Using state of the art quantum calculations, we have studied the electronic and transport properties of a variety of nanotube-based structures relevant for the design of nanoscale electronic devices. We have investigated the conductance of carbon nanotubes under mechanica distortions such as bending, defects and tube-tube contacts, and analyzed the behavior of carbon nanotube-metal contacts with the aim of explaining the anomalously large contact resistance observed in nanotube devices. Our results provide a clear interpretation of recent experimenta findings and suggest avenues for the use of carbon nanotubes in electromechanical systems.

High strain conditions can lead to a variety of atomic transformations in nanotubes, which usually occur via successive bond rotations. The energetic barrier for the rotation is dramatically lowered by strain, and ab initio results for its strain dependence are presented. While very high strain rates must lead to tube breakage, (n,m) nanotubes with n, m < 14 can display plastic flow under suitable conditions. This occurs through the formation of a 5-7-7-5 defect, which then splits into two 5-7 pairs. The index of the tube changes between the 5-7 pairs, potentially leading to metal-semiconductor junctions. The high strain conditions can be imposed on the tube via, e.g., AFM tip manipulations, and we show that such procedures can lead to intratube device formation.

The defects and the index changes occurring during the mechanical transformations also affect the electrical properties of nanotubes. We have computed the quantum conductances of strained defective and deformed tubes using the tight binding method. The results show that the defect density and the contacts play key roles in reducing the conductance at the Fermi energy. We also explored the role of bending in changing the electrical properties and found that mechanical deformations affect differently the transport properties of achiral and chiral nanotubes. Our results are in good agreement with recent experimental data.

We present the results of a large-scale molecular dynamics investigation of addimers on strained carbon nanotubes. We find that addimers induce a new set of transformations that lead to the formation of extended defects that are actually short segments of tubes of altered helicity. As these defects wrap themselves about the circumference of the nanotube, this suggests that the combination of addimers and strain may well lead to the formation of nanotube-based quantum dots. The formation of these quantum dots is most favorable for the (n.O) zigzag tubes. For these tubes, addimers induce plastic transformations in tubes that normally display brittle behavior.

The results of extensive theoretical studies of the properties of interfaces and surfaces of the wide-gap III-V nitride semiconductors are reviewed. The phenomena that we have investigated include band offsets and transport properties in nitride-based devices, surface reconstruction energetics and adsorbate-substrate interactions. In the modelling of realistic blue-laser multiquantum well structures such as In0.2Ga0.8N/In1−xGaxN (x > 0.8) superlattices, pyro- and piezo-electric effects are found to be strong enough to reduce the interband recombination rate and limit the efficiency of an actual device. We have also studied the influence of growth conditions and surface polarity upon the morphology of (0001) GaN surfaces, which are the primary growth faces. The charge transfer between the Ga and N atoms in GaN and the very large electronegativity of nitrogen are found to play decisive roles in determining the stable reconstructions. The behavior of Mg at the Ga-terminated (0001) surface has also been investigated. We find that Mg in the Gasubstitutional site is preferred to adatom sites on the surface. Further, our results suggest that Mg prefers to segregate to the surface.

The results of extensive theoretical studies of group IV impurities and surface and interface properties of nitrides are presented and compared with available experimental data. Among the impurities, we have considered substitutional C, Si, and Ge. CN is a very shallow acceptor, and thus a promising p-type dopant. Both Si and Ge are excellent donors in GaN. However, in AlGaN alloys the DX configurations are stable for a sufficiently high Al content, which quenches the doping efficiency. At high concentrations, it is energetically favorable for group IV impurities to form nearest-neighbor Xcation-XN pairs. Turning to surfaces, AIN is known to exhibit NEA. We find that the NEA property depends sensitively on surface reconstruction and termination. At interfaces, the strain effects on the band offsets range from 20% to 40%, depending on the substrate. The AIN/GaN/InN interfaces are all of type I, while the A10.5Ga0.5 N/A1N zinc-blende (001) interface may be of type II. Further, the calculated bulk polarizations in wurtzite AIN and GaN are -1.2 and -0.45 μC/cm2, respectively, and the interface contribution to the polarization in the GaN/AlN wurtzite multi-quantum-well is small.

The results of theoretical studies of the bulk and interface properties of nitrides are presented. As a test the bulk properties, including phonons of GaN at the Γ-point, are calculated and found to be in excellent agreement with the experimental data. At interfaces, the strain effects on the band offsets range from 20% to 40%, depending on the substrate. The AlN/GaN/InN interfaces are all of type I, while the Al0.5Ga0.5N on A1N zinc-blende (001) interface is of type II. Further, an interface similar to those used in the recent blue laser diodes is of type I and does not have any electronically active interface states. The valence band-offset in the (0001) GaN on A1N interface is -0.57 eV and the conduction band-offset is 1.87 eV.

The electron affinity of a semiconductor defines the relationship of the vacuum level and the semiconductor band structure. It is dependent on the atomic orbitals of the material and the surface termination. We report experimental and theoretical results that support the presence of a negative electron affinity on AlN and the Al rich AlGaN alloys. The GaN surface is found to exhibit a (positive) electron affinity of 3.3eV. The experimental measurements employ UV-photoemission spectroscopy on in situ gas-source MBE samples and on CVD samples. Theoretical results indicate that the (negative) electron affinity of AlN depends sensitively on the surface reconstruction and adatom termination. The experimental dependence of the electron affinity on alloy concentration is presented. The results indicate that AlGaN alloys with band gap similar or greater than that of diamond will exhibit a negative electron affinity. Field emission results are reported, and the characteristics are similar to those obtained from a diamond film. Issues related to cold cathode electronic devices based on NEA surfaces are noted.

We have investigated Si (100) homoepitaxy in variety of different temperature regimes. In the high temperature step flow regime, the growth properties of the different steps play an important role. The binding sites and diffusion barriers for a Si adatom moving over the buckled Si(100) surface and single-height steps were investigated with the ab initio Car-Parrinello scheme. The SA step edge was found to be a relatively poor sink for adatoms. By contrast, growth takes place much more rapidly at the SB step edges, so that one can understand the relatively fast growth observed at the ends of dimer rows. We have also investigated Si(100) homoepitaxy with classical molecular dynamics simulations at very low temperatures, where typically an amorphous deposit forms. By tuning the energy of the incoming atomic beams, one can lower the temperature of the amorphous to crystalline transition considerably and thereby enhance epitaxial growth.

We have developed a set of techniques for performing large scale ab initio calculations using multigrid accelerations and a real-space grid as a basis. The multigrid methods permit efficient calculations on ill-conditioned systems with long length scales or high energy cutoffs. We discuss the design of pseudopotentials for real-space grids, and the computation of ionic forces. The technique has been applied to several systems, including an isolated C60 molecule, the wurtzite phase of GaN, a 64-atom cell of GaN with the Ga d-states in valence, and a 443-atom protein. The method has been implemented on both vector and parallel architectures. We also discuss ongoing work on O(N) implementations and solvated biomolecules.

It has been shown experimentally that the growth of carbon nanotubes in an arc discharge is open-ended. This is surprising, because dangling bonds at the end of open tubes make the closed tube geometry more favorable energetically. Recently, it has been proposed that the large electric fields present at the tip of tube is the critical factor that keeps the tube open. We have studied the effects of the electric field on the growth of the nanotubes via ab initio molecular dynamics simulations. Surprisingly, it is found that the electric field cannot play a significant role in keeping the tubes open, implying that some other mechanism must be important. Extensive studies of the energetics and simulations of the growth of tubes were performed using a threebody Tersoff-Brenner potential. Our results show that there exists a critical diameter of ∼ 3 nm above which a defect-free growth of a straight tubule is possible. Narrower tubes stabilize configurations with adjacent pentagons that lead to tube-closure and termination of the growth. This explains the absence of tube narrower than 2.2 nm in arc discharge experiments.

The results of an extensive theoretical study of native defects in GaN and of vacancies in AlN are presented. We have considered cation and anion vacancies, antisites, and intersti-tials. The computations were carried out using quantum molecular dynamics, in supercells containing 72 atoms. Due to the wide gap of nitrides, the formation energies of defects depend strongly on the position of the Fermi level. The N vacancy in GaN introduces a shallow donor level that may be responsible for the n-type character of as-grown GaN.Other defects introduce deep states in the gap, with strongly localized wave functions.

The reconstruction patterns of Si- and C-terminated surfaces of wurtzite SiC are studied by ab initio molecular dynamics. The (1×1) relaxed, (1×2) buckled, and (2×1) л-bonded chain geometries are considered. In the (l×1) geometry, inward relaxation of the C-terminated surface is much stronger than that of the Si-terminated surface. The C-terminated surface is stable with respect to (2×1) buckled reconstruction, but the Si-terminated surface is not. At both surfaces, the (2×1) л-bonded chain geometry is energetically the most favorable. The Si-C л-bonded chains are buckled and slightly dimerized. In both cases, the outermost atoms are carbons, due to the bond length constraints of the л-bonded chain reconstruction.

We have examined the distribution of the neutral dangling bond defect states, T30, as a function of the local disorder. T30 defects in a-Si play an important role in many of the current models of the metastable photoconductivity. To understand the relationship between the T30 defect and its bonding environment, the Local Density of States (LDOS) for under-coordinated Si atoms in disordered environments are calculated using the cluster-Bethe lattice method, CBLM. Our Hamiltonian employs the tight-binding parameters of an sp3 orbital basis containing both 1st and 2nd nearest-neighbor interaction terms fit to c-Si band structure. Averaged LDOS of atoms with various bond angle distortions are calculated in order to demonstrate the relationship between the standard deviation in bond angle and the width of the defect states. The CBLM is also used to determine the extent of the valence band tails as a function of the standard deviation in bond angle. In addition, the LDOS of clusters with 2 dangling bonds are examined to determine the degree that their energy levels split due to their interaction with each other.

Electronic applications of diamond require control over native defects as well as the ability to dope it p- and n-type. B is an excellent p-type dopant, but n-type doping has proven very difficult. Diamond films have also been very difficult to anneal, indicating a high activation energy for self-diffusion. We have investigated the properties of native defects and impurities through large-scale band structure and Car-Parrinello calculations. We indeed find that the activation energy for self-diffusion is very high in the intrinsic material, but it decreases by as much as 3 eV in either p- or n-type material. P, Li, and Na are shallow donors, but their solubilities are too low for incorporation into diamond through in-diffusion. It is energetically favorable for B and N to dissolve in diamond, which explains their prevalence in natural diamond. The calculations explain for the first time the reasons for the distortion of atoms around N from the fully tetrahedral site, as well as why N is a deep rather than a shallow donor. We also consider the effects of simultaneous doping with N and B on the thermodynamic equilibrium between diamond and graphite.

We have systematically investigated the formation of electronic states in the region of the conduction and valence band edges of a Si as functions of variations in the bond angle distributions. Local Density of States (LDOS) for Si atoms in disordered environments have been calculated using the cluster Bethe lattice method with a tight-binding Hamiltonian containing both first and second nearest neighbor interaction terms. LDOS for atoms with bond angle dis ortions in the nearest neighbor and second neighbor shells are compared and contrasted, both showing an influence on the LDOS near the gap. We also consider the role of the second neighbor term in the Hamiltonian by comparing the DOS for a distoned infinite Bethe lattice using Hamiltonians with and without the second neighbor interactions. It is found that in this case the second neighbor interaction terms cause greater conduction band tailing than using the nearest neighbor interaction terms alone.

We report the first structure optimization and quantum molecular dynamics simulations for solid C60. The symmetry-unconstrained optimization results in nearly ideal buckminsterfullerene structure. This is due to the closed shell nature of C60 and the weakness of the intermolecular interactions in the solid. The lack of substantial intermolecular interactions allows for rotations at relatively low temperatures and these rotations are observed during simulations. Although the zero temperature structure consists of alternating single and double bonds, this distinction becomes blurred at moderate temperatures. However, computer generated movies show that the cage structure is preserved even at high temperatures, despite vibrational motion with substantial amplitude.

The energetics and structures of metallic clusters containing up to 55 atoms are studied by the Car-Parrinello (quantum-molecular dynamics) method with Al chosen as a paradigm. It is found that the structural energy differences between small cluster (icosahedral) and bulk (fee) structures are surprisingly small, indicating that the icosahedron-fee structural transition can occur very early in Al clusters. Simulated annealing studies for 13- and 55-atom clusters, where both perfectly symmetric icosahedral and cuboctahedral (fee) structures exist, show that the distortions from the ideal structures are substantial. For the 55-atom cluster several inequivalent but energetically nearly degenerate structures are found, which is likely to lead to floppiness at finite temperatures as well as a low melting point. Although the structure factors for the annealed structures are nearly identical, they are very different from those of either of the ideal structures. The computed IPs and EAs differ by less than 0.1 eV for weakly annealed cuboctahedral and icosahedral clusters, making the structural identification on the basis of IP and EA measurements very difficult. The quantum-mechanical results are also used to develop a classical potential for long-time molecular dynamics simulations of large clusters.

We have investigated, via parameter-free calculations, the effects of hydrostatic and nonhydrostatic strains on the energetics of defect formation and self-diffusion in silicon. The three microscopic mechanisms, vacancy, interstitial, and concerted exchange, have very similar activation enthalpies at zero pressure but exhibit different behavior with hydrostatic pressure. Our results suggest that experiments performed at different pressures can determine the relative contributions of each of these mechanisms. The calculations also show that the neutral Si vacancy has a negative relaxation volume, with the nearest neighbors of the vacancy relaxing inwards, in contrast to the Si (111) surface. Large nonhydrostatic strains, which are present in e.g. Si/GexSi1-x pseudomorphic heterostractures, substantially reduce the formation energy of the tetrahedral interstitial, but do not affect the formation energy of the vacancy. These findings suggest that, aside from being another useful tool for the investigation of self-diffusion in Si, nonhydrostatic strain may significantly affect annealing and impurity diffusion in strained heterostructures. In particular, the interstitial-assisted impurity diffusion may proceed more rapidly in Si lattice-matched to GexSi1-x, but be slowed down in GexSi1-x lattice-matched to Si. The compressed GexSi1-x layers may thus act as diffusion barriers for impurities diffusing with help of native interstitials, such as B or P.

First-principles calculations were used to study Li, Na, and P as prospective shallow donors in diamond. As expected, P prefers the substitutional site while Li and Na are interstitial donors. All three impurities were found to be shallow. However, their solubilities are very low, which makes them unsuitable for incorporation into diamond via in-diffusion. Instead, kinetic trapping during growth or ion implantation must be used. Interstitial impurities are particularly appropriate for ion implantation, since there is no need to replace host atoms. Considering the stability of the impurity at the dopant site, substitutional P is expected to diffuse by the vacancy mechanism and to have a high activation energy by analogy to self-diffusion. For Li and Na, the activation energies for interstitial channel diffusion are 0.85 and 1.6 eV, respectively. Li is thus a fast diffuser even at room temperature, while Na would remain stable up to moderate temperatures.