Modification of the electronic properties of the TiO2 (1 1 0) surface upon deposition of the ultrathin conjugated organic layers

A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO₂ (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (E_F) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO₂ (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO₂ (1 1 0) interface. Band bending in the TiO₂ substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO₂ (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.     

Structure of vacant electronic states of an oxidized germanium surface upon deposition of perylene tetracarboxylic dianhydride films

This paper presents the results of the investigation of the interface potential barrier and vacant electronic states in the energy range of 5 to 20 eV above the Fermi level (E_F) in the deposition of perylene tetracarboxylic dianhydride (PTCDA) films on the oxidized germanium surface ((GeO₂)Ge). The concentration of oxide on the (GeO₂)Ge surface was determined by X-ray photoelectron spectroscopy. In the experiments, we used the recording of the reflection of a test low-energy electron beam from the surface, implemented in the mode of total current spectroscopy. The theoretical analysis involves the calculation of the energy and spatial distribution of the orbitals of PTCDA molecules by the density functional theory (DFT) using B3LYP functional with the basis 6-31G(d), followed by the scaling of the calculated values of the orbital energy according to the procedure well-proven in the studies of small organic conjugated molecules. The pattern of changes in the fine structure of the total current spectra with increasing thickness of the PTCDA coating on the (GeO₂)Ge surface to 6 nm was studied. At energies below 9 eV above E_F, there is a maximum of the density of unoccupied electron states in the PTCDA film, formed mainly by π* molecular orbitals. The higher density maxima of unoccupied states are of σ* nature. The formation of the interface potential barrier in the deposition of PTCDA at the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface, E_vac–E_F, from 4.6 ± 0.1 to 4.9 ± 0.1 eV. This occurs when the PTCDA coating thickness increases to 3 nm, and upon further deposition of PTCDA, the work function of the surface does not change, which corresponds to the model of formation of a limited polarization layer in the deposited organic film.     

Electronic and thermodynamic properties of B2-FeSi from first principles

The electronic and thermodynamic properties of B2-FeSi have been investigated using the first-principles method based on the plane-wave basis set. The calculated equilibrium lattice constant is in good agreement with available experimental and theoretical data. Our results have shown that B2-FeSi was a narrow gap semiconductor of above 0.055 eV and exhibited metallic characteristics. The density of states (DOS) can also describe orbital mixing. Using the quasi-harmonic Debye model, the thermodynamic properties of B2-FeSi have been analyzed. Variations of the Debye temperature Θ_D, thermal expansion α, heat capacity C_v, entropy S and the Grüneisen parameter γ on temperature T and pressure P were obtained successfully in the ranges of 0-2400 K and 0-140 GPa.     

Quantum size effects in the optical properties of organic superlattices containing 3, 4, 9, 10 perylene tetracarboxylic dianhydride (PTCDA)

A Frenkel exciton model is applied to ultrathin films of PTCDA confined between layers of a material with electronic transitions in a different energetic region. This model accounts for the elongation of an effective internal vibration in the relaxed excited geometry of a molecule and for the transfer of an electronic excitation between different molecular sites. The comparison of the model calculations with experimental findings reveals that due to the modified conditions at the organic interfaces, boundary layers of the PTCDA films show blue-shifted transition energies with respect to inner molecular layers surrounded by the same material. The resulting changes of the lowest vibronic subband contribute further to the distinct absorption line shapes.     

Electronic properties of the polycrystalline tin dioxide interface with conjugated organic layers

The results on the electronic structure of the unoccupied electronic states of the polycrystalline SnO₂ in the energy range from 5 eV to 25 eV above the Fermi level are presented. The modification of the electronic structure and of the surface potential upon deposition of the ultrathin films of copper phthalocyanine (CuPc) and of perylene tetracarboxylic acid dianhydride (PTCDA) film onto the SnO₂ surface were studied using the very low energy electron diffraction (VLEED) method and the total current spectroscopy (TCS) measurement scheme. A substantial attenuation of the TCS signal coming from the SnO₂ surface was observed upon formation of a 1.5–2 nm thick organic deposit layer while no new spectral features from the deposit were distinguishable. It was observed that the electronic structure typical for the organic films was formed within the organic deposit thickness range from 2 nm to 7 nm. The interfacial charge transfer was characterized by the formation of the polarization layer up to 5 nm thick in the organic films. The PTCDA deposition on SnO₂ was accompanied by the negative charge transfer onto the organic layer and to the 0.65 eV increase the surface work function. At the CuPc/SnO₂ interface, the negative charge was transferred to the SnO₂ surface and the overall surface work function decreased by 0.15 eV.     

First-principles study on the structural and electronic properties of ultrathin ZnO nanofilms

Using first-principles density-functional calculations, we have studied the structural and electronic properties of ultrathin ZnO {0001} nanofilms. The structural parameters, the charge densities, band structures and density of states have been investigated. The results show that there are remarkable charge transfers from Zn to O atoms in the ZnO nanofilms. All the ZnO nanofilms exhibit direct wide band gaps compared with bulk counterpart, and the gap decreases with increased thickness of the nanofilms. The decreased band gap is associated with the weaker ionic bonding within layers and the less localization of electrons in thicker films. A staircase-like density of states occurs at the bottom of conduction band, indicating the two-dimensional quantum effects in ZnO nanofilms.     

Electronic properties of Li-doped zigzag graphene nanoribbons

Zigzag graphene nanoribbons (ZGNRs) are known to exhibit metallic behavior. Depending on structural properties such as edge status, doping and width of nanoribbons, the electronic properties of these structures may vary. In this study, changes in electronic properties of crystal by doping Lithium (Li) atom to ZGNR structure are analyzed. In spin polarized calculations are made using Density Functional Theory (DFT) with generalized gradient approximation (GGA) as exchange correlation. As a result of calculations, it has been determined that Li atom affects electronic properties of ZGNR structure significantly. It is observed that ZGNR structure exhibiting metallic behavior in pure state shows half-metal and semiconductor behavior with Li atom.     

Electronic structure and magnetic properties of the compound CeCuIn

Magnetization, magnetic susceptibility, electrical resistivity, thermoelectric power and X-ray photoemission measurements were performed on a polycrystalline sample of CeCuIn. This compound crystallizes in a hexagonal structure of the ZrNiAl type. The magnetic data indicate that CeCuIn remains paramagnetic down to 1.9 K with a paramagnetic Curie temperature of −13 K and an effective magnetic moment equal to 2.5 μ_B. The electrical resistivity has metallic character, yet in the entire temperature range studied here, it is a strongly nonlinear function of temperature. The temperature dependence of the thermoelectric power is dominated by a small positive maximum near 76 K and a deep negative minimum at about 16 K. Above 150 K the thermopower exhibits a Mott's type behavior. The positive sign of the Seebeck coefficient in this temperature region indicates that the holes are dominant charge and heat carriers. The structure of Ce 3d_5/2 and Ce 3d_3/2 XPS spectra has been interpreted in terms of the Gunnarsson-Schönhammer theory. Three final-state contributions f⁰, f¹ and f² are clearly observed, which exhibit a spin-orbit splitting Δ_SO≈18.7 eV. The appearance of the 3d⁹f⁰ component is a clear evidence of the intermediate valence behavior of Ce. From the intensity ratio I(f⁰)/[I(f⁰)+I(f¹)+I(f²)] the 4f-occupation number is estimated to be 0.95. In turn, the ratio I(f²)/[I(f¹)+I(f²)]=0.08 yields a measure of the hybridization energy that is equal to 45 meV.     

Electronic properties of single-molecule junction: Effect of the molecular distortion

For a model system consisting of a benzenedithio (BDT) molecule sandwiched between two Au plates, the electronic properties as a function of different BDT geometry are investigated using density functional theory. The distorted BDT structures are got through stretching the electrode distance. The corresponding electronic properties, including the spatial distribution of the frontier orbits, the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital levels and density of states at the Fermi energy are determined. It reveals that the molecular distortion essentially determines electronic structures. The result should be beneficial to understand the stress-dependent or structure-dependent transport mechanism of electrons of the BDT junction.     

Electronic,dielectric and mechanical properties of MoS2/SiC hybrid bilayer: A first principle study

The electronic, mechanical and dielectric properties of lateral MoS₂/SiC heterobilayer are investigated using first principles calculations. Among various stacking conformations, the energetically favorable stackings namely AA₂ and AB′₁ have been considered in the present study. The band gap of the heterobilayer shows reduction as compared to constituent monolayers which also remains stacking dependent. The electronic band-gap is further tunable by applying mechanical strain and perpendicular electric field that rendered heterostructures from semiconductor to metal at critical value of applied strain/field. The stacking of heterobilayer strongly influence its mechanical properties e.g. ultimate tensile strength of considered two favorable stacking differ by more than 50%; the ultimate tensile strain of 17% and 21% respectively has been calculated for two different stackings. The static dielectric constant also shows tunability on heterostructuring the constituent monolayers as well as applying strain and field. These tunable properties of MoS₂/SiC may be useful for the device applications at nanoscale.     

Electronic structure and optical properties of substitutional and interstitial phosphor-doped ZnO

Using first-principles method, electronic structure and optical properties of phosphorus-doped ZnO for the possible substitutional (P_Zn, P_O) and interstitial (P_tet, P_oct) doping are investigated. P_O gives p-type conductivity, but others show n-type. P_O and P_tet has a significant difference in optical properties due to the contribution of P 3p states at Fermi level.     

Influences of surface effects and large deformation on the resonant properties of ultrathin silicon nanocantilevers

The purpose of the present work is to quantify the influences of the discrete nature, the surface effects, and the large deformation on the bending resonant properties of long and ultrathin 〈100〉 silicon nanocantilevers. We accomplish this by using an analytical semi-continuum Keating model within the framework of nonlinear, finite deformation kinematics. The semi-continuum model shows that the elastic behaviors of the silicon nanocantilevers are size-dependent and surface-dependent, which agrees well with the molecular dynamics results. It also indicates that the dominant effect on the fundamental resonant frequency shift of the silicon nanocantilever is adsorption-induced surface stress, followed by the discrete nature and surface reconstruction, whereas surface relaxation has the least effect. In particular, it is found that a large deformation tends to increase the nonlinear fundamental frequency of the silicon nanocantilever, depending not only on its size but also on the surface effects. Finally, the resonant frequency shifts due to the adsorption-induced surface stress predicted by the current model are quantitatively compared with those obtained from the experimental measurement and the other existing approach. It is noticed that the length-to-thickness ratio is the key parameter that correlates the deviations in the resonant frequencies predicted from the current model and the empirical formula.     

Influences of surface effects and large deformation on the resonant properties of ultrathin silicon nanocantilevers

The purpose of the present work is to quantify the influences of the discrete nature,the surface effects,and the large deformation on the bending resonant properties of long and ultrathin 100 silicon nanocantilevers.We accomplish this by using an analytical semi-continuum Keating model within the framework of nonlinear,finite deformation kinematics.The semi-continuum model shows that the elastic behaviors of the silicon nanocantilevers are size-dependent and surfacedependent,which agrees well with the molecular dynamics results.It also indicates that the dominant effect on the fundamental resonant frequency shift of the silicon nanocantilever is adsorption-induced surface stress,followed by the discrete nature and surface reconstruction,whereas surface relaxation has the least effect.In particular,it is found that a large deformation tends to increase the nonlinear fundamental frequency of the silicon nanocantilever,depending not only on its size but also on the surface effects.Finally,the resonant frequency shifts due to the adsorption-induced surface stress predicted by the current model are quantitatively compared with those obtained from the experimental measurement and the other existing approach.It is noticed that the length-to-thickness ratio is the key parameter that correlates the deviations in the resonant frequencies predicted from the current model and the empirical formula.     

Electronic properties of cesium ultrathin coatings on the Ga-rich GaAs(100) surface

The cesium submonolayer coatings on the Ga-rich GaAs(100) surface at different coverages have been investigated by threshold photoemission spectroscopy. The electronic spectra of surface states and the ion-ization energies are analyzed. At a cesium coverage of about one-half the monolayer, the spectrum exhibits two narrow adsorption-induced bands below the Fermi level. This indicates that cesium atoms interacting with gallium dimers occupy two nonequivalent positions. It is found that the gallium broken bonds are saturated at the cesium coverage of ～0.7 monolayer, and the adsorption bonding is predominantly covalent in character. At the coverages close to the monolayer, broad bands with energies of 1.9, 2.05, and 2.4 eV have been observed for the first time. These bands can be associated with the excitation of cesium islands, cesium clusters, and surface cesium plasmon, respectively. The results obtained suggest two adsorption stages characterized by the formation of strong and weak bonds.     

Electronic structure and magnetic properties of BaTi1-xMnxO3

The electronic structure and magnetic properties of polycrystalline BaTi_1-xMn_xO₃ (x = 0–0.1) compounds prepared by solid-state reactions were studied. The results revealed that the increase in Mn content (x) did not change the oxidation numbers of Ba (+2) and Ti (+4) in BaTi_1-xMn_xO₃. However, there is the change in Mn valence that Mn^3+,4+ ions coexist in the samples with x = 0.01–0.04 while Mn⁴⁺ ions are almost dominant in the samples with x = 0.06–0.1. We also point out that Mn³⁺ and Mn⁴⁺ ions substitute for Ti⁴⁺ and prefer locating in the tetragonal and hexagonal BaTiO₃ structures, respectively, in which the hexagonal phase constitutes soon as x = 0.01. Particularly, all the samples exhibit room-temperature ferromagnetism. Ferromagnetic order increases with increasing x from 0 to 0.02, but decreases as x ≥ 0.04. We think that ferromagnetism in BaTi_1-xMn_xO₃ is related to lattice defects and/or exchange interactions between Mn³⁺ and Mn⁴⁺ ions.     

Electronic properties of a molecular system with Platinum

The electronic properties are studied using a finite homogeneous molecule called Trans-platinum-linked oligo(tetraethenylethenes). This system is composed of individual molecules such as benzene rings, platinum, Phosphore and Sulfur. The mechanism for the study of the electron transport through this system is based on placing the molecule between metal contacts to control the current through the molecular system.We study this molecule based on the tight-binding approach for the calculation of the transport properties using the Landauer-Büttiker formalism and the Fischer-Lee relationship, based on a semi-analytic Green's function method within a real-space renormalization approach. Our results show a significant agreement with experimental measurements.     

Comments on “Electronic and thermodynamic properties of B2-FeSi from first principles” [Physica B 406 (2011) 363-367]

Iron monosilicides (FeSi) is an important material with very interesting properties that can be harnessed for technological applications. Our attention has been drawn to the so-called first principle study of the electronic and thermodynamic properties of B2-FeSi by Zhao et al. (Physica B 406 (2011) 363-367) using pseudopotential plane wave method. They reported that FeSi in B2 phase is a narrow band gap material with a band gap of 0.05 eV using a generalized gradient approximation (GGA) potential implemented within the density functional theory (DFT) approximation. This comment comes to address an important oversight by these authors in the interpretation of their results.     

Electronic structure of the conduction band upon the formation of ultrathin fullerene films on the germanium oxide surface

The results of the investigation of the electronic structure of the conduction band in the energy range 5–25 eV above the Fermi level E_F and the interfacial potential barrier upon deposition of aziridinylphenylpyrrolofullerene (APP-C₆₀) and fullerene (C₆₀) films on the surface of the real germanium oxide ((GeO₂)Ge) have been presented. The content of the oxide on the (GeO₂)Ge surface has been determined using X-ray photoelectron spectroscopy. The electronic properties have been measured using the very low energy electron diffraction (VLEED) technique in the total current spectroscopy (TCS) mode. The regularities of the change in the fine structure of total current spectra (FSTCS) with an increase in the thickness of the APP-C₆₀ and C₆₀ coatings to 7 nm have been investigated. A comparison of the structures of the FSTCS maxima for the C₆₀ and APP-C₆₀ films has made it possible to reveal the energy range (6–10 eV above the Fermi level E_F) in which the energy states are determined by both the π* and σ* states and the FSTCS spectra have different structures of the maxima for the APP-C₆₀ and unsubstituted C₆₀ films. The formation of the interfacial potential barrier upon deposition of APP-C₆₀ and C₆₀ on the (GeO₂)Ge surface is accompanied by an increase in the work function of the surface E_vac–E_F by the value of 0.2–0.3 eV, which corresponds to the transfer of the electron density from the substrate to the organic films under investigation. The largest changes occur with an increase in the coating thickness to 3 nm, and with further deposition of APP-C₆₀ and C₆₀, the work function of the surface changes only slightly.     

AlSb掺Mn、Fe的电子结构和光学性质

本文基于第一性原理平面波赝势(PWP)和广义梯度近似(GGA)方法,对闪锌矿型AlSb的超晶胞、掺入杂质Mn和Fe超晶胞进行结构优化处理。计算了三种体系下AlSb超晶胞的电子结构、Mullkien电荷数和光学性质,详细研究了其能带结构、电子态密度、电荷布局分布和光学性质。结果表明：在Mn,Fe掺杂AlSb体系中,由于空穴密度的增加,禁带宽度减小,材料表现出半金属行为,且在可见光区电子跃迁明显增强。