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Surface states and electronic structure of polar and nonpolar InN - An in situ photoelectron spectroscopy study

Valence band structure and surface states of InN with (0001), (000-1), (1-100), and (11-20) orientation were investigated in situ after growth using photoelectron spectroscopy. Depending on surface orientation, different occupied surface states are identified and differentiated from bulk contributions. For N-polar, m-plane, and a-plane InN, the surface states are located at the valence band maximum, while In-polar InN features surface states close to the Fermi level. The surface band alignment correlates with the position of surface states. For InN(0001), a much larger surface downward band bending is observed compared to N-polar, m-plane, and a-plane InN, where almost flat band conditions occur.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A combined electron-ion spectrometer for studying complete kinematics of molecular dissociation upon shell selective ionization

A combined electron-ion spectrometer has been built to study dissociation kinematics of molecular ions upon various electronic decay processes ensuing from ionization of neutral molecules. The apparatus can be used with various ionization agents. Ion time-of-flight (ToF) spectra arising from various electronic decay processes are acquired by triggering the ToF measurement in coincidence with energy analyzed electrons. The design and the performance of the spectrometer in a photoionization experiment is presented in detail. Electron spectra and ion time of flight spectra resulting from valence and 2p{sub 1/2} ionization of Argon and those from valence ionization of CO are presented to demonstrate the capability of the instrument. The fragment ion spectra show remarkable differences (both kinematic and cross sectional) dependent on the energy of the ejected electron, corresponding to various electron loss and decay mechanisms in dissociative photoionization of molecules.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Interfacial band configuration and electrical properties of LaAlO{sub 3}/Al{sub 2}O{sub 3}/hydrogenated-diamond metal-oxide-semiconductor field effect transistors

In order to search a gate dielectric with high permittivity on hydrogenated-diamond (H-diamond), LaAlO{sub 3} films with thin Al{sub 2}O{sub 3} buffer layers are fabricated on the H-diamond epilayers by sputtering-deposition (SD) and atomic layer deposition (ALD) techniques, respectively. Interfacial band configuration and electrical properties of the SD-LaAlO{sub 3}/ALD-Al{sub 2}O{sub 3}/H-diamond metal-oxide-semiconductor field effect transistors (MOSFETs) with gate lengths of 10, 20, and 30 μm have been investigated. The valence and conduction band offsets of the SD-LaAlO{sub 3}/ALD-Al{sub 2}O{sub 3} structure are measured by X-ray photoelectron spectroscopy to be 1.1 ± 0.2 and 1.6 ± 0.2 eV, respectively. The valence band discontinuity between H-diamond and LaAlO{sub 3} is evaluated to be 4.0 ± 0.2 eV, showing that the MOS structure acts as the gate which controls a hole carrier density. The leakage current density of the SD-LaAlO{sub 3}/ALD-Al{sub 2}O{sub 3}/H-diamond MOS diode is smaller than 10{sup −8} A cm{sup −2} at gate bias from −4 to 2 V. The capacitance-voltage curve in the depletion mode shows sharp dependence, small flat band voltage, and small hysteresis shift, which implies low positive and trapped charge densities. The MOSFETs show p-type channel and complete normally off characteristics with threshold voltages changing from −3.6 ± 0.1 to −5.0 ± 0.1 V dependent on the gate length. The drain current maximum and the extrinsic transconductance of the MOSFET with gate length of 10 μm are −7.5 mA mm{sup −1} and 2.3 ± 0.1 mS mm{sup −1}, respectively. The enhancement mode SD-LaAlO{sub 3}/ALD-Al{sub 2}O{sub 3}/H-diamond MOSFET is concluded to be suitable for the applications of high power and high frequency electrical devices.

36 MATERIALS SCIENCE↗

Site-dependent Si KL{sub 23}L{sub 23} resonant Auger electron spectra following inner-shell excitation of Cl{sub 3}SiSi(CH{sub 3}){sub 3}

Spectator resonant Auger electron spectra with the Si 1s photoexcitation of Cl{sub 3}SiSi(CH{sub 3}){sub 3} have been measured using an electron spectroscopic technique combined with undulator radiation. The transition with the highest intensity in the total ion yield (TIY) spectrum, coming from excitation of a Si 1s electron on the Cl-side into a vacant valence orbital, generates the resonant Auger decay in which the excited electron remains in this valence orbital. Photoexcitation of 1s electrons into some Rydberg orbitals induces Auger shake-down transitions, because higher-lying Rydberg orbitals in the two Si atoms closely positioned hold spatially overlapping considerably. A broad TIY peak slightly above the 1s ionization thresholds appreciably yields resonant Auger decays in which a slow photoelectron is re-captured into a higher-lying Rydberg orbital. The normal Auger peak shape at this photon energy is distorted due to a post-collision interaction effect. These findings provide a clear understanding on properties of the excited orbitals which are ambiguous in the measurement of the TIY only.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved value for the silicon free exciton binding energy

The free exciton binding energy is a key parameter in silicon material and device physics. In particular, it provides the necessary link between the energy threshold for valence to conduction band optical absorption and the bandgap determining electronic properties. The long accepted low temperature binding energy value of 14.7 ± 0.4 meV is reassessed taking advantage of developments subsequent to its original determination, leading to the conclusion that this value is definitely an underestimate. Using three largely independent experimental data sets, an improved low temperature value of 15.01 ± 0.06 meV is deduced, in good agreement with the most comprehensive theoretical calculations to date.

36 MATERIALS SCIENCE↗

Morphology, electrical, and optical properties of heavily doped ZnTe:Cu thin films

We report on a study of the physical properties of ZnTe:Cu films with Cu content up to ∼12 at. % prepared using rf magnetron sputtering. The composition and lateral homogeneities are studied using X-ray photoelectron spectroscopy (XPS). Atomic force microscopy measurements on films deposited at different substrate temperatures (up to 325 °C) yielded activation energy of 12 kJ/mole for the grains growth. The results of XPS and electrical and optical measurements provide evidence for the formation of the ternary zinc copper telluride alloy in films containing Cu concentration above ∼4 at. %. The XPS results suggest that copper is incorporated in the alloy with oxidation state Cu{sup 1+} so that the alloy formula can be written Zn{sub 1−y}Cu{sub y} Te with y = 2−x, where x is a parameter measuring the stoichiometry in the Cu site. The formation of this alloy causes appreciable shift in the binding energies of the XPS peaks besides an IR shift in the energy band gap. Detailed analysis of the optical absorption data revealed the presence of two additional transitions, besides the band gap one, originating from the Γ{sub 8} and Γ{sub 7} (spin-orbit) valence bands to a donor level at ∼0.34 eV below the Γ{sub 6} conduction band. This interpretation yields a value for the valence band splitting energy Δ≅ 0.87 eV independent of copper concentration. On the other hand, the mechanism of formation of the alloy is tentatively explained in terms of a point defect reaction in which substitutional Cu defect Cu{sub Zn} is also created. Assuming that substitutional Cu is the dominant acceptor in the Zn rich alloy as in ZnTe, its formation energy was determined to be 1.7 eV close to the theoretical value (1.41 eV) in ZnTe.

36 MATERIALS SCIENCE↗

Heterojunction band offsets and dipole formation at BaTiO{sub 3}/SrTiO{sub 3} interfaces

We used a complement of photoemission and cathodoluminescence techniques to measure formation of the BaTiO{sub 3} (BTO) on SrTiO{sub 3} (STO) heterojunction band offset grown monolayer by monolayer by molecular beam epitaxy. X-ray photoemission spectroscopy (XPS) provided core level and valence band edge energies to monitor the valence band offset in-situ as the first few crystalline BTO monolayers formed on the STO substrate. Ultraviolet photoemission spectroscopy (UPS) measured Fermi level positions within the band gap, work functions, and ionization potentials of the growing BTO film. Depth-resolved cathodoluminescence spectroscopy measured energies and densities of interface states at the buried heterojunction. Kraut-based XPS heterojunction band offsets provided evidence for STO/BTO heterojunction linearity, i.e., commutativity and transitivity. In contrast, UPS and XPS revealed a large dipole associated either with local charge transfer or strain-induced polarization within the BTO epilayer.

36 MATERIALS SCIENCE↗

Combined photoelectron, collision-induced dissociation, and computational studies of parent and fragment anions of N-paranitrophenylsulfonylalanine and N-paranitrophenylalanine

After synthesizing the compounds N-paranitrophenylsulfonylalanine (NPNPSA) and N-paranitrophenylalanine (NPNPA), the photoelectron spectrum of the valence anion of N-paranitrophenylsulfonylalanine (NPNPSA){sup −}, was measured and the collision-induced dissociation (CID) pathways of deprotonated N-paranitrophenylsulfonylalanine (NPNPSA-H){sup −} and deprotonated N-paranitrophenylalanine (NPNPA-H){sup −} were determined. Pertinent calculations were conducted to analyze both sets of experimental data. From the valence anion photoelectron spectrum of (NPNPSA){sup −}, the adiabatic electron affinity (AEA) of NPNPSA was determined to be 1.7 ± 0.1 eV, while the vertical detachment energy (VDE) of (NPNPSA){sup −} was found to be 2.3 ± 0.1 eV. Calculations for four low lying conformers of (NPNPSA){sup −} gave AEA values in the range of 1.6–2.1 eV and VDE values in the range of 2.0–2.4 eV. These calculations are in very good agreement with the experimental values. While the NPNPA anion (NPNPSA){sup −} was not observed experimentally it was studied computationally. The six low lying (NPNPSA){sup −} conformers were identified and calculated to have AEA values in the range of 0.7–1.2 eV and VDE values in the range of 0.9–1.6 eV. CID was used to study the fragmentation patterns of deprotonated NPNPA and deprotonated NPNPSA. Based on the CID data and calculations, the excess charge was located on the delocalized π-orbitals of the nitrobenzene moiety. This is made evident by the fact that the dominant fragments all contained the nitrobenzene moiety even though the parent anions used for the CID study were formed via deprotonation of the carboxylic acid. The dipole-bound anions of both molecules are studied theoretically using the results of previous studies on nitrobenzene as a reference.

74 ATOMIC AND MOLECULAR PHYSICS↗

Band-structure analysis from photoreflectance spectroscopy in (Ga,Mn)As

Modulation photoreflectance spectroscopy has been applied to study the band-structure evolution in (Ga,Mn)As epitaxial layers with increasing Mn content. Structural and magnetic properties of the layers were characterized with high-resolution X-ray diffractometry and SQUID magnetometery, respectively. The revealed results of decrease in the band-gap-transition energy in the (Ga,Mn)As layers with increasing Mn content are interpreted in terms of a disordered valence band, extended within the band gap, formed, in highly Mn-doped (Ga,Mn)As, as a result of merging the Mn-related impurity band with the host GaAs valence band.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Origin of improved scintillation efficiency in (Lu,Gd){sub 3}(Ga,Al){sub 5}O{sub 12}:Ce multicomponent garnets: An X-ray absorption near edge spectroscopy study

In the recent successful improvement of scintillation efficiency in Lu{sub 3}Al{sub 5}O{sub 12}:Ce driven by Ga{sup 3+} and Gd{sup 3+} admixture, the “band-gap engineering” and energy level positioning have been considered the valid strategies so far. This study revealed that this improvement was also associated with the cerium valence instability along with the changes of chemical composition. By utilizing X-ray absorption near edge spectroscopy technique, tuning the Ce{sup 3+}/Ce{sup 4+} ratio by Ga{sup 3+} admixture was evidenced, while it was kept nearly stable with the Gd{sup 3+} admixture. Ce valence instability and Ce{sup 3+}/Ce{sup 4+} ratio in multicomponent garnets can be driven by the energy separation between 4f ground state of Ce{sup 3+} and Fermi level.

36 MATERIALS SCIENCE↗

Interfacial band alignment and structural properties of nanoscale TiO{sub 2} thin films for integration with epitaxial crystallographic oriented germanium

We have investigated the structural and band alignment properties of nanoscale titanium dioxide (TiO{sub 2}) thin films deposited on epitaxial crystallographic oriented Ge layers grown on (100), (110), and (111)A GaAs substrates by molecular beam epitaxy. The TiO{sub 2} thin films deposited at low temperature by physical vapor deposition were found to be amorphous in nature, and high-resolution transmission electron microscopy confirmed a sharp heterointerface between the TiO{sub 2} thin film and the epitaxially grown Ge with no traceable interfacial layer. A comprehensive assessment on the effect of substrate orientation on the band alignment at the TiO{sub 2}/Ge heterointerface is presented by utilizing x-ray photoelectron spectroscopy and spectroscopic ellipsometry. A band-gap of 3.33 ± 0.02 eV was determined for the amorphous TiO{sub 2} thin film from the Tauc plot. Irrespective of the crystallographic orientation of the epitaxial Ge layer, a sufficient valence band-offset of greater than 2 eV was obtained at the TiO{sub 2}/Ge heterointerface while the corresponding conduction band-offsets for the aforementioned TiO{sub 2}/Ge system were found to be smaller than 1 eV. A comparative assessment on the effect of Ge substrate orientation revealed a valence band-offset relation of ΔE{sub V}(100) > ΔE{sub V}(111) > ΔE{sub V}(110) and a conduction band-offset relation of ΔE{sub C}(110) > ΔE{sub C}(111) > ΔE{sub C}(100). These band-offset parameters are of critical importance and will provide key insight for the design and performance analysis of TiO{sub 2} for potential high-κ dielectric integration and for future metal-insulator-semiconductor contact applications with next generation of Ge based metal-oxide field-effect transistors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Correlation between the electronic and atomic structure, transport properties, and oxygen vacancies on La{sub 0.7}Ca{sub 0.3}MnO{sub 3} thin films

We present a study of the role of oxygen vacancies on the atomic and electronic structure and transport properties on a 20 nm thick La{sub 0.7}Ca{sub 0.3}MnO{sub 3} film grown by the pulsed laser deposition method on a SrTiO{sub 3} (001) substrate. The results show that oxygen vacancies induce an atomic structure modification characterized by the movement of the La/Ca cations to the perovskite regular position, by the reduction of the MnO{sub 6} basal plane rotation, and by a cooperative tilting of the octahedra along the out-of-plane direction. The out-of-plane lattice parameter increases due to the reduction of the Mn valence upon oxygen vacancies creation. As a consequence, a shift of the Metal-to-Insulator transition to lower temperatures is found to occur. We discuss the influence of the competitive phenomena of manganese valence and Mn-O-Mn bond distortion on the transport properties of manganite thin films.

36 MATERIALS SCIENCE↗

Microscopic origin of the π states in epitaxial silicene

We investigated the electronic properties of epitaxial silicene on ZrB{sub 2}(0001) thin film grown on Si(111) by means of low-temperature scanning tunneling spectroscopy and density functional theory calculations. The position of silicon atoms and thus, the localization of the valence and conduction states were deducted from the comparison of the spectra and the computed local density of states. We point out the strong contribution of p{sub z} orbitals of specific atoms to those states which indicates the π character of the conduction and valence bands. A clear correlation between hybridization of the orbitals of the Si atoms and the buckling was evidenced.

36 MATERIALS SCIENCE↗

Electronic structure of Al- and Ga-doped ZnO films studied by hard X-ray photoelectron spectroscopy

Al- and Ga-doped sputtered ZnO films (AZO, GZO) are semiconducting and metallic, respectively, despite the same electronic valence structure of the dopants. Using hard X-ray photoelectron spectroscopy we observe that both dopants induce a band in the electronic structure near the Fermi level, accompanied by a narrowing of the Zn 3d/O 2p gap in the valence band and, in the case of GZO, a substantial shift in the Zn 3d. Ga occupies substitutional sites, whereas Al dopants are in both substitutional and interstitial sites. The latter could induce O and Zn defects, which act as acceptors explaining the semiconducting character of AZO and the lack of variation in the optical gap. By contrast, mainly substitutional doping is consistent with the metallic-like behavior of GZO.

36 MATERIALS SCIENCE↗

Ionization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy

Strong-field induced ionization and dissociation dynamics of vinyl bromide, CH{sub 2}=CHBr, are probed using femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy. Strong-field ionization is initiated with an intense femtosecond, near infrared (NIR, 775 nm) laser field. Femtosecond XUV pulses covering the photon energy range of 50-72 eV probe the subsequent dynamics by measuring the time-dependent spectroscopic features associated with transitions of the Br (3d) inner-shell electrons to vacancies in molecular and atomic valence orbitals. Spectral signatures are observed for the depletion of neutral C{sub 2}H{sub 3}Br, the formation of C{sub 2}H{sub 3}Br{sup +} ions in their ground (X{sup ~}) and first excited (A{sup ~}) states, the production of C{sub 2}H{sub 3}Br{sup ++} ions, and the appearance of neutral Br ({sup 2}P{sub 3/2}) atoms by dissociative ionization. The formation of free Br ({sup 2}P{sub 3/2}) atoms occurs on a timescale of 330 ± 150 fs. The ionic A{sup ~} state exhibits a time-dependent XUV absorption energy shift of ∼0.4 eV within the time window of the atomic Br formation. The yield of Br atoms correlates with the yield of parent ions in the A{sup ~} state as a function of NIR peak intensity. The observations suggest that a fraction of vibrationally excited C{sub 2}H{sub 3}Br{sup +} (A{sup ~}) ions undergoes intramolecular vibrational energy redistribution followed by the C–Br bond dissociation. The C{sub 2}H{sub 3}Br{sup +} (X{sup ~}) products and the majority of the C{sub 2}H{sub 3}Br{sup ++} ions are relatively stable due to a deeper potential well and a high dissociation barrier, respectively. The results offer powerful new insights about orbital-specific electronic processes in high field ionization, coupled vibrational relaxation and dissociation dynamics, and the correlation of valence hole-state location and dissociation in polyatomic molecules, all probed simultaneously by ultrafast table-top XUV spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunnel optical radiation in In{sub x}Ga{sub 1−x}N

An investigation of tunnel optical radiation in epitaxial layers of n-type In{sub x}Ga{sub 1−x}N grown on p-type GaN by novel plasma based migration enhanced epitaxy is presented. Experimental results of electro-luminescence spectra for In{sub x}Ga{sub 1−x}N/p−GaN hetero-junctions were obtained and they show two well expressed optical bands - one in range 500-540 nm and other in range 550-610 nm. An interesting detail is that each band begins and ends by sharp drops of the radiation, which nearly approach zero. A theoretical investigation of the unusual behavior of these spectra was done using LCAO electron band structure calculations. The optical ranges of these bands show that the radiation occurs in the In{sub x}Ga{sub 1−x}N region. In fact, substitutions of In atoms in Ga sites creates defects in the structure of In{sub x}Ga{sub 1−x}N and the corresponding LCAO matrix elements are found on this basis. The LCAO electron band structures are calculated considering the interactions between nearest-neighbor orbitals. Electron energy pockets are found in both the conduction and the valence bands at the Γ point of the electron band structures. Also it is found that these pockets are separated by distances, for which there is overlapping between the electron wave functions describing localized states belonging to the pockets, and as a result tunnel optical radiation can take place. This type of electron transition - between such a pocket in the conduction band and a pocket in the valence band - occurs in In{sub x}Ga{sub 1−x}N, causing the above described optical bands. This conclusion concurs with the fact that the shapes of these bands change with change of the applied voltage.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Probing the electronic structure and Au–C chemical bonding in AuC{sub 2}{sup −} and AuC{sub 2} using high-resolution photoelectron spectroscopy

We report photoelectron spectroscopy (PES) and high-resolution PE imaging of AuC{sub 2}{sup −} at a wide range of photon energies. The ground state of AuC{sub 2}{sup −} is found to be linear (C{sub ∞v}, {sup 1}Σ{sup +}) with a …8π{sup 4}4δ{sup 4}17σ{sup 2}9π{sup 4}18σ{sup 2} valence configuration. Detachments from all the five valence orbitals of the ground state of AuC{sub 2}{sup −} are observed at 193 nm. High-resolution PE images are obtained in the energy range from 830 to 330 nm, revealing complicated vibronic structures from electron detachment of the 18σ, 9π, and 17σ orbitals. Detachment from the 18σ orbital results in the {sup 2}Σ{sup +} ground state of neutral AuC{sub 2}, which, however, is bent due to strong vibronic coupling with the nearby {sup 2}Π state from detachment of a 9π electron. The {sup 2}Σ{sup +}–{sup 2}Π vibronic and spin-orbit coupling results in complicated vibronic structures for the {sup 2}Σ{sup +} and {sup 2}Π{sub 3/2} states with extensive bending excitations. The electron affinity of AuC{sub 2} is measured accurately to be 3.2192(7) eV with a ground state bending frequency of 195(6) cm{sup −1}. The first excited state ({sup 2}A′) of AuC{sub 2}, corresponding to the {sup 2}Π{sub 3/2} state at the linear geometry, is only 0.0021 eV above the ground state ({sup 2}A′) and has a bending frequency of 207(6) cm{sup −1}. The {sup 2}Π{sub 1/2} state, 0.2291 eV above the ground state, is linear with little geometry change relative to the anion ground state. The detachment of the 17σ orbital also results in complicated vibronic structures, suggesting again a bent state due to possible vibronic coupling with the lower {sup 2}Π state. The spectrum at 193 nm shows the presence of a minor species with less than 2% intensity relative to the ground state of AuC{sub 2}{sup −}. High-resolution data of the minor species reveal several vibrational progressions in the Au–C stretching mode, which are assigned to be from the metastable {sup 3}Π{sub 2,1,0} spin-orbit excited states of AuC{sub 2}{sup −} to the {sup 2}Π{sub 3/2,1/2} spin-orbit states of neutral AuC{sub 2}. The spin-orbit splittings of the {sup 3}Π and {sup 2}Π states are accurately measured at the linear geometry. The current study provides a wealth of electronic structure information about AuC{sub 2}{sup −} and AuC{sub 2}, which are ideal systems to investigate the strong Σ–Π and spin-orbit vibronic couplings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic processes and polarizability of sodium atom in Debye plasmas

Dynamic processes including excitation and ionization, and spectrum parameters including the oscillator strengths, dipole polarizabilities from the orbital 3s,3p of sodium atom embedded in weakly coupled plasma are investigated in the entire energy range of a non-relativistic regime. The interaction between the valence electron and the atomic core is simulated by a model potential, and the plasma screening of the Coulomb interaction between charged particles is described by the Debye-Hückel model. The screening of Coulomb interactions reduces the number of bound states, decreases their binding energies, broadens their radial distribution of electron wave functions, and significantly changes the continuum wave functions including the amplitudes and phase-shift. These changes strongly affect the dipole matrix elements between the bound-bound and bound-continuum states, and even the oscillator strengths, the photo-ionization cross sections and the dipole polarizabilities. The plasma screening effect changes the interaction between the valence electron and the atomic core into a short-range potential. The energy behaviors of photo-ionization cross sections are unfolded, for instance, its low-energy behavior (obeying Wigner threshold law), and the appearance of multiple shape and virtual-state resonances when the upper bound states emerge into the continuum. The Combet-Farnoux and Cooper minima in the photo-ionization cross sections are also investigated, and here, the Cooper minima appear not only for the l→l+1 channel but also for l→l−1 one, different from that of hydrogen-like ions in a Debye plasma, which appear only in the l→l+1 channel. The total static electric dipole polarizabilities monotonously and dramatically increase with the plasma screening effect increasing, which are similar to those of hydrogen-like ions and lithium atom. Comparison of calculated results for the oscillator strength, the photo-ionization cross section and polarizability with the results of other authors, when available, is made.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗