Surface chemistry on a polarizable surface: Coupling of CO with KTaO3(001).

Polarizable materials attract attention in catalysis because they have a free parameter for tuning chemical reactivity. Their surfaces entangle the dielectric polarization with surface polarity, excess charge, and orbital hybridization. How this affects individual adsorbed molecules is shown for the incipient ferroelectric perovskite KTaO3. This intrinsically polar material cleaves along (001) into KO- and TaO2-terminated surface domains. At TaO2 terraces, the polarity-compensating excess electrons form a two-dimensional electron gas and can also localize by coupling to ferroelectric distortions. TaO2 terraces host two distinct types of CO molecules, adsorbed at equivalent lattice sites but charged differently as seen in atomic force microscopy/scanning tunneling microscopy. Temperature-programmed desorption shows substantially stronger binding of the charged CO; in density functional theory calculations, the excess charge favors a bipolaronic configuration coupled to the CO. These results pinpoint how adsorption states couple to ferroelectric polarization.

Competing electronic states emerging on polar surfaces.

Excess charge on polar surfaces of ionic compounds is commonly described by the two-dimensional electron gas (2DEG) model, a homogeneous distribution of charge, spatially-confined in a few atomic layers. Here, by combining scanning probe microscopy with density functional theory calculations, we show that excess charge on the polar TaO2 termination of KTaO3(001) forms more complex electronic states with different degrees of spatial and electronic localization: charge density waves (CDW) coexist with strongly-localized electron polarons and bipolarons. These surface electronic reconstructions, originating from the combined action of electron-lattice interaction and electronic correlation, are energetically more favorable than the 2DEG solution. They exhibit distinct spectroscopy signals and impact on the surface properties, as manifested by a local suppression of ferroelectric distortions.

Ultrafast disordering of vanadium dimers in photoexcited VO2.

Many ultrafast solid phase transitions are treated as chemical reactions that transform the structures between two different unit cells along a reaction coordinate, but this neglects the role of disorder. Although ultrafast diffraction provides insights into atomic dynamics during such transformations, diffraction alone probes an averaged unit cell and is less sensitive to randomness in the transition pathway. Using total scattering of femtosecond x-ray pulses, we show that atomic disordering in photoexcited vanadium dioxide (VO2) is central to the transition mechanism and that, after photoexcitation, the system explores a large volume of phase space on a time scale comparable to that of a single phonon oscillation. These results overturn the current understanding of an archetypal ultrafast phase transition and provide new microscopic insights into rapid evolution toward equilibrium in photoexcited matter.

Zn Vacancy Formation Energy and Diffusion Coefficient of CVT ZnO Crystals in the Sub-Surface Micron Region.

By using positron annihilation spectroscopy methods, we have experimentally demonstrated the creation of isolated zinc vacancy concentrations >1020 cm-3 in chemical vapor transport (CVT)-grown ZnO bulk single crystals. X-ray diffraction ω-rocking curve (XRC) shows the good quality of ZnO single crystal with (110) orientation. The depth analysis of Auger electron spectroscopy indicates the atomic concentrations of Zn and O are almost stoichiometric and constant throughout the measurement. Boltzmann statistics are applied to calculate the zinc vacancy formation energies (Ef) of ~1.3-1.52 eV in the sub-surface micron region. We have also applied Fick's 2nd law to calculate the zinc diffusion coefficient to be ~1.07 × 10-14 cm2/s at 1100 °C. The zinc vacancies began annealing out at 300 °C and, by heating in the air, were completely annealed out at 700 °C.

Prototypical Organic-Oxide Interface: Intramolecular Resolution of Sexiphenyl on In2O3(111).

The performance of an organic semiconductor device is critically determined by the geometric alignment, orientation, and ordering of the organic molecules. Although an organic multilayer eventually adopts the crystal structure of the organic material, the alignment and configuration at the interface with the substrate/electrode material are essential for charge injection into the organic layer. This work focuses on the prototypical organic semiconductor para-sexiphenyl (6P) adsorbed on In2O3(111), the thermodynamically most stable surface of the material that the most common transparent conducting oxide, indium tin oxide, is based on. The onset of nucleation and formation of the first monolayer are followed with atomically resolved scanning tunneling microscopy and noncontact atomic force microscopy (nc-AFM). Annealing to 200 °C provides sufficient thermal energy for the molecules to orient themselves along the high-symmetry directions of the surface, leading to a single adsorption site. The AFM data suggests an essentially planar adsorption geometry. With increasing coverage, the 6P molecules first form a loose network with a poor long-range order. Eventually, the molecules reorient into an ordered monolayer. This first monolayer has a densely packed, well-ordered (2 × 1) structure with one 6P per In2O3(111) substrate unit cell, that is, a molecular density of 5.64 × 1013 cm-2.

Polarity compensation mechanisms on the perovskite surface KTaO3(001).

The stacking of alternating charged planes in ionic crystals creates a diverging electrostatic energy-a "polar catastrophe"-that must be compensated at the surface. We used scanning probe microscopies and density functional theory to study compensation mechanisms at the perovskite potassium tantalate (KTaO3) (001) surface as increasing degrees of freedom were enabled. The as-cleaved surface in vacuum is frozen in place but immediately responds with an insulator-to-metal transition and possibly ferroelectric lattice distortions. Annealing in vacuum allows the formation of isolated oxygen vacancies, followed by a complete rearrangement of the top layers into an ordered pattern of KO and TaO2 stripes. The optimal solution is found after exposure to water vapor through the formation of a hydroxylated overlayer with ideal geometry and charge.

Resolving the Structure of a Well-Ordered Hydroxyl Overlayer on In2O3(111): Nanomanipulation and Theory.

Changes in chemical and physical properties resulting from water adsorption play an important role in the characterization and performance of device-relevant materials. Studies of model oxides with well-characterized surfaces can provide detailed information that is vital for a general understanding of water-oxide interactions. In this work, we study single crystals of indium oxide, the prototypical transparent contact material that is heavily used in a wide range of applications and most prominently in optoelectronic technologies. Water adsorbs dissociatively already at temperatures as low as 100 K, as confirmed by scanning tunneling microscopy (STM), photoelectron spectroscopy, and density functional theory. This dissociation takes place on lattice sites of the defect-free surface. While the In2O3(111)-(1 × 1) surface offers four types of surface oxygen atoms (12 atoms per unit cell in total), water dissociation happens exclusively at one of them together with a neighboring pair of 5-fold coordinated In atoms. These O-In groups are symmetrically arranged around the 6-fold coordinated In atoms at the surface. At room temperature, the In2O3(111) surface thus saturates at three dissociated water molecules per unit cell, leading to a well-ordered hydroxylated surface with (1 × 1) symmetry, where the three water OWH groups plus the surface OSH groups are imaged together as one bright triangle in STM. Manipulations with the STM tip by means of voltage pulses preferentially remove the H atom of one surface OSH group per triangle. The change in contrast due to strong local band bending provides insights into the internal structure of these bright triangles. The experimental results are further confirmed by quantitative simulations of the STM image corrugation.

Well-Ordered In Adatoms at the In_{2}O_{3}(111) Surface Created by Fe Deposition.

Metal deposition on oxide surfaces usually results in adatoms, clusters, or islands of the deposited material, where defects in the surface often act as nucleation centers. Here an alternate configuration is reported. After the vapor deposition of Fe on the In_{2}O_{3}(111) surface at room temperature, ordered adatoms are observed with scanning tunneling microscopy. These are identical to the In adatoms that form when the sample is reduced by heating in ultrahigh vacuum. Density functional theory calculations confirm that Fe interchanges with In in the topmost layer, pushing the excess In atoms to the surface where they arrange as a well-ordered adatom array.

The structures of interstitial hydrogen centers in VO2 in the dilute limit from their vibrational properties and theory.

The introduction of a large concentration of H into VO2 is known to suppress the insulating phase of the metal-insulator transition that occurs upon cooling below 340 K. We have used infrared spectroscopy and complementary theory to study the properties of interstitial H and D in VO2 in the dilute limit to determine the vibrational frequencies, thermal stabilities, and equilibrium positions of isolated interstitial H and D centers. The vibrational lines of several OH and OD centers were observed to have thermal stabilities similar to that of the hydrogen that suppresses the insulating phase. Theory associates two of the four possible OH configurations for Hi in the insulating VO2 monoclinic phase with OH lines seen by experiment. Furthermore, theory predicts the energies and vibrational frequencies for configurations with Hi trapped near a substitutional impurity and suggests such defects as candidates for additional OH centers that have been observed.

Highly sensitive simple homodyne phase detector for ultrasonic pulse-echo measurements.

We have designed and built a modern versatile research-grade instrument for ultrasound pulse-echo probing of the elastic properties of a wide range of materials under laboratory conditions. The heart of the instrument lies in an AD8302 microchip: a gain and phase detector from Analog Devices, Inc. To construct the device, we have implemented a schematic that utilizes the homodyne principle for signal processing instead of the traditional superheterodyne approach. This design allows one to measure phase shifts with high precision and linearity over the entire range of 0°-360°. The system is simple in construction and usage; it makes ultrasound measurements easily accessible to a broad range of researchers. It was tested by measuring the temperature dependence of the ultrasound speed and attenuation in a KTa0.92Nb0.08O3 (KTN) single crystal at a frequency of ∼40 MHz. The tests were performed in the vicinity of the ferroelectric transitions where the large variations of the speed and attenuation demand a detector with outstanding characteristics. The described detector has a wide dynamic range and allows for measuring in a single run over the whole temperature range of the ferroelectric transitions, rather than just in limited intervals available previously. Moreover, due to the wide dynamic range of the gain measurements and high sensitivity this instrument was able to reveal previously unresolvable features associated with the development of the ferroelectric transitions of KTN crystals.

Metallization of vanadium dioxide driven by large phonon entropy.

Phase competition underlies many remarkable and technologically important phenomena in transition metal oxides. Vanadium dioxide (VO2) exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two alternative starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics and a Mott MIT where strong electron-electron correlations drive charge localization. A key missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of the transition. Here we report that the entropy driving the MIT in VO2 is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our ab initio calculations identify softer bonding in the tetragonal phase, relative to the monoclinic phase, as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. Our study illustrates the critical role of anharmonic lattice dynamics in metal oxide phase competition, and provides guidance for the predictive design of new materials.

31P magic angle spinning NMR study of flux-grown rare-earth element orthophosphate (monazite/xenotime) solid solutions: evidence of random cation distribution from paramagnetically shifted NMR resonances.

We present (31)P magic angle spinning nuclear magnetic resonance spectra of flux-grown solid solutions of La(1-x)Ce(x)PO4 (x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y(1-x)M(x)PO4 (M = V(n+), Ce(3+), Nd(3+), x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic V(n+), Ce(3+), and Nd(3+) in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensities of these peaks are related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La(3+) or Y(3+) with the paramagnetic substitutional species Ce(3+) and Nd(3+). The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the (31)P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

Ultraviolet luminescence of ScPO4, AlPO4 and GaPO4 crystals.

The luminescence of self-trapped excitons (STEs) was previously observed and described for the case of tetragonal-symmetry ScPO4 single crystals. The subject band in this material is situated in the UV spectral range of ∼210 nm or ∼5.8 eV. In the present work, we are both expanding this earlier luminescence study and seeking to identify similar luminescence phenomena in other orthophosphate crystals, i.e., AlPO4 and GaPO4. These efforts have proven to be successful--in spite of the structural differences between these materials and ScPO4. Specifically we have found that for AlPO4 and GaPO4, in addition to an α-quartz-like STE, there is a UV luminescence band that is similar in position and decay properties to that of ScPO4 crystals. Potentially this represents an STE in AlPO4 and GaPO4 crystals that is analogous to the STE of ScPO4 and other orthophosphates. The decay kinetics of the UV luminescence of ScPO4 was studied over a wide temperature range from 8 to 300 K, and they exhibited some unusual decay characteristics when subjected to pulses from an F2 excimer laser (157 nm). These features could be ascribed to a triplet state of the STE that is split in a zero magnetic field. A fast decay of the STE was detected as well, and therefore, we conclude that, in addition to the slow luminescence corresponding to a transition from the triplet state, there are singlet-singlet transitions of the STE. Time-resolved spectra of the slow and fast decay exhibit a small shift (∼0.15 eV) indicating that the singlet-triplet splitting is small and the corresponding wavefunction of the STE is widely distributed over the atoms of the ScPO4 crystal where the STE is created.

New family of cerium halide based materials: CeX3·ROH compounds containing planes, chains, and tetradecanuclear rings.

Six members of a new family of cerium-halide-based materials with promising scintillation behavior have been synthesized in single crystal form, and their crystal structures were determined. Specifically, these new compounds are [(CeCl(3))(7)(BuOH)(16)(H(2)O)(2)]·(BuOH)(2) (1), (CeBr(3))(14)(BuOH)(36) (2), [(CeCl(3))(7)(1-PrOH)(16)(H(2)O)(2)]·(1-PrOH)(2) (3), [(CeBr(3))(7)(1-PrOH)(18)]·(1-PrOH)(2) (4), [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2) (5), and CeCl(3)(sec-BuOH)(2)(H(2)O) (6). Additionally, the scintillation ability of compound 1 was established. The structures of these cerium-halide-based materials consist of catenated tetradecanuclear rings that arrange themselves into three distinct structural motifs which contain the largest lanthanide-based ring structures reported to date; the different motifs are obtained by involving specific alcohols during synthesis. Specifically, n-butanol and n-propanol lead to 1-D chains of tetradecanuclear rings, and iso-butanol leads to 2-D parquet-patterned sheets of rectangular tetradecanuclear rings, while sec-butanol results in a zigzag 1-D chain structure. One of the compounds, [(CeCl(3))(6)(iBuOH)(15)]·(iBuOH)(2), has been shown to scintillate with a light yield of up to 1920 photons/MeV, and due to the presence of protons, it should be capable of detecting high energy neutrons without the necessity of prior thermalization. Furthermore, it also appears to be the first cerium-based compound that scintillates in spite of the fact that water coordinates to two of the Ce(III) centers within the structure.

Dielectric-constant-enhanced hall mobility in complex oxides.

The high dielectric constant of doped ferroelectric KTa(1-x)Nb(x)O(3) is shown to increase dielectric screening of electron scatterers, and thus to enhance the electronic mobility, overcoming one of the key limitations in the application of functional oxides. These observations are based on transport and optical measurements as well as band structure calculations.

Photoinduced formation of zinc nanoparticles by UV laser irradiation of ZnO.

Simple exposure of single-crystal ZnO to 193 nm excimer laser radiation at room temperature results in unexpected coloration. The gray to nearly black colored material, seen principally in the irradiated laser spot, is superficial. We present unambiguous evidence that this coloration is due to high densities of metallic Zn nanoparticles growing on the exposed surface of the crystal. Higher fluence laser exposure generates accumulated surface metal just outside of the irradiated spot. We suggest that the near surface bulk is photodecomposing; thermally driven diffusion leads to surface Zn metal aggregation.

Photoinduced phase transition in VO2 nanocrystals: ultrafast control of surface-plasmon resonance.

We study the ultrafast insulator-to-metal transition in nanoparticles of VO2, obtained by ion implantation and self-assembly in silica. The nonmagnetic, strongly correlated compound VO2 undergoes a reversible phase transition, which can be photoinduced on an ultrafast time scale. In the nanoparticles, prompt formation of the metallic state results in the appearance of surface-plasmon resonance. We achieve large, ultrafast enhancement of optical absorption in the near-infrared spectral region that encompasses the wavelength range for optical-fiber communications. One can further tailor the response of the nanoparticles by controlling their shape.

Contamination in the Rare-Earth Element Orthophosphate Reference Samples.

Several of the fourteen rare-earth element (plus Sc and Y) orthophosphate standards grown at Oak Ridge National Laboratory in the 1980s and widely distributed by the Smithsonian Institution's Department of Mineral Sciences, are significantly contaminated by Pb. The origin of this impurity is the Pb2P2O7 flux that is derived from the thermal decomposition of PbHPO4. The lead pyrophosphate flux is used to dissolve the oxide starting materials at elevated temperatures (≈1360 °C) prior to the crystal synthesis. Because these rare-earth element standards are extremely stable under the electron beam and considered homogenous, they have been of enormous value to electron probe micro-analysis (EPMA). The monoclinic, monazite structure, orthophosphates show a higher degree of Pb incorporation than the tetragonal xenotime structure, orthophosphates. This paper will attempt to describe and rationalize the extent of the Pb contamination in these otherwise excellent materials.