Endohedral impurities in carbon nanotubes

A generalization of the Anderson model that includes pseudo-Jahn-Teller impurity coupling is proposed to describe distortions of an endohedral impurity in a carbon nanotube. Within mean-field theory, spontaneous axial symmetry breaking is found when the vibronic coupling strength g exceeds a critical value. The effective potential is found to have O(2) symmetry, in agreement with numerical calculations. For metallic zigzag nanotubes endohedrally doped with transition metals in the dilute limit, the low-energy properties of the system may display two-channel Kondo behavior; however, strong vibronic coupling is seen to exponentially suppress the Kondo energy scale.     

Electronic structure of Yb<Superscript>3+</Superscript> impurity centers in fluorites

The electronic structure and g factors of simple impurity centers and hexamer ytterbium clusters in fluorites have been calculated in terms of the exchange charge model. Preliminarily, their local crystal structures have been calculated in the framework of the shell model with the inclusion of lattice distortions near the impurity.     

Hole trapping at Al impurities in silica: a challenge for density functional theories

The atomic geometry and electronic structure around a neutral substitutional Al impurity in silica is investigated using either the unrestricted Hartree-Fock (UHF) approximation, or Beckes three-parameter hybrid functional (B3LYP). It is found that the B3LYP functional fails to describe the structural distortions around the Al impurity, while the UHF results are consistent with experimental information. We argue that the failure of the B3LYP functional is caused by the incomplete self-interaction cancellation usually present in density functional theories.     

Effects of phosphorus-doping upon the electronic structures of single wall carbon nanotubes

The phosphorus-doped single wall carbon nanotube (PSWCNT) is studied by using First-Principle methods based on Density Function Theory (DFT). The formation energy, total energy, band structure, geometry structure and density of states are calculated. It is found that the formation energy of the P-doped single carbon nanotubes increases with diameters; the total energy of carbon nanotubes with the same diameter decreases as the doping rate increases. The effects of impurity position on the impurity level are discussed. It illustrates that the position of the impurity level may depend on the C-P-C bond angle. According to the above results, it is feasible to substitute a carbon atom with a phosphorus atom in SWCNT. It is also found that P-doped carbon nanotubes are N type semiconductor. Supported by the Natural Science Foundation of Fujian Province of China (Grant No. A0220001)     

Electric-field gradients at Ta impurities in Sc2O3 semiconductor

In this work we present an ab initio study of Ta-doped Sc₂O₃ semiconductor. Calculations were performed at dilute Ta impurities located at both cationic sites of the host structure, using the Augmented Plane Wave plus Local Orbitals (APW+lo) method. The structural atomic relaxations and the electric-field gradients (EFG) were studied for different charge states of the cell in order to simulate different ionization states of the double-donor Ta impurity. From the results for the EFG tensor at Ta impurity sites and the comparison with experimental results obtained using the Time-Differential γ–γ Perturbed-Angular-Correlations technique we could determined the structural distortions induced by the Ta impurity and the electronic structure of the doped-semiconductor.     

Neutron diffraction study of the nano-inhomogeneities of the sphalerite crystal structure induced by magnetoactive 3d ions in II–VI solid solutions

It is shown by means of the thermal neutron diffraction method that, during the doping of Zn-chalcogenide semiconductor crystals with 3d ions, elongated distortions whose spatial topology depends on the type of impurity can be formed in the sphalerite modification based on the initial crystal structure. Experimental results are discussed using the concept of vibronic interaction induced by foreign ions with partially filled outer electron shells in the cubic crystal field.     

Investigations of the local lattice distortions and the EPR parameters for the orthorhombic Pt3+ center in YAG

The local lattice distortions and the EPR parameters (anisotropic g factors and the hyperfine structure constants) for the orthorhombic Pt³⁺ center in YAG are theoretically investigated from the perturbation formulas of these parameters for a 5d⁷ ion in an orthorhombically elongated octahedron. The [ PtO₆] ^9- cluster on Al³⁺ site is found to experience the axial elongation of about 0.01 Å along Z axis, and the planar impurity-ligand bond lengths suffer the relative variation of about 0.11 Å? along X and Y axes due to the Jahn-Teller effect. As a result, the above local lattice distortions produce significant orthorhombic deformation, whereas the original slight trigonal distortion of the host [ AlO₆] ^9- octahedron is entirely depressed by the Jahn-Teller effect. The calculated EPR parameters based on the above lattice distortions show good agreement with the experimental data, and the local structure of the impurity center is also discussed.     

Tetragonal distortions of the octahedral environments of Cr3+, Fe3+ and Gd3+ ions in A2CdF4 (A = Rb,Cs) and ACdF3 crystals

Abstract

The tetragonal distortions of local octahedral environments of Cr³⁺, Fe³⁺ and Gd³⁺ ions in Rb₂CdF₄, Cs₂CdF₄, RbCdF₃ and CsCdF₃ crystals have been studied by analyzing their EPR spectra. From the studies, it is found that the tetragonal distortions for Cr³⁺ and Fe³⁺ impurity ions, which substitute Cd²⁺ and have nearly the same ionic radius, are close to each other, whereas that for Gd³⁺ impurity ion, having a larger ionic radius, is larger than those for Cr³⁺ and Fe³⁺ ions in the same crystal. It appears that not only the impurity-ligand distance, but also the tetragonal distortions of impurity centres in crystals are closely related to the size of impurity.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Tip-induced distortions in STM imaging of carbon nanotubes

By means of STM measurements and fully self-consistent transport calculations we analyze how STM trajectories for the mapping of nanostructures on surfaces are affected by the atomic structure of the tip. For the particular case of carbon nanotubes we show that considerable distortions of the STM trajectory with respect to the actual structure, position and diameter of the nanotube can occur for certain tip geometries. Comparison between theory and experiment can allow to characterize and correct these distortions.     

The influence of hydrogen impurities on the atomic and electronic structures of carbyne crystals

An ab initio DFT study of atomic and electronic structure of carbyne crystals was carried out. The influence of hydrogen impurities on carbyne structure was investigated. Calculations with atomic relaxations showed that carbon chains in the carbyne crystal structure are bow-like curved; free-energy calculations showed that the most probable lengths of those chains are four and six atoms, which is in a good agreement with experiments. Carbyne-crystal electronic-structure analysis showed that there is a small gap of 0.09 eV near the Fermi level in four-atomic carbyne, while there is no such gap in six-atomic carbyne. In studying of the hydrogen impurity influence on the atomic and electronic structure of carbyne crystals, hydrogen atoms were embedded in two directions: across and along carbon chains in the crystal. As a result we found that the crystal structure is not distorted in the case of hydrogen embedded across the chains, while the type of bonding between carbon atoms in carbon chains in the carbyne crystal structure depended on the impurity concentration. The crystal structure was distorted when hydrogen was embedded along the chains. The concentration of impurities influences the conductivity of a carbyne crystal.     

Stability and electronic properties of carbon nanotubes doped with transition metal impurities

We apply first-principles method to investigate the effect of the diameter on the stability and electronic properties of zigzag carbon nanotubes doped with iron, nickel and manganese impurity atoms. In this contribution we follow the evolution of the electronic and structural properties as a function of the nanotube diameter. As a general result, we found that the binding energy decreases with the increasing nanotube radius. Additionally, depending on the interaction of transition metal impurity with the tubular carbon structure, it is observed that the total magnetization varies with the tube diameter due to hybridization and confinement effects. It is also shown that such magnetization varies with the curvature radius, increasing for manganese impurity atoms and decreasing for iron and nickel.     

The effect of crystal lattice distortions on the electronic band structure and optical properties of the N,V- and N,Na-doped anatase

The crystal structure, energy band structure and optical absorption of the N,V-doped and N,Na-doped anatase are studied by means of the first-principle pseudo-potential plane wave and linear muffin-tin orbitals methods. We show that the nitrogen and vanadium atoms have a tendency to form covalently bonded pairs. The crystal lattice distortions associated with doping essentially affect the optical absorption. With doping the impurity bands emerge in the band gap of the host anatase, however, a noticeable increase of optical absorption takes place at the energy only above 3 eV. Possible impact of this effect on the photocatalytic activity of the doped anatase is outlined.     

Ab initio thermodynamic characteristics of the formation of oxygen vacancies,and boron,carbon, and nitrogen impurity centers in anatase

Using the ab initio projector augmented wave (PAW) method, calculations are performed for the electronic energy-band structure of titanium dioxide having the structure of anatase doped with boron, nitrogen, and carbon. Thermodynamic characteristics are determined for the formation of impurity centers, such as the preference energy for the interstitial position, the energy of impurity oxidation, and the energy of oxygen vacancy formation. It is shown that under the conditions of thermodynamic equilibrium the interstitial position of boron atoms is stable, whereas carbon atoms, depending on the oxygen pressure, can occupy both interstitial positions and substitutional positions of oxygen atoms, and nitrogen atoms replace oxygen atoms. It is shown that the presence of oxygen vacancies promotes the thermodynamic stability of carbon and nitrogen atoms. The obtained densities of electronic states correspond to ESR spectroscopy data, which indicates the presence of spin-polarized electrons in the states of the oxygen vacancy.     

LDC-CNTFET: A carbon nanotube field effect transistor with linear doping profile channel

In this paper, a novel carbon nanotube field effect transistor with linear doping profile channel (LDC-CNTFET) is presented. The channel impurity concentration of the proposed structure is at maximum level at source side and linearly decreases toward zero at drain side. The simulation results show that the leakage current, on-off current ratio, subthreshold swing, drain induced barrier lowering, and voltage gain of the proposed structure improve in comparison with conventional CNTFET. Also, due to spreading the impurity throughout the channel region, the proposed structure has superior performance compared with a single halo CNTFET structure with equal saturation current. Design considerations show that the proposed structure enhances the device performance all over a wide range of channel lengths.     

The influence of local distortions on the static and dynamic properties of copper and silver eightfold-coordinated Jahn-Teller complexes in mixed crystals with a fluorite-type structure

The influence of local distortions on the structure and properties of copper and silver impurity Jahn-Teller complexes in mixed crystals, namely, Ca_xSr_1?x F₂: Me ²⁺ and Sr_1?x Ba_xF₂: Me ²⁺ (0≤x≤1, Me ²⁺=Cu²⁺ or Ag²⁺), is investigated using electron paramagnetic resonance (EPR) spectroscopy at frequencies of 9.3 and 37 GHz in the temperature range 4.2–250 K. Local distortions of the tensile and compressive types are induced by Ca²⁺, Sr²⁺, and Ba²⁺ impurity ions incorporated into the first or second coordination sphere of the cationic environment of the Me ²⁺ impurity ion during crystal growth.     

Local structure of bivalent copper centers in SrF2 crystals: An ENDOR spectroscopic study

Structural distortions of the SrF₂ crystal lattice near the bivalent copper impurity Jahn-Teller center are investigated by the ENDOR method (v=9.3 GHz, T=4.2 K). The approximate directions and the magnitudes of displacements of a Cu²⁺ impurity ion and its surrounding F^? ions are determined with respect to one of the anionic networks in the crystal matrix. The tensor components for the ligand hyperfine interaction (LHFI) with fluorine ions separated from the impurity by a distance R≤6.2 Å are obtained from the angular dependences of the location of the ENDOR resonance lines. It is found that the parameters of magnetic interactions between the impurity and these ligands contain the contributions determined by the covalence of bonds in the impurity complex and the polarization of electron shells of the ligands.     

Neutron diffraction investigation of specific features of the structure of ultrafine (nano) materials

The specific features of the atomic crystal structure of solids with small (<100 nm) sizes of particles in ultrafine (nano) powders have been investigated. It has been shown that, in contrast to the case of coarsegrained materials, distortions of the atomic order occur as an inhomogeneous deformation in surface layers. The distributions of impurity atoms (in the case of a solid solution) and the second phase (in the case of multiphase systems) from the center to the periphery are also inhomogeneous. The atomic distribution function along the radius of a nanoparticle, which characterizes its atomic structure as intermediate between the crystalline and amorphous structures, has been constructed.     

Defect modes due to substitutional impurities in FCC lattice: Green's function approach

Lattice dynamical study of monoatomic fcc crystals containing substitutional impurities has been made by the Green's function technique, using group theory. The impurity and its 12 nearest neighbors constitute an XY₁₂ impurity space having O_h symmetry. The phonon Green function matrix is analyzed according to the irreducible representations of the point group pertaining to the substitutional impurity in the fcc lattice. The effects due to change in mass at the impurity site and the change in nearest neighbor force constants for the impurity-host atom interactions are taken into account. Analytical expressions for the various modes of vibrations pertaining to the defect space have been obtained. Local mode frequencies due to various substitutional impurities, corresponding to F_1u mode (defect atom moving) have been computed. A special model is chosen for the defecthost force and it is assumed that there are no distortions of the lattice structure due to the defect. A Kihara hardcore potential with parameters fitted to neutron data has been used to compute lattice dynamics and Green functions of the host lattices. Our theoretical results have been compared with available experimental and theoretical results. Our results show reasonably good agreement with experimental results.     

Impurity induced interactions in diluted La2CuO4

A non-magnetic impurity, such as Zn, doped into a non-frustrated antiferromagnet can induce substantial frustrating interactions among the spins surrounding it and result in an enhanced suppression of the antiferromagnetic order. In addition, the strength of the intra-plane exchange couplings surrounding impurities is reduced by the lattice distortions. Using quantum Monte Carlo, we calculate the initial suppression rate of the staggered magnetization in a two-dimensional diluted Heisenberg antiferromagnet with both frustrating interaction and lattice distortion induced by the impurity. We find that the lattice distortion alone cannot explain the experimental results, while the dominant effect of enhanced order suppression is due to the frustrating interaction.