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 structure of the conduction band of the interface region of ultrathin films of substituted perylenedicarboximides and the germanium oxide surface

The results of the investigation of the electronic structure of the conduction band and the interfacial potential barrier during the formation of interfaces of dioctyl-substituted perylenedicarboximide (PTCDI-C₈) and diphenyl-substituted perylenedicarboximide (PTCDI-Ph) ultrathin films with the oxidized germanium surface have been presented. The experimental results have been obtained using the very low energy electron diffraction (VLEED) technique in the total current spectroscopy (TCS) mode at energies in the range from 5 to 20 eV above the Fermi level E_F. The positions of the maxima of the fine structure of total current spectra (FSTCS) of the PTCDI-C₈ and PTCDI-Ph films differ significantly in the energy range from 9 to 20 eV above the Fermi level E_F, which can be associated with the difference between the substituents of the chosen molecules, dioctyl- and diphenyl-, respectively. At the same time, the positions of the lowenergy maxima in the FSTCS spectra at an energy 6–7 eV above the Fermi level E_F for the PTCDI-C₈ and PTCDI-Ph films almost coincide with each other. It has been suggested that these maxima are attributed to the electronic states of the perylene core of the molecules under investigation. The process of the formation of interfacial potential barriers of the PTCDI-C₈ and PTCDI-Ph films with the oxidized germanium surface has been analyzed. It has been found that the work functions of the surface, E_vac–E_F, differ little from 4.6 ± 0.1 eV over the entire range of organic coating thicknesses from 0 to 6 nm.     

Electronic properties of ultrathin films based on pyrrolofullerene molecules on the surface of oxidized silicon

Results of the investigation into the interface formation during the deposition of the films based on aziridinylphenylpyrrolofullerene (APP-C₆₀) up to 8 nm thick on the surface of the oxidized silicon substrate are presented. The procedure of detecting reflection of testing low-energy electron beam from the surface implemented in the total current spectroscopy mode with a change in the incident electron energy from 0 to 25 eV is used. The structure of maxima in the total current spectra induced by the APP-C₆₀ deposited film is established, and the character of interrelation of these maxima with π* and σ* energy bands in the studied materials is determined. It is revealed due to analyzing the variation in intensities of the total current spectra of the deposited APP-C₆₀ film and the (SiO₂)n-Si substrate that the APP-C₆₀ film is formed at the early deposition stage with the coating thickness thinner than one monolayer without the formation of the intermediate modified organic layer. As the APP-C₆₀/(SiO₂)n-Si interface is formed, the work function of the surface increases by 0.7 eV, which corresponds to the transfer of the electron density from substrate (SiO₂)n-Si toward the film APP-C₆₀. The optical absorption spectra of the APP-C₆₀ films are measured and compared with the spectra of films of unsubstituted C₆₀.     

Growth of germanium thin films on the W(100) surface

The growth of Ge thin films on the surface of a textured predominantly (100)-oriented tungsten ribbon is studied by thermal desorption spectrometry at different substrate temperatures over a wide range of coverages. The mechanism of growth of the Ge films at T = 300 K is similar to a layer-by-layer mechanism. For T > 300 K, the films grow through the Stranski-Krastanov mechanism, according to which the completion of the monolayer coverage is followed by the formation of three-dimensional crystallites; as a result, the desorption kinetics changes. For small coverages (i.e., in the absence of lateral interactions), the activation energy of Ge desorption from W(100) is E = 4.9 ± 0.2 eV. In a monolayer, this activation energy decreases to E = 3.9 ± 0.2 eV due to the repulsive lateral interactions. The energy of pairwise lateral interactions is determined to be ω = 0.3 eV.     

Estimation of changes in parameters of a crystal lattice and energy bands upon variation in the size of nanocrystals and nanofilms of silicides prepared by ion implantation

Changes in the parameters of the crystal lattice and energy bands of CoSi₂ nanofilms and nanocrystals formed in the surface Si layers by ion implantation combined with annealing are studied. It is shown that the band gap E _g of CoSi₂/Si(100) nanofilms with the thickness θ ≤ 40–50 Å is higher by ～0.1 eV than for “thick” films; in the case of nanocrystals, E _g is 0.3–0.4 eV higher than for macrocrystals.     

Influence of electromagnetic radiation on the phase composition of clustered CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The effect of white and UV radiation on the phase composition of amorphous CN _x films are studied by X-ray diffraction analysis and visible-range spectroscopy. The films have variable-range atomic order and consist of amorphous graphite clusters (30 Å) crystalline clusters (50–100 Å) of graphite, diamond, and carbon nitride phases; and intercluster medium with long-range (1–2 Å) atomic order. It is shown that irradiation of the films by white light facilitates the growth of fine graphite clusters. Irradiation by UV light suppresses the growth of the graphite and carbon nitride phases, favoring the growth of the diamond phase (1.5%). It is demonstrated that a change in the mesoscopic phase composition of the CN _x films causes a change in the energy gap width in the visible range from E _g = 0.75 eV for the films irradiated by white light to E _g = 1.75 eV for those exposed to UV radiation.     

Ab-initio study of structural,elastic, thermal,electronic and magnetic properties of quaternary Heusler alloys CoMnCrZ (Z = Al,As, Si,Ge)

First-principles approach is used to study the structural, electronic and magneticproperties of CoMnCrZ (Z = Al,Si, Ge and As) quaternary Heusler compounds, using full-potential linearized augmentedplane wave (FP-LAPW) scheme within the generalized gradient approximation (GGA). Thecomputed equilibrium lattice parameters agree well with the available theoretical data.The obtained negative formation energy shows that CoMnCrZ (Z = Al, Si, Ge, As) compounds have strongstructural stability. The elastic constants C _ij are calculatedusing the total energy variation with strain technique. The polycrystalline elastic moduli(namely: the shear modulus, Young’s modulus, Poisson’s ratio, sound velocities, Debyetemperature and melting temperature were derived from the obtained single-crystal elasticconstants. The ductility mechanism for the studied compounds is discussed via the elasticconstants C _ij . Our calculationswith the GGA approximation predict that CoMnCrGe, CoMnCrAl, CoMnCrSi and CoMnCrAs arehalf-metallic ferrimagnets (HMFs) with a half-metallic gap E _HM of 0.03 eV, 0.19 eV,0.34 eV and 0.50 eV for, respectively. We also find that the half-metallicity ismaintained on a wide range of lattice constants.     

Low-temperature spray-pyrolysis of FeS2 films and their electrical and optical properties

Iron disulfide (FeS₂) films with a wide range of electrical resistivities 100 Ω cm ? ρ ? 800 kΩ cm, a high adhesion to the substrate, and a resistance to aggressive media have been prepared by the spray pyrolysis of aqueous solutions of the salts FeCl₃ · 6H₂O and (NH₂)₂CS at low temperatures in the range 250°C ? T _S ? 400°C. It has been found that the FeS₂ films have a high transmittance T ≈ 60–70% and are characterized by a sharp transmission edge. It has been shown that the optical band gap for direct (E _g ^op = 2.19–2.78 eV) and indirect (E _g ^′op = 1.26–1.36 eV) optical transitions depends on the conditions of film preparation.     

Effect of heating of the electronic subsystem on the thermal stability of the C<Subscript>60</Subscript> and C<Subscript>20</Subscript> fullerenes and (C<Subscript>20</Subscript>)<Subscript>2</Subscript> cluster molecule

The effect of heating of the electronic subsystem on the thermal stability of C₆₀ and C₂₀ fullerenes and a (C₂₀)₂ cluster molecule is investigated theoretically. It is demonstrated that the excitation of electrons to upper energy levels in accordance with the Fermi-Dirac distribution function does not lead to a substantial change in the activation energy E _a for decay of the C₂₀ fullerene. The stability of the C₆₀ fullerene and the (C₂₀)₂ cluster molecule likewise does not change radically. However, the inclusion of corrections associated with the finite sizes of the heat bath leads to the activation energy E _a which is in better agreement with the calculated height of the potential barrier preventing the cluster decay.     

Electronic structure and energies of interatomic bonds in the TiSi<Subscript>2</Subscript> compound with a <Emphasis Type="Italic">C</Emphasis>49 crystal structure

Full-electron calculations of the electronic structure of the TiSi₂ compound in the structural modification C49 are performed using the augmented-plane-wave method. The total energy, the electronic band structure, and the density of states are calculated for an extended translational unit cell Ti₄Si₈, which is formed during the growth of a silicon nanowire on a p-Si substrate. Calculations are also carried out for two orthorhombic unit cells of the nonstoichiometric compositions Ti₃Si₉ and Ti₅Si₇. The energies of the interatomic bonds are determined to be E _Si-Si = 1.8 eV, E _Ti-Ti = 2.29 eV, and E _Ti-Si = 4.47 eV. The dependence of the total energy of the unit cell E _tot(V) on the unit cell volume V is obtained by optimizing the unit cell volume. The bulk modulus B ₀ = 132 GPa is determined from the Murnaghan equation of state for solids and the dependence E _tot (V). This value of the bulk modulus is used to estimate the activation energy for interstitial diffusion of silicon atoms Q _i(Si) ≈ 0.8 eV.     

Spin-Wave Resonance in Ge : Mn Thin Films with Percolation Magnetic Ordering

The mechanism of excitation and propagation of spin waves in Ge: Mn thin films with different nominal manganese concentrations (2, 4, and 8 at % Mn) with percolation magnetic ordering is explored. Concentration dependencies of Curie temperature T_C(n) and spin wave rigidity D(n) are determined, which enables to find the index of correlation distance. An exotic percolation magnetic state of samples of Ge: Mn thin films is confirmed by rectifying experimental dependences D(n) and D/T_C(n) in coordinates accepted in the percolation theory.     

Structure and stability of two-dimensional systems of C<Subscript>20</Subscript> fullerenes

Two-dimensional systems of C₂₀ fullerenes connected to each other by strong covalent bonds have been investigated. Several isomers differing in the type of intercluster bonds have been revealed. The lifetimes τ of the (C₂₀) _{M × M} complexes with M = 2 and 3 at T = 1800–3300 K have been directly calculated using the molecular dynamics method. It has been shown that these complexes lose their periodic cluster structure due usually to the coalescence of two or several neighboring C₂₀ fullerenes. The activation energy of this process determined by analyzing the τ(T) dependence appears to be E _a ≈ 2.5 eV in agreement with the calculations of the heights of the potential barriers preventing the coalescence. At high temperatures T > 2400 K, the decay of C₂₀ fullerenes entering into the complex is possible.     

Carbon segregation on a tungsten surface

New measurements are performed and a comprehensive analysis of experimental data is made on the dependence of equilibrium carbon coverage θ on a tungsten surface on its temperature and the degree of carbon loading. It is shown that if the volume is free of carbon, the variation of θ for T≥1400 K can be approximately described by the balance between the carbon flows through the boundary with the activation energy for transition into the bulk E₁=4.6 eV and the segregation energy ΔE=1.7 eV. For tungsten loaded preliminarily with carbon to a content of ≈10^?2 at. %, the θ(T) relation cannot be described in terms of the equilibrium conditions with constant E₁ and ΔE, because these quantities depend on the degree of carbon loading; E₁ grows from 4.6 to 6.8 eV and ΔE grows from 1.7 to 2.3 eV with an increase in carbon content from 0 to 10^?2 at. %. These variations are attributed to the bonds becoming stronger in carbon-loaded tungsten with increasing carbon content.     

Optical properties and mechanisms of current flow in Cu<Subscript>2</Subscript>ZnSnS<Subscript>4</Subscript> films prepared by spray pyrolysis

Thin films Cu₂ZnSnS₄ (up to 0.9 μm thick) with p-type conductivity and band gap E_g = 1.54 eV have been prepared by the spray pyrolysis of 0.1 M aqueous solutions of the salts CuCl₂ · 2H₂O, ZnCl₂ · 2H₂O, SnCl₄ · 5H₂O, and (NH₂)₂CS at a temperature T_S = 290°C. The electrophysical properties of the films have been analyzed using the model for polycrystalline materials with electrically active grain boundaries. The energy and geometric parameters of the grain boundaries have been determined as follows: the height of the barriers is E_b ≈ 0.045–0.048 eV, and the thickness of the depletion region is δ ≈ 3.25 nm. The effective concentrations of charge carriers p₀ = 3.16 × 10¹⁸ cm^–3 and their mobilities in crystallites μ_p = 85 cm²/(V s) have been found using the technique for determining the kinetic parameters from the absorption spectra of thin films at a photon energy hν ≈ E_g. The density of states at grain boundaries N_t = 9.57 × 10¹¹ cm^–2 has been estimated.     

Fine and hyperfine structure of <Emphasis Type="Italic">P</Emphasis>-wave levels in muonic hydrogen

Corrections of order α ⁵ and α ⁶ are calculated for muonic hydrogen in the fine-structure interval ΔE ^fs = E(2P _3/2) − E(2P _1/2) and in the hyperfine structure of the 2P _1/2-and 2P _3/2-wave energy levels. The resulting values of ΔE ^fs = 8352.08 μeV, ΔẼ ^hfs(2P _1/2) = 7819.80 μeV, and ΔẼ ^hfs(2P _3/2) = 3248.03 μeV provide reliable guidelines in performing a comparison with relevant experimental data and in more precisely extracting the experimental value of the (2P–2S) Lamb shift in the muonic-hydrogen atom. Original Russian Text ? A.P. Martynenko, 2008, published in Yadernaya Fizika, 2008, Vol. 71, No. 1, pp. 126–136.     

Activation energy of ion motion in the nanodimensional lattice of LaF<Subscript>3</Subscript> superionic conductor

Quantum chemistry calculations of the intracrystalline potential relief in the nanolattice of LaF₃ superionic crystal that contains 1200 ions and measures 3.5 × 2.0 × 2.2 nm along the x, y, and z axis, respectively, have been performed. Using the MOPAC 2012 program package, the potential relief profile has been simulated in the central part of the nanolattice for an elementary act of disordering in the lowest melting sublattice of F₁ ions. It has been found that the height E _m of barriers that prevent the motion of F₁ in the dielectric phase of LaF₃ crystal equals 0.37 eV and decreases to 0.15 eV in the superionic state. In addition, activation energy E _a of F₁ sublattice disordering in the dielectric and superionic states is equal to 0.16 and 0.04 eV, respectively. The profiles of the potential relief calculated on the xy and xz faces of the LaF₃ 3D nanolattice for the case when an F₁ ion moves along the x crystal axis in the dielectric state are presented. The corresponding energy barriers are 1.5–2.0 times lower than those at the center of the LaF₃ nanlattice.     

Excitation of the Yb II transitions terminating on the low-lying odd levels

Excitation of the transitions from the even levels of a singly charged ytterbium ion that terminate on the low-lying odd levels 4f ¹³(² F°)6s ^{2 2} F°, 4f ¹⁴(¹ S)6p ² P°, and 4f ¹³(² F°_7/2)5d6p(³ D)³[3/2]° is experimentally studied by measuring 51 excitation cross sections at an electron energy of 50 eV, and 16 optical excitation functions are determined within the electron energy range 0–200 eV. The largest magnitudes of the measured cross sections exceed 3 × 10^?17 cm².     

Charge transfer over localized states in a TlS single crystal

It is revealed that TlS single crystals exhibit a variable range hopping conduction along a normal to their natural layers at temperatures T ≤ 230 K in a dc electric field and a nonactivated hopping conduction at low temperatures in strong electric fields. Estimates are made for the density of states near the Fermi level (N _F = 2.8 × 10²⁰ eV^?1 cm^?3 and their energy spread (ΔW = 0.02 eV), the localization radius (a = 33 Å), the average jump distance in the region of activated (R _av(T) = 40 Å) and nonactivated (R _av(F) = 78 Å) hopping conduction, and also the drop in the charge carrier potential energy along the jump distance in an electric field F: eFR = 0.006 and 0.009 eV at F = 7.50 × 10³ and 1.25 × 10⁴ V/cm, respectively.     

On the born relation for crystals with diamond and sphalerite structure

The experimental data on the elastic constants C_ij for crystals with diamond and sphalerite structure at T=293 K were used to check the Born relation Δ4C₁₁(C₁₁?C₄₄)/(C₁₁+C₁₂)²=1. The relation was shown to be satisfied with a low accuracy for diamond due to a large scatter in the C_ij experimental values and with accuracies of 8.3, 7.6, 1.6, and 1.0% for Si, SiC, Ge, and α-Sn, respectively. For II–VI, III–V, and I–VII compounds with sphalerite structure, Λ was found to systematically deviate from unity toward lower values, and it was shown that the quantity (1-Λ) can be used to estimate the bond ionicity in these crystals. The effect of anharmonicity on the Λ values for Ge, Si, GaAs, InAs, and ZnSe was estimated; this effect was found to be insignificant.     

Evolution of surface morphology during the growth of amorphous and polycrystalline silicon films

The evolution of the surface morphology of LPCVD poly-Si films (deposition temperature 620°C), a-Si films (deposition temperature 550°C) and poly-Si films, obtained by the crystallization of a-Si is investigated in the thickness range 40–500 nm. It is found that upon an increase in the thickness from 40 to 500 nm, the surface roughness (parameters S _q , S _z , S _v ) is increased for poly-Si, while in the case of a-Si and poly-Si obtained by crystallization a-Si, on the contrary, decreases. The correlation length (S _al ) increases for all three types of silicon films. Poly-Si films, obtained by the crystallization of a-Si, as compared to LPCVD poly-Si films have a significantly lower surface roughness, respectively, S _q two times less at a thickness of 40 nm and sixteen times less at 500 nm. In contrast to thick films, thin a-Si films (at thicknesses of less than 40 nm) have a granular structure, which is especially pronounced at an average thickness of about 20 nm and there is a maximum on the dependence of the roughness S _q on the thickness.