Chemical bond approach to the electronic structure of amorphous semiconductors

The electronic structure of amorphous semiconductors with various compositions is described by the assembly of bonding, antibonding and lone-pair orbitals. Energy levels for these orbitals are calculated by extended Hückel theory. Broadening of the levels due to the interaction among chemical bonds and/or lone-pairs is determined empirically. The present calculation is free from detailed atomic structures. The changes of densities of valence states, average energy gaps and optical gaps with composition are calculated for various amorphous semiconductors. The results agree rather well with the observed ones.     

X-ray photoelectron spectroscopy of bulk glassy Se under Ar ion bombardment

It has been found that Ar ion bombardment produces reversible changes in the XPS structure of the valence band of glassy Se. The result of ion bombardment is that the 4 p bonding and non-bonding peaks merge to give a single broad peak at a binding energy similar to that of the non-bonding peak. This merger of the bonding and non-bonding peaks occurs in density of state calculations when the dihedral angle between adjacent bonds is allowe to take any angle. It is concluded, therefore, that ion bombardment introduces a random dihedral angle into the glassy structure, which subsequently relaxes to give the fixed dihedral angle, but with a random direction which density of states calculations and diffraction work indicate as the structure of the glass.     

Influence of plasma power and substrate temperature on structure of nanocrystalline germanium carbon thin films by VHF plasma CVD

The influence of plasma power and substrate temperature on the structure of nanocrystalline germanium carbon thin films was investigated. Films were deposited by the very high frequency plasma chemical vapor deposition technique using hydrogen diluted monomethylgermane (MMG). Plasma power strongly affected the decomposition of hydrogen and MMG. Crystalline volume fraction and bonding states of the atoms in the films depends on plasma power and substrate temperature. FT-IR measurements also revealed that Ge–H_n and CH_n bonds are sensitive to these factors.     

Application of the DV-Xα cluster method to calculations of the electronic structure of silicate and phosphate glasses

The electronic structure of simple silicate and phosphate clusters, which are assumed to exist in rapidly quenched Li₂O---SiO₂ and Li₂O---P₂O₅ glasses, has been calculated by the discrete variational (DV)-Xα molecular orbital method. The calculations have been carried out for several sizes of clusters, namely, tetrahedral units (SiO₄⁴⁻ and PO₄³⁻), dimers (Si₂O₇⁶⁻ and P₂O₇⁴⁻), and trimers (Si₃O₉⁶⁻ and P₃O₉³⁻). For both systems the valence electronic state is characterized by an occupied valence band, with O 2p components, and an unoccupied band of Si or P orbitals, separated by an energy gap. The energy gap between the highest occupied molecular orbital (HOMO) and the loest unoccupied molecular orbital (LUMO) decreases with increasing cluster size. A mulliken population analysis show that the negative effective charge on the non-bridging oxygens is decreased with decreasing energy gap. The bond order of the Si---O and P---O bonds, and thus the strength of these bonds, is increased with increasing cluster size.     

Vibrational properties of As2S3 glass

Vibrational densities of states and infrared and Raman spectra have been calculated for a structural model of As₂S₃ glass. The calculations are based on simple semi-empirical forms for interatomic potentials, electric dipole moment and Raman polarizability. The bands of the calculated spectra agree well with those of the observed infrared and Raman spectra of As₂S₃ glass in intensity and position, although a small concentration of the wrong SS bonds remains in the structural model and causes an additional peak in the higher frequency region. The calculated depolarization ratio of the Raman spectra is consistent with the observed one.     

Light-induced annealing of hole trap states: A new aspect of light-induced changes in hydrogenated amorphous silicon

Details of light-induced annealing of hole trap state in undoped hydrogenated amorphous silicon (a-Si:H) have been studied; it has been found that prolonged illumination significantly reduces the density of hole trap states in the energy range deeper than 0.5 eV, and subsequent thermal annealing increases the density of hole trap states and restored the sample to the initial state before the illumination. We can speculate, from the experimental results and discussion in this work, that defect conversion processes are taking place during the long exposure to light; Si dangling bonds are generated from the precursors or latent sites which manifested as hole trap states located between 0.5 and 0.7 eV from the top of the valence band.     

An investigation of the atomic bonding present in amorphous chalcogenide materials by electron spectroscopy

The atomic bonding in amorphous switching materials based on tellurium and germanium has been shown to be largely dependent on the germanium atoms. The results of examination by electron spectroscopy show that germanium atoms can possess five different forms of chemical bonding. These are elemental, oxidised, ‘glassy’, and two states associated with the interatomic compound GeTe. The ‘glassy’ and compound forms of germanium have been found in the amorphous materials. Tellurium, however, shows no significant different in bonding from its elemental state in these materials.     

Localized valence states in the forbidden gap of non-crystalline tetracene

Employing the thermally stimulated current technique the existence of three distinct gaussian trap distributions in vapor-deposited tetracene layers has been established. In layers formed at T_f ? 130 K the valence band is split into a distribution of localized states, the width being σ ? 0.06 eV, and the density N_t equal to the molecular density. Upon increasing T_f from 130 to 180 K, both N_t and σ decrease, indicating a decrease of structural disorder. For $\text{T}{}_{\mathrm{<mtext>f</mtext>}}\text{? 180}\text{K}$ the center of the trap distribution is at E₀ = 0.07 eV above the valence band. At T_f = 180 K an optimum quasi amorphous structure is formed which still lacks long-range order, but in which short-range order is present to a degree that in local regions a narrow valence band can be established. Trap distributions centered near 0.4 and 0.7 eV with a width of 0.07 and 0.1 eV, respectively, and containing about 10¹⁵ states/cm^?3, are almost independent of film formation condition, and are probably also of structural origin.     

An XPS study of the early stages of silver photodiffusion in Ag/a-As2S3 films

X-ray induced structural changes at the Ag/As₂S₃ interface are investigated using X-ray photoelectron spectroscopy on the samples prepared within the spectrometer. The as-prepared film consists of stable heteropolar As–S bonds as well as ∼16% S (and As) atoms in lower (higher) electron density configurations such as the –S–S– (–As–As–) segments with ‘wrong’ homopolar bonds. Two distinct stages of the X-ray induced diffusion are revealed. At first, silver reacts with atoms within –S–S– like segments to form Ag–S bonds. In the second stage, the Ag–S bonds decompose due to the reaction of S with As atoms within the –As–As– ‘wrong’ segments to form As–S heteropolar bonds, and silver diffuses away from the interface into the film. The results provide guideline for enhancing silver photodiffusion in chalcogenide glass. The irradiation of the (Ag–Te)/As₂S₃ sample with X-rays shows that not only Ag, but Te also diffuses away from the surface.     

Structure and properties of Ge2.5PSx glasses

Ge_2.5PS_x glasses were studied with a combination of Raman spectroscopy, nuclear magnetic resonance, and neutron diffraction. From these experiments the distribution of bonding configurations was determined, and used to explain the compositional dependence of the index of refraction and the glass transition temperature. On reducing the sulfur content of these glasses below the stoichiometric amount, the sulfur deficit is accommodated by the progressive loss of the non-bridging sulfur of SPS_3/2 groups, followed by the conversion of the resultant PS_3/2 groups into species such as P₄S₃ characterized by P-P bonding. The presence of metal-metal bonds involving germanium, found in samples with the lowest sulfur content, was found to be the most important structural feature in determining the optical response.     

Influence of surface treatments on crystalline germanium heterojunction solar cell characteristics

Hydrogenated amorphous Si (a-Si:H) has been applied to crystalline germanium (c-Ge) heterojunction solar cells and the influence of the surface treatments applied before a-Si:H deposition process has been studied. We found that PH₃ exposure treatment after surface oxide removal by annealing is effective to improve c-Ge heterojunction solar cell performance. The conversion efficiency of the c-Ge heterojunction solar cell applied PH₃ exposure treatment was up to 5.29% and the solar cell had better temperature coefficient than the c-Ge homojunction solar cell. These results suggest that the c-Ge substrate surface after oxide removal by annealing is covered with negatively charged dangling bonds, and the phosphorus adsorbed onto the c-Ge surface provides electron as a donor and corrects the band bending induced by negatively charged dangling bonds.     

Structural study of (As2S3)0.6(GeS2)0.4 glass

(As₂S₃)_0.6(GeS₂)_0.4 glass in non-irradiated and γ-irradiated states has been studied by using high-energy synchrotron X-ray diffraction, extended X-ray absorption fine structure spectroscopy, and positron annihilation lifetime spectroscopy. The experimental results are explained by the local changes around As and Ge atoms upon irradiation. These changes are suggested to involve chemical bonds distortion, formation of defective bonds with wrong coordination, rotation of structural units and appearance of additional free volume in the glass network.     

Viscosity of germanium sulfide melts

Viscosities of Ge_xS_1−x melts (0.30⩽x⩽0.44) have been measured by penetration viscometry from 10⁷ to 10¹³ Pa s. The temperature dependence of equilibrium viscosities in this range can be expressed approximately by a simple Arrhenius equation. Both the heat capacity change at the glass transition and the activation energy of viscous flow monotonously increase with germanium content as predicted by the Adam–Gibbs theory. Therefore, the connectivity of the germanium–sulfur network is reduced due to decreasing concentration of sulfur which causes increasing fragility of the undercooled liquid. The glass transition temperature exhibits a maximum near the GeS₂ composition where heteropolar bonds are predominantly formed.     

X-ray photoelectron spectroscopy of silica in theory and experiment

Fourier deconvolved X-ray photoelectron spectroscopy (XPS) valence band spectra obtained from crystalline and amorphous silica, used in conjuction with the results of quantum chemical calculations of the SiO₄ tetrahedral unit and other spectrometric measurements (soft X-ray emission, UV absorption and reflectivity, photoconductivity, photoinjection and energy loss spectroscopy), suggest a reinterpretation of the electronic band structure of silica that is consistent with all the data. A unique method for pinning the Fermi level of insulators to that of a metal calibrant is described, resulting in the ability to obtain absolute binding energies of the electronic levels in wide bandgap insulators. Observe peaks in UV reflectivity and energy loss spectra of silica are all assigned to direct interband transitions, and no excitonic states need be involved to explain the data. Upper and lower limits for the bandgap of dry crystalline (α-quartz) and amorphous (Corning Code 7940 glass) silica are adjusted downward from the 8.9 eV bandgap proposed by DiStefano and Eastman [1] to 7.8–5.55 eV for α-quartz and 7.3–5.05 eV for fused silica, respectively. This in no way compromises the obvious insulating properties of silica in MOS devices, since the conductivity is governed by the high barrier height (～3.8 eV in the case of gold) for metal-insulator electron transfer. The lowered bandgap results from increased low-energy electron density in the valence band, which we ascribe to the 1t₁ molecular orbital predicted by various quantum formalisms, but heretofore not detected experimentally in bulk (thick) silica. Disappearances of this orbital and rearrangement of the non-binding 5t₂ and 1e orbitals in silicas rich in silanols (OH), as may be the case for thin-film silica on Si metals, would increase the bandgap to 8.3 eV, in better agreement with previous determinations.     

Band alignment at the interfaces of Al2O3 and ZrO2-based insulators with metals and Si

Internal photoemission of electrons was used to determine the band alignment in metal (Mg, Al, Ni, Cu, Au)-oxide-silicon structures with Al₂O₃- and ZrO₂-based insulators. For Al₂O₃- and ZrO₂ layers grown on Si by atomic layer deposition the barrier height between the Si valence band and the oxide conduction band was found to be 3.25 and 3.1 eV, respectively. Thermal oxidation of the Si/oxide stacks results in a barrier height increase to ≈4 eV for both cases due to formation of a silicate interlayer. However, there is a significant sub-threshold electron emission both from silicon and metals, indicating a high density of states in the band gap of the insulators. These states largely determine the electron transport across metal oxides and may also account for a significant dipole component of the potential barrier at the metal/ZrO₂ and metal/Al₂O₃ interfaces.     

Modulated photoconductivity method for investigation of band gap states distribution in silicon-based thin films

It has been demonstrated that the well known modulated photocurrent technique can be modified to escape imperfect data in intrinsic parameters of amorphous and microcrystalline silicon films and to simplify measurements of the density of localized states distribution in the band gaps of these semiconductors. The information on the density-of-states distribution can be extracted from temperature dependence measurements of the constant and modulated components of the photoconductivity in the film illuminated by the light modulated with some selected frequencies. The modified method has been applied to microcrystalline hydrogenated silicon films with n- and p-type conduction. The study has demonstrated that the tail of the density-of-states distribution near the valence band of microcrystalline hydrogenated silicon is less steep than that near the conduction band.     

Modelling of point defects in monoclinic zirconia

We present the results of plane wave density functional theory calculations of oxygen vacancies and interstitial oxygen atoms in monoclinic zirconia. After calculating the incorporation energies and structures of interstitial oxygen atoms and formation energies of neutral oxygen vacancies, we consider the electron affinities and ionisation potentials of these defects. These properties are especially important at the silicon/oxide interface in MOSFET devices, where silicon may serve as an electron and hole source. The results demonstrate that interstitial oxygen atoms and positively charged oxygen vacancies can trap electrons if the electron source (band offset) is higher than ∼2 eV above the top of the zirconia valence band.     

Zn掺杂纤锌矿CdSe电子结构和光学性质的第一性原理研究

采用密度泛函理论中的广义梯度近似平面波超软赝势方法,计算研究了不同浓度Zn原子掺杂纤锌矿结构CdSe的电子与光学性质.结果显示:随着Zn掺杂浓度的升高,纤锌矿Cd1-xZnxSe的体积在减小,形成能降低,掺杂越容易,稳定性变高;Zn掺杂引起导带底向高能方向移动,禁带宽度逐渐增加;掺杂后形成的Zn-Se键具有更大的密立根重叠布居数,表现出更强的共价性;体系的直接带隙宽度增加,导致光电子跃迁峰向高能方向发生蓝移;在紫外光区9.75eV左右,掺杂体系的吸收强度达到最大,能量损失最小.     

Top‐seeded growth,optical properties and theoretical studies of noncentrosymmetric Te2V2O9

A single crystal of Te₂V₂O₉ with dimensions of 15×15×5 mm³ has been grown by the top‐seeded growth method. Infrared and transmission spectra indicate the transmission cutoff wavelength of Te₂V₂O₉ crystal is about 620 nm in visible region and 6.2 μm in infrared region. In addition, band structure and density of states calculations of Te₂V₂O₉ were carried out using the total‐energy code CASTEP based on density functional theory. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural model of glassy CdGeAs2

Attempts to construct structural models of glassy CdGeAs₂ are described. Microcrystal models with normal and appropriately distorted crystallites gave poor fits with the experiment. Relaxed random network models, in which force constants and equilibrium distances and angles obtained by an energy relaxation of the crystal were used to minimize their free energy, provided excellent agreement with experiment if only even-numbered rings and, therefore, no wrong bonds were allowed to form.