Epitaxial ferromagnetic films of Cr-doped TiO₂ anatase (CrxTi₁-xO₂-x/₂) were grown on LaA1O3(001) using oxygen-plasma assisted molecular beam epitaxy. Cr K-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 ~0.6 µB/Cr atom.
2004. "Room-Temperature Ferromagnetism in Ion-Implanted Co-Doped TiO₂(110) Rutile." Applied Physics Letters 84(22):4466-4468. Abstract Interest in diluted magnetic semiconductros (DMS) is growing rapidly within the emerging field of spintronics. For example, the ability to efficiently inject spin-polarized carriers into nonmagnetic semiconductor heterostructures creates new and exciting possibilities for utilizing DMS materials in spin-based devices. Several III-V and II-VI semiconductor materials doped with magnetic transition metal elements have been explored. Although these materials show promising behavior in some cases, most exhibit Curie temperatures of ~170 K or less. It has recently been shown that certain oxide semiconductors doped with magnetic transition elements show room-temperature ferromagnetism.
2004. "Room Temperature Ferromagnetism in Ion-implanted Co-doped TiO₂(110) Rutile." Applied Physics Letters 84(22):4466-4468. Abstract Ferromagnetic Co-doped rutile TiO₂ singel crystals were successfully synthesized by high temperature ion implantation and charaterized by a variety of techniques. Co is uniformly distrubuted to the depth of ~300nm with an average concentration of ~2 at. %, except in the near-surface region, where the concentration is ~3 at. %. Magnetic measurements reval ferromagnetic behavior at room temperature with an effective saturation magnetization of ~0.6 ub/Co atom. The Co formal oxidation state is found to be +2 throughouth the implanted region, and no Co(0) is detected.
2004. "Growth and Properties of molecular beam epitaxially grown ferromagnetic Fe-doped TiO2 rutile films on TiO2." Applied Physics Letters 84(18):3531-3533. Abstract 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.
2004. "Experimental Determination of Valence Band Maxima for SrTiO3, TiO2, and SrO and the Associated Valence Band Offsets with Si(001)." Journal of Vacuum Science and Technology B--Microelectronics and Nanometer Structures 22(4):2205-2215. Abstract Abstract We address the issue of accurate determination of the energy at the top of the valence band for SrTiO₃(001) single crystals, as well as TiO₂(001) anatase and SrO epitaxial films. These measurements are of critical importance in determining valence band offsets for oxides in heterojunctions involving these materials. Three different methods are presented and compared: (1) fitting Gaussian broadened theoretical densities of states to x-ray excited valence band spectra, (2) finding the intersection of a regression line that spans the linear portion of the x-ray excited valence band leading edge with the background between the valence band maximum and the Fermi level, and, (3) determining the energy at which high-resolution ultraviolet photoemission intensity of the leading edge goes to zero. We find that method 1 is not reliable due to limitations in the accuracy of density functional theory when applied to these oxides. In contrast, methods 2 and 3 give physically reasonable results that are in good mutual agreement. The difference in VBM between method 1 and methods 2 & 3 is 0.4 – 0.6 eV, depending on the oxide. The true valence band maximum can be directly and accurately measured using methods 2 & 3 provided the experiment is carried out with adequate energy resolution. PACS numbers: 79.60.Jv a)Electronic mail: sa.chambers@pnl.gov
2004. "Accurate Valence Band Maximum Determination for SrTiO₃(001) ." Surface Science 554(2-3):81-89. Abstract We reexamine a well-established method for determining valence band maxima in semiconductors based on fitting photoemission spectra to theoretical densities of states. This technique is inaccurate for certain oxides because electronic structure methods predict too sharp a leading edge rise, which in turn appears to stem from an underestimation of the extent of metal-oxygen hybridization at the top of the valence band. In contrast, extrapolating the x-ray excited leading edge to the energy axis, in combination with the energy at which the UV-excited leading edge intensity goes to zero, yields consistent and reliable results that are useful for accurate band offset determinations.
2003. "Band Offsets for the Epitaxial TiO₂/SrTiO₃/Si(001) System." Applied Physics Letters 83(18):3734-3736. Abstract 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 flat-band 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. PACS numbers: 79.60.Jv, 72.25.Dc
2003. "Local Co Structure in Epitaxial Cox Ti₁-xO₂-x Anatase." Physical Review. B, Condensed Matter and Materials Physics 67(10):22-25, art. no. 100401. Abstract The quest for diluted magnetic semiconductors (DMS) which retain their magnetism at and above room temperature is spanning several classes of materials. Such materials are critically important in the development of spintronics as spin injectors for semiconductor heterostructures that can operate without cryogenic cooling. Group IV, III-V, and II-VI DMS materials typically exhibit Curie temperatures (Tc) well below ambient due to weak interaction of the magnetic impurities. Calculations based on the Zener model of magnetism suggest that the strongest interaction is that mediated by holes, and experimental studies carried out to date have borne out this prediciton. One notable exception is that of Mn-doped GaN, which grows n-type by gas-source molecular beam epitaxy under certain conditions, and appears to be ferromagnetic at room temperature. In addition, it has recently been shown that at least one oxide semiconductor - Co-doped TiO₂ anatase or CoxTi₁-xO₂-x - is ferromagnetic well above room temperature when doped n-type by oxygen vacancies for x < ~0.1, but the mechanism of magnetism remains unknown.
2003. "Clusters and Magnetism in Epitaxial Co-doped TiO₂ Anatase." Applied Physics Letters 82(8):1257-1259. Abstract We show that under certain conditions, highly Co-enriched Ti0₂ anatase clusters nucleate on epitaxial Ti0₂ anatase grown on LaA₁O₃(001) by oxygen plasma assisted molecular beam epitaxy. In the most extreme cases, virtually all incident Co segregates to the clusters, yielding a nanoscale ferromagnitic 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
2002. "Laminar Growth of Ultrathin Metal Films on Metal Oxides: Co on Hydroxylated alpha-Al₂O₃(0001)." Science 297(5582):827-831. Abstract We show that monolayer quantities of Co metal, deposited in ultrahigh vacuum, wet the alpha-Al₂O₃(0001) surface as prepared by oxygen plasma cleaning at room temperature. While this cleaning procedure removes adventitious carbon, it does not remove the monolayer of hydroxyls resulting from dissociative chemisorption of water vapor accompanying air exposure. O 1s core-level spectra taken at grazing emission establish the presence of the OH monolayer, which is manifested in the presence of a peak ~1.7eV to higher binding energy relative to the lattice oxygen peak. After 0.3 ML Co deposition at 300K, the OH O 1s peak intensity is greatly reduced. After interaction with the surface, ~2/3 of the Co in this dose is metallic, while the remainder is Co(II). A 0.8 ML Co deposition results in a larger metallic to ionic Co ratio. First-principles density functional theory has been used to investigate several possible surface reactions that give rise to wetting. All that emit water are endothermic. However, those that emit H₂ are exothermic. Initial Co adatoms promote the removal of two H atoms per Co, and each donates two electrons to the remaining O- ions as cation sites are occupied. Exothermicity is great for the isolated process (i.e. a single Co reacting with the surface). However, the presence of residual OH and metallic Co following 0.3 ML deposition suggests metallic Co must also be present to catalyze the reaction. Metallic Co adataoms exhibit strong d-d binding to oxidized Co(II), thus producing wetting.
2002. "Epitaxial Growth and Properties of MBE Grown Ferromagnetic Co-doped TiO₂ Anatase Films on SrTiO₃(001) and LaAlO₃(001)." Thin Solid Films 418(2):197-210. Abstract We have investigated the heteroepitaxial growth and materials properties of pure and Co-doped TiO₂ anatase on SrTiO₃(001) and LaAlO₃(001), grown by oxygen plasma assisted molecular beam epitaxy. This material is a promising new diluted magnetic semiconductor that shows large magnetization and a Curie temperature well above room temperature. We have found that epitaxial films with the highest crystalline quality and most uniform distribution of Co result when a rather slow growth rate (~0.01 nm/sec) is used over a substrate temperature range of 550 degrees Celcius to 600 degrees celcius. These conditions result in layer-by-layer growth of single-crystal films, and a very low density of extremely small nanocrystalline inclusions. In contrast, growth at a higher rate (~0.04 nm/sec) leads to extensive formation of secondary phase rutile nanocrystals to which Co diffuses and segregates. The rutile nanocrystals nucleate on the evolving anatase film surface in such a way that lattice strain between the two phases is minimized. Co appears to substitute for Ti in the lattice and exhibits a ⁺² formal oxidation state. Both pure and Co-doped films are typically n-type semiconductors despite the lack of intentional n-type doping, although a wide range of conductivities is observed.
2002. "Growth of MoO3 films by oxygen plasma assisted molecular beam epitaxy." Thin Solid Films 414(2):205-215. Abstract The growth of MoO₃ films on SrLaAlO₄(0 0 1), a substrate lattice-matched to b-MoO , by oxygen plasma assisted molecular beam epitaxy was characterized using reflection high-energy electron diffraction (RHEED), X-ray photoelectron spectroscopy, Xray diffraction (XRD), and atomic force and scanning tunneling microscopies (AFM and STM).It was found that the flux of reactive oxygen species to the surface was not high enough to maintain the proper stoichiometry, even at the lowest measurable deposition rates. Therefore, the films were grown by depositing Mo in small increments and then allowing the Mo to oxidize. At 675 K, the films grew epitaxially but in a three-dimensional manner. XRD of films grown under these conditions revealed atetragonal structure that has not been previously observed in bulk MoO₃ samples.
2001. "Surface Sensitive Fe 2p Photoemission Spectra for alpha-Fe₂O₃ (0001) - The Influence of Symmetry and Crystal-Field Strength." Physical Review. B, Condensed Matter 64(20):205414-205420. Abstract We have measured high-energy-resolution Fe 2p photoelectron spectra for ⍺-Fe₂O₃/⍺-Al₂O₃(0001) grown by oxygen-plasma-assisted molecular beam epitaxy at emission angles chosen to enhance bulk and surface contributions. We quantitatively reproduce the subtle lineshape differences in these spectra by taking into account the break in symmetry and change in crystal field splitting generated by the presence of the surface.
2001. "The Role of Oxide Ionicity in Electronic Screening at Oxide/Metal Interfaces." Physical Review. B, Condensed Matter 64:075410-1 - 075410-6. Abstract Metal and oxygen core-level Auger and photoemission spectra have been measured from ultra-thin epitaxial films of Cr₂O₃ and Fe₂O₃ on Pt(111). The binding energy shifts of monolayer films relative to thicker films reveal a much smaller extent of screening by the metal substrate than that reported earlier for MgO/Ag(001). This finding suggests that the higher degree of bond covalency in Cr₂O₃ and Fe₂O₃ relative to MgO results in more effective intrinsic screening of charge transfer processes, rendering the metal much less effective for extrinsic screening. As a result, the metal is expected to have a negligible effect on the optical, electronic and magnetic properties of the oxide.