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At least 1,279 records · Page 71

Unoccupied Electron States and the Formation of Interface between Films of Dimethyl-Substituted Thiophene–Phenylene Coolygomers and Oxidized Silicon Surface

The unoccupied electron states and the boundary potential barrier during deposition of ultrathin films of dimethyl-substituted thiophene–phenylene coolygomers of the type of CH{sub 3}–phenylene–thiophene–thiophene–phenylene–CH{sub 3} (CH{sub 3}–PTTP–CH{sub 3}) on an oxidized silicon surface have been studied. The electronic characteristics have been measured in the energy range from 5 to 20 eV above the Fermi level using total current spectroscopy (TCS). The structure of the CH{sub 3}–PTTP–CH{sub 3} film surfaces has been studied by atomic force microscopy (AFM), and the atomic compositions of the films have been studied by X-ray photoelectron spectroscopy (XPS). The changes in the maximum intensities measured by the TCS method obtained from the deposited CH{sub 3}–PTTP–CH{sub 3} film and from the substrate during increasing in the organic coating thickness to 6 nm is discussed. The formation of the boundary potential barrier in the n-Si/SiO{sub 2}/CH{sub 3}–PTTP–CH{sub 3} is accompanied by the decrease in the surface work function from 4.2 ± 0.1 to 4.0 ± 0.1 eV as the organic coating thickness increases to 3 nm. The ratio of atomic concentrations C: S in the CH{sub 3}–PTTP–CH{sub 3} films well corresponds to the chemical formula of CH{sub 3}–PTTP–CH{sub 3} molecules. The roughness of the CH{sub 3}–PTTP–CH{sub 3} coating surface was not higher than 10 nm on the ~10 × 10 μm areas as the total CH{sub 3}–PTTP–CH{sub 3}-layer thickness was about 100 nm.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Origins of enhanced thermoelectric power factor in topologically insulating Bi{sub 0.64}Sb{sub 1.36}Te{sub 3} thin films

In this research, we report the enhanced thermoelectric power factor in topologically insulating thin films of Bi{sub 0.64}Sb{sub 1.36}Te{sub 3} with a thickness of 6–200 nm. Measurements of scanning tunneling spectroscopy and electronic transport show that the Fermi level lies close to the valence band edge, and that the topological surface state (TSS) is electron dominated. We find that the Seebeck coefficient of the 6 nm and 15 nm thick films is dominated by the valence band, while the TSS chiefly contributes to the electrical conductivity. In contrast, the electronic transport of the reference 200 nm thick film behaves similar to bulk thermoelectric materials with low carrier concentration, implying the effect of the TSS on the electronic transport is merely prominent in the thin region. The conductivity of the 6 nm and 15 nm thick film is obviously higher than that in the 200 nm thick film owing to the highly mobile TSS conduction channel. As a consequence of the enhanced electrical conductivity and the suppressed bipolar effect in transport properties for the 6 nm thick film, an impressive power factor of about 2.0 mW m{sup −1} K{sup −2} is achieved at room temperature for this film. Further investigations of the electronic transport properties of TSS and interactions between TSS and the bulk band might result in a further improved thermoelectric power factor in topologically insulating Bi{sub 0.64}Sb{sub 1.36}Te{sub 3} thin films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Realizing tunable Fermi level in SnTe by defect control

The tuning of the Fermi level in tin telluride, a topological crystalline insulator, is essential for accessing its unique surface states and optimizing its electronic properties for applications such as spintronics and quantum computing. In this study, we demonstrate that the Fermi level in tin telluride can be effectively modulated by controlling the tin concentration during chemical vapor deposition synthesis. By introducing tin-rich conditions, we observed a blue shift in the x-ray photoelectron spectroscopy core-level peaks of both tin and tellurium, indicating an upward shift in the Fermi level. Further, this shift is corroborated by a decrease in work function values measured via ultraviolet photoelectron spectroscopy, confirming the suppression of Sn vacancies. Our findings provide a low-cost, scalable method to achieve tunable Fermi levels in tin telluride, offering a significant advancement in the development of materials with tailored electronic properties for next-generation technological applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

CdS and Cd-Free Buffer Layers on Solution Phase Grown Cu2ZnSn(SxSe1- x)4 :Band Alignments and Electronic Structure Determined with Femtosecond Ultraviolet Photoemission Spectroscopy

The heterojunctions formed between solution phase grown Cu2ZnSn(SxSe1- x)4(CZTS,Se) and a number of important buffer materials including CdS, ZnS, ZnO, and In2S3, were studied using femtosecond ultraviolet photoemission spectroscopy (fs-UPS) and photovoltage spectroscopy. With this approach we extract the magnitude and direction of the CZTS,Se band bending, locate the Fermi level within the band gaps of absorber and buffer and measure the absorber/buffer band offsets under flatband conditions. We will also discuss two-color pump/probe experiments in which the band bending in the buffer layer can be independently determined. Finally, studies of the bare CZTS,Se surface will be discussed including our observation of mid-gap Fermi level pinning and its relation to Voc limitations and bulk defects.

Haight, Richard↗

Solute atmospheres at dislocations

In this study, a two-dimensional plane strain elastic solution is determined for the Cottrell solute atmosphere around an edge dislocation in an infinitely long cylinder of finite radius (the matrix), in which rows of solutes are represented by cylindrical rods with in-plane hydrostatic misfit (axial misfit is also considered). The periphery of the matrix is traction-free, thus introducing an image solute field which generates a solute-solute interaction energy that has not been considered previously. The relevant energy for the field of any distribution of solutes coexistent with a single edge dislocation along the (matrix) cylinder axis is determined, and coherency effects are discussed and studied. Monte Carlo simulations accounting for all pertinent interactions over a range of temperatures are found to yield solute distributions different from classical results, namely, (1) Fermi-Dirac condensations at low temperatures at the free surface, (2) the majority of the atmosphere lying within an unexpectedly large non-linear interaction region near the dislocation core, and (3) temperature-dependent asymmetrical solute arrangements that promote bending. The solute distributions at intermediate temperatures show a 1/r dependence in agreement with previous linearized approximations. With a standard state of solute corresponding to a mean concentration, c 0 , the relevant interaction energy expression presented in this work is valid when extended to large concentrations for which Henry's Law and Vegard's Law do not apply.

36 MATERIALS SCIENCE↗

Photoluminescence studies of polycrystalline Cu(In,Ga)Se{sub 2}: Lateral inhomogeneities beyond Abbe's diffraction limit

We analyze Cu(In,Ga)Se{sub 2} absorbers with a scanning near-field optical microscope (SNOM) by photoluminescence (PL). Such measurements allow one to extract local fluctuations of the integral PL yield, the quasi-Fermi level splitting, and the material composition in the submicron range. However, the experimental findings depend strongly on the surface roughness of the absorber: If the surface is rough, artifact-prone correlations between surface contour and PL features measured by SNOM can be found that complicate the study of recombination effects. For smooth surfaces, such correlations no longer exist and the influence of grain boundaries on the integral PL yield and the quasi-Fermi level splitting is revealed. The method also allows a detailed determination of the local band gaps in neighboring grains and their spatial variation inside, and thus of possibly local changes in chemical composition of different grains.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Coulomb Electron Interaction between an Adsorbate and Substrate: a Model of a Surface Dimer

The Coulomb interaction in the adsorption (adsorbate—substrate) system is reduced to a short-range repulsion between electrons of the adsorbed particle and atom of the substrate, which form a surface dimer. It is shown that allowance for this interaction leads to increased charge transfer between components of the dimer and decreased charge transfer between the dimer and metal substrate, which is caused by variation of the Fermi level in the adsorption system.

74 ATOMIC AND MOLECULAR PHYSICS↗

Density of Electronic States in the Conduction Band of Ultrathin Films of Naphthalenedicarboxylic Anhydride and Naphthalenetetracarboxylic Dianhydride on the Surface of Oxidized Silicon

The results of examination of the electronic structure of the conduction band of naphthalenedicarboxylic anhydride (NDCA) films in the process of their deposition on the surface of oxidized silicon are presented. These results were obtained using total current spectroscopy (TCS) in the energy range from 5 to 20 eV above the Fermi level. The energy position of the primary maxima of the density of unoccupied states (DOUS) of an NDCA film was determined based on the experimental TCS data and calculated data and compared with the position of the DOUS maxima of a naphthalenetetracarboxylic dianhydride (NTCDA) film. The theoretical analysis involved calculating the energies and the spatial distribution of orbitals of the molecules under study at the B3LYP/6-31G(d) DFT (density functional theory) level and correcting the obtained energies in accordance with the procedure that was proven effective in earlier studies of the conduction band of films of small conjugated organic molecules. It was found that the DOUS maxima of the NTCDA film in the studied energy interval from 5 to 20 eV above the Fermi level are shifted toward lower electron energies by 1–2 eV relative to the corresponding DOUS maxima of the NDCA film Subdivision of the Ufa Federal Research Centre of the.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Charge transfer interactions in oligomer coated gold nanoclusters

Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, which could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Untangling charge-order dependent bulk states from surface effects in a topological kagome metal ScV 6 Sn 6

Kagome metals with charge density wave (CDW) order exhibit a broad spectrum of intriguing quantum phenomena. The recent discovery of the novel kagome CDW compound ScV 6 Sn 6 has spurred significant interest. However, understanding the interplay between CDW and the bulk electronic structure has been obscured by a profusion of surface states and terminations in this quantum material. Here, in this study, we employ photoemission spectroscopy and potassium dosing to elucidate the complete bulk band structure of ScV 6 Sn 6 , revealing multiple van Hove singularities near the Fermi level. We surprisingly discover a robust spin-polarized topological Dirac surface resonance state at the M point within the twofold van Hove singularities. Assisted by first-principles calculations, the temperature dependence of the k z -resolved angle-resolved photoemission spectroscopy spectrum provides unequivocal evidence for the proposed $\sqrt{3}$×$\sqrt{3}$×3 charge order over other candidates. Our work not only enhances the understanding of the CDW-dependent bulk and surface states in ScV 6 Sn 6 , but also establishes an essential foundation for potential manipulation of the CDW order in kagome materials.

36 MATERIALS SCIENCE↗

Solar energy protects steels against corrosion: Enhanced protection capability achieved by NiFeOx decorated BiVO4 photoanode

Highlights: • Steel corrosion is inhibited by coupling to irradiated photoanode. • NiFeO{sub x} promotes charge transfer from BiVO{sub 4} to connected steel. • BiVO{sub 4} composite photoanode decreases the self-corrosion potential of 316 steel by 256 mV. - Abstract: Coupling n-type semiconductor photoelectrode with steels provides protection from corrosion for the latter by pumping electrons produced by water oxidation reaction in a sustainable way. Although the concept of the photocathodic protection of steels has been proposed for about two decades, this technique is still far away from practical applications due to the limited protection capability. In this work, we reported that the BiVO{sub 4} photoanode significantly decreases the self-corrosion potential of 316 steel by 166 mV, and the decoration of NiFeO{sub x} films onto BiVO{sub 4} further shifts the self-corrosion potential by ∼90 mV negatively, which exhibits an excellent protection capability. The protection capability of the photoelectrode to steel is limited by the relative position of the Fermi level of the semiconducting material, and confined by the thermodynamics of the surface reactions on the semiconductor-electrolyte interface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interaction of Zinc Oxide Nanoparticles with Water: Implications for Catalytic Activity

Novel technological applications in catalysis and bactericidal formulation have emerged for zinc oxide (ZnO) nanoparticles owing to their ability to generate reactive oxygen species by fostering H 2 O dissociation. Rational improvement of those properties requires a mechanistic understanding of ZnO nanoparticle reactivity, which is currently lacking. In this work, we determine the structural and electronic properties of nanometer-sized ZnO, determine the binding energetics of H 2 O adsorption, and compare to an extended macroscopic surface. We show that the electronic density of states of ZnO nanoparticles is size-dependent, exhibiting a decreasing bandgap with the increase of nanoparticle diameter. The electronic states near the Fermi energy dominantly arise from O 2p states, which are spatially localized on “reactive” surface O atoms on the nanoparticle edges that are doubly coordinated. The frontier electronic states localized at the low coordinated atoms induce a spontaneous dissociation of H 2 O at the nanoparticle edges. The surface Zn and O atoms have inhomogeneous electronic and geometrical/topological properties, thus providing nonequivalent sites for dissociative and molecular H 2 O adsorption. The free energy of H 2 O binding is dominated by the electronic DFT interaction energy, which is site-dependent and correlated with the Bader charge of surface Zn atom. Entropy is found to stabilize the bound form, because the increase in the vibrational contribution is greater than the decrease in the translational and rotational contribution, whereas solvation stabilizes the unbound state. The absence of rough edges on an extended, macroscopic ZnO surface prevents spontaneous dissociation of a single H 2 O. This study underlies the importance of coupling geometrical and electronic degrees of freedom in determining the reactivity of nanoparticles and provides a simple elucidation of the superior catalytic activity of ZnO nanoparticles compared to ZnO in macroscopic forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Variations in the Chemical and Electronic Impact of Post-Deposition Treatments on Cu(In,Ga)(S,Se) 2 Absorbers

We present a comparative study that focuses on the variability of post-deposition treatments (NaF-PDT and KF-PDT) and their impact on the chemical and electronic structure of chalcopyrite thin film solar cell absorbers. For this purpose, two 'extreme' chalcopyrite absorber systems are studied: Cu(In,Ga)(S,Se)2 with industrial relevance (STION), and Cu(In,Ga)Se2 with 'research grade' properties (NREL). Samples were subjected to NaF-PDT and KF-PDT, and investigated using x-ray and ultra-violet photoelectron spectroscopy, Auger electron spectroscopy, as well as synchrotron-based soft x-ray emission spectroscopy. Considerably different alkali-induced effects are found for the two systems. In particular, we only detect a PDT-related Cu depletion on the NREL absorber surfaces (and only on those leading to high-efficiency devices). We also observe a reduction in the surface S/Se ratio for all alkali-treated STION absorbers, in addition to the presence of sulfates after the KF-PDT. After processing the PDT absorbers to fully operating cells, we find that the PDT temperature has a significant impact on the resulting device efficiencies - both the NREL and STION absorbers can result in high-efficiency and low-efficiency devices, depending on KF-PDT processing parameters. The absorbers of low-efficiency KF-PDT devices show the largest Cu surface content after PDT, causing the valence band maximum to be closer to the Fermi energy, thus possibly leading to less efficient charge-carrier separation and/or enhanced recombination at the interface. Finally, we find varying degrees of Na, K, and/or F residuals on the different absorber surfaces after PDT, indicating a potential 'hidden' parameter in employing PDTs for improved solar cell performance.

14 SOLAR ENERGY↗

Fast Fermi and gradient drift acceleration of electrons at nearly perpendicular collisionless shocks

Electrons can be reflected and effectively energized at quasi-perpendicular shocks. At a curved shock this process is most prominent where the upstream magnetic field and the shock surface are tangent. A theoretical explanation of the underlying physical mechanism in terms of fast Fermi acceleration has been proposed in the literature. The theory uses properties of the de Hoffmann-Teller frame and assumes conservation of magnetic moment in a static, simplified shock profile. Here, the discussion is extended in order to clarify certain aspects of the reflection process and to pinpoint the physical mechanisms that are operative and dominant from the viewpoint of the normal incidence frame. By reducing the analysis to the essential physical content and solving the pertinent energy equation, the equivalence of fast Fermi and gradient drift acceleration is shown.

Krauss-Varban, D.↗

Contactless electroreflectance studies of surface potential barrier for N- and Ga-face epilayers grown by molecular beam epitaxy

Two series of N- and Ga-face GaN Van Hoof structures were grown by plasma-assisted molecular beam epitaxy to study the surface potential barrier by contactless electroreflectance (CER). A clear CER resonance followed by strong Franz-Keldysh oscillation of period varying with the thickness of undoped GaN layer was observed for these structures. This period was much shorter for N-polar structures that means smaller surface potential barrier in these structures than in Ga-polar structures. From the analysis of built-in electric field it was determined that the Fermi-level is located 0.27 ± 0.05 and 0.60 ± 0.05 eV below the conduction band for N- and Ga-face GaN surface, respectively.

36 MATERIALS SCIENCE↗

Surface magnetism of the carbon foam: An ab-initio theoretical study

By means of ab-initio calculations, we study the surface magnetism of carbon foam, a carbon allotrope constructed by both the sp{sup 2} and sp{sup 3} hybridized carbon atoms. It is found that the sp{sup 3}-terminated surface and sp{sup 2}-terminated surface with hydrogen saturation (sp{sup 2}H) have the antiferromagnetic and ferromagnetic ground states, respectively. And the corresponding phase transition temperatures of these two surfaces are estimated to exceed 100 K. In addition, the magnetic moment of the sp{sup 2}H surface can be effectively modulated by strain. More interestingly, at the level of generalized gradient approximation, as the lattice are stretched, a bulk bandgap will open. And in such a bandgap, the sp{sup 2}H surface states can form spin polarized Dirac cones at K(K′) point. Thus, in the vicinity of the Fermi level, only the electron with a specific spin behaves like a Dirac Fermion.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Effective Hamiltonian for surface states of topological insulator thin films with hexagonal warping

The effective Hamiltonian of the surface states on semi-infinite slabs of the topological insulators (TI) Bi{sub 2}Te{sub 3} and Bi{sub 2}Se{sub 3} require the addition of a cubic momentum hexagonal warping term on top of the usual Dirac fermion Hamiltonian in order to reproduce the experimentally measured constant energy contours at intermediate values of Fermi energy. In this work, we derive the effective Hamiltonian for the surface states of a Bi{sub 2}Se{sub 3} thin film incorporating the corresponding hexagonal warping terms. We then calculate the dispersion relation of the effective Hamiltonian and show that the hexagonal warping leads distorts the equal energy contours from the circular cross sections of the Dirac cones.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Two types of surface states in topological crystalline insulators

Topological crystalline insulators (TCIs) are new states of matter whose topological distinction relies on the crystal symmetry of periodic solids. The first material realization of TCIs has recently been predicted and observed in IV-VI semiconductor SnTe and related alloys. By combining k∙p theory and band structure calculation, we present a unified approach to study topological surface states on various crystal surfaces of these TCI materials based on the electronic structure of the bulk. Depending on the surface orientation, we find two types of surface states with qualitatively different properties. Specifically, the (111) surface states consist of four Dirac cones centered at $\overline{Γ}$ and $\overline{m}$, while Dirac cones on (001) and (110) surfaces are located at non-time-reversal-invariant momenta. The latter types of surface states exhibit a Lifshitz transition as a function of Fermi energy, which is joined by a Van Hove singularity in the density of states arising from saddle points in the band structure.

36 MATERIALS SCIENCE↗