Atomic scale engineering of carbon nanotubes

Carbon nanotubes, seamless cylinders made from carbon atoms, have outstanding characteristics: inherent nano-size, record-high Young’s modulus, high thermal stability and chemical inertness. They also have extraordinary electronic properties: in addition to extremely high conductance, they can be both metals and semiconductors without any external doping, just due to minute changes in the arrangements of atoms. As traditional silicon-based devices are reaching the level of miniaturisation where leakage currents become a problem, these properties make nanotubes a promising material for applications in nanoelectronics. However, several obstacles must be overcome for the development of nanotube-based nanoelectronics. One of them is the ability to modify locally the electronic structure of carbon nanotubes and create reliable interconnects between nanotubes and metal contacts which likely can be used for integration of the nanotubes in macroscopic electronic devices. In this thesis, the possibility of using ion and electron irradiation as a tool to introduce defects in nanotubes in a controllable manner and to achieve these goals is explored. Defects are known to modify the electronic properties of carbon nanotubes. Some defects are always present in pristine nanotubes, and naturally are introduced during irradiation. Obviously, their density can be controlled by irradiation dose. Since different types of defects have very different effects on the conductivity, knowledge of their abundance as induced by ion irradiation is central for controlling the conductivity. In this thesis, the response of single walled carbon nanotubes to ion irradiation is studied. It is shown that, indeed, by energy selective irradiation the conductance can be controlled. Not only the conductivity, but the local electronic structure of single walled carbon nanotubes can be changed by the defects. The presented studies show a variety of changes in the electronic structures of semiconducting single walled nanotubes, varying from individual new states in the band gap to changes in the band gap width. The extensive simulation results for various types of defect make it possible to unequivocally identify defects in single walled carbon nanotubes by combining electronic structure calculations and scanning tunneling spectroscopy, offering a reference data for a wide scientific community of researchers studying nanotubes with surface probe microscopy methods. In electronics applications, carbon nanotubes have to be interconnected to the macroscopic world via metal contacts. Interactions between the nanotubes and metal particles are also essential for nanotube synthesis, as single walled nanotubes are always grown from metal catalyst particles. In this thesis, both growth and creation of nanotube-metal nanoparticle interconnects driven by electron irradiation is studied. Surface curvature and the size of metal nanoparticles is demonstrated to determine the local carbon solubility in these particles. As for nanotube-metal contacts, previous experiments have proved the possibility to create junctions between carbon nanotubes and metal nanoparticles under irradiation in a transmission electron microscope. In this thesis, the microscopic mechanism of junction formation is studied by atomistic simulations carried out at various levels of sophistication. It is shown that structural defects created by the electron beam and efficient reconstruction of the nanotube atomic network, inherently related to the nanometer size and quasi-one dimensional structure of nanotubes, are the driving force for junction formation. Thus, the results of this thesis not only address practical aspects of irradiation-mediated engineering of nanosystems, but also contribute to our understanding of the behaviour of point defects in low-dimensional nanoscale materials.

Influence of External Light Waves on the Thermoelectric Power Under Strong Magnetic Field in Ultrathin Films, Quantum Wires and Quantum Dots of Optoelectronic Materials

In this paper, an attempt is made to study the influence of external light waves on the thermoelectric power under strong magnetic field (TPSM) in ultrathin films (UFs), quantum wires (QWs) and quantum dots (QDs) of optoelectronic materials whose unperturbed dispersion relation of the conduction electrons are defined by three and two band models of Kane together with parabolic energy bands on the basis of newly formulated electron dispersion laws in each case. We have plotted the TPSM as functions of film thickness, electron concentration, light intensity and wavelength for UFs, QWs and ODs of InSb, GaAs, Hg1-xCdxTe and In1-xGaxAsyP1-y respectively. It appears from the figures that for UFs, the TPSM increases with increasing thickness in quantum steps, decreases with increasing electron degeneracy exhibiting entirely different types of oscillations and changes with both light intensity and wavelength and these two latter types of plots are the direct signature of light waves on opto-TPSM. For QWs, the opto-TPSM exhibits rectangular oscillations with increasing thickness and shows enhanced spiky oscillations with electron concentration per unit length. For QDs, the opto-TPSM increases with increasing film thickness exhibiting trapezoidal variations which occurs during quantum jumps and the length and breadth of the trapezoids are totally dependent on energy band constants. Under the condition of non-degeneracy, the results of opto-TPSM gets simplified into the well-known form of classical TPSM equation which the function of three constants only and being invariant of the signature of band structure.

Biaxial strain induced electrical inhomogenities and phase separation in the ferromagnetic metallic phase in thin films of La0.7Ca0.3MnO3: A scanning tunneling potentiometry/spectroscopy study

We have investigated the effect of biaxial strain on local electrical/electronic properties in thin films of La0.7Ca0.3MnO3 with varying degrees of biaxial strain in them. The local electrical properties were investigated as a function of temperature by scanning tunneling spectroscopy (STS) and scanning tunneling potentiometry (STP), along with the bulk probe like conductance fluctuations.The results indicate a positive correlation between the lattice mismatch biaxial strain and the local electrical/electronic inhomogenities observed in the strained sample. This is plausible since the crystal structure of the manganites interfere rather strongly with the magnetic/electronic degrees of freedom. Thus even a small imbalance (biaxial strain) can induce significant changes in the electrical properties of the system.

Organization of Mn-Clusters in pcu and bcu Networks: Synthesis, Structure, and Properties

Two new anionic inorganic-organic hybrid compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5), I, and H3O](2)Mn-7(mu(3)-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8), II have been prepared by employing mild solvothennal methods. Both the compounds have three-dimensionally extended structures formed by Mn-6 and Mn-7 clusters, respectively. The connectivity between Mn-6 and Mn-7 clusters and 4,4'-sulfonyldibenzoic acid anions (SDBA(2-)) results in a six connected pcu network in I and an eight connected bcu network in II. The presence of hydronium ion (H-3(O+)) along with the solvent molecules in the channels of both the compounds suggested proton conduction in the solids. Proton conductivity studies gave values of similar to 3 x 10(-4) Omega(-1) cm(-1) 98% relative humidity in both the compounds. The high activation energies indicate a vehicle mechanism in the compounds I and II. Magnetic studies indicate antiferromagnetic behavior in both the compounds.

Electronic Structure Evolution across the Peierls Metal-Insulator Transition in a Correlated Ferromagnet

Transition metal compounds often undergo spin-charge-orbital ordering due to strong electron-electron correlations. In contrast, low-dimensional materials can exhibit a Peierls transition arising from low-energy electron-phonon-coupling-induced structural instabilities. We study the electronic structure of the tunnel framework compound K2Cr8O16, which exhibits a temperature-dependent (T-dependent) paramagnetic-to-ferromagnetic- metal transition at T-C = 180 K and transforms into a ferromagnetic insulator below T-MI = 95 K. We observe clear T-dependent dynamic valence (charge) fluctuations from above T-C to T-MI, which effectively get pinned to an average nominal valence of Cr+3.75 (Cr4+:Cr3+ states in a 3:1 ratio) in the ferromagnetic-insulating phase. High-resolution laser photoemission shows a T-dependent BCS-type energy gap, with 2G(0) similar to 3.5(k(B)T(MI)) similar to 35 meV. First-principles band-structure calculations, using the experimentally estimated on-site Coulomb energy of U similar to 4 eV, establish the necessity of strong correlations and finite structural distortions for driving the metal-insulator transition. In spite of the strong correlations, the nonintegral occupancy (2.25 d-electrons/Cr) and the half-metallic ferromagnetism in the t(2g) up-spin band favor a low-energy Peierls metal-insulator transition.

Optimizing the Curie temperature of pseudo-binary RxR2-x ' Fe-17 (R, R ' = rare earth) for magnetic refrigeration

Several pseudo-binary RxR2-x'Fe-17 alloys (with R = Y, Ce, Pr, Gd and Dy) were synthesized with rhombohedral Th2Zn17-type crystal structure determined from x-ray and neutron powder diffraction. The choice of compositions was done with the aim of tuning the Curie temperature (T-C) in the 270 +/- 20 K temperature range, in order to obtain the maximum magneto-caloric effect around room temperature. The investigated compounds exhibit broad isothermal magnetic entropy changes, Delta S-M(T), with moderate values of the refrigerant capacity, even though the values of Delta S-M(Peak) are relatively low compared with those of the R2Fe17 compounds with R = Pr or Nd. The reduction on the Delta S-M(Peak) is explained in terms of the diminution in the saturation magnetization value. Furthermore, the Delta S-M(T) curves exhibit a similar caret-like behavior, suggesting that the magneto-caloric effect is mainly governed by the Fe-sublattice. A single master curve for Delta S-M/Delta S-M(Peak)(T) under different values of the magnetic field change are obtained for each compound by rescaling of the temperature axis.

Angular dependence of domain wall resistivity in artificial magnetic domain structures.

We exploit the ability to precisely control the magnetic domain structure of perpendicularly magnetized Pt/Co/Pt trilayers to fabricate artificial domain wall arrays and study their transport properties. The scaling behavior of this model system confirms the intrinsic domain wall origin of the magnetoresistance, and systematic studies using domains patterned at various angles to the current flow are excellently described by an angular-dependent resistivity tensor containing perpendicular and parallel domain wall resistivities. We find that the latter are fully consistent with Levy-Zhang theory, which allows us to estimate the ratio of minority to majority spin carrier resistivities, rho downward arrow/rho upward arrow approximately 5.5, in good agreement with thin film band structure calculations.

Electronic and magnetic properties of Ti(2)O(3), Cr(2)O(3), and Fe(2)O(3) calculated by the screened exchange hybrid density functional.

The electronic and magnetic properties of the transition metal sesqui-oxides Cr(2)O(3), Ti(2)O(3), and Fe(2)O(3) have been calculated using the screened exchange (sX) hybrid density functional. This functional is found to give a band structure, bandgap, and magnetic moment in better agreement with experiment than the local density approximation (LDA) or the LDA+U methods. Ti(2)O(3) is found to be a spin-paired insulator with a bandgap of 0.22 eV in the Ti d orbitals. Cr(2)O(3) in its anti-ferromagnetic phase is an intermediate charge transfer Mott-Hubbard insulator with an indirect bandgap of 3.31 eV. Fe(2)O(3), with anti-ferromagnetic order, is found to be a wide bandgap charge transfer semiconductor with a 2.41 eV gap. Interestingly sX outperforms the HSE functional for the bandgaps of these oxides.

Spray drying: An alternative synthesis method for polycationic oxide compounds

Synthesis of polycationic compounds by the spray-drying technique is an interesting alternative in the domain of aqueous precursor synthesis methods. Spray drying yields high quality samples with good reproducibility. The possibility of scaling up for production of large quantities with fast processing time is well established by the commercial availability of powders of various compositions. In this paper, we have discussed the advantages and limitations of this method and demonstrated its interest by synthesizing a few polycationic compounds selected for their attractive properties of thermoelectricity [Bi1.68Ca2Co1.69O 8, La0.95A0.05CoO3 (A=Ca, Sr, Ba)] or magnetoresistance [La0.70A0.30MnO3 (A=Sr, Ba)]. We have confirmed the quality of these samples by reporting their structure, magnetic and transport properties. © 2010 Elsevier Ltd All rights reserved.

Magnetic coupling properties of rare-earth metals (Gd, Nd) doped ZnO: First-principles calculations

The electronic structure and magnetic coupling properties of rare-earth metals (Gd, Nd) doped ZnO have been investigated using first-principles methods. We show that the magnetic coupling between Gd or Nd ions in the nearest neighbor sites is ferromagnetic. The stability of the ferromagnetic coupling between Gd ions can be enhanced by appropriate electron doping into ZnO Gd system and the room-temperature ferromagnetism can be achieved. However, for ZnO Nd system, the ferromagnetism between Nd ions can be enhanced by appropriate holes doping into the sample. The room-temperature ferromagnetism can also be achieved in the n-conducting ZnO Nd sample. Our calculated results are in good agreement with the conclusions of the recent experiments. The effect of native defects (V-Zn, V-O) on the ferromagnetism is also discussed. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3176490]

Revised ab initio natural band offsets of all group IV, II-VI, and III-V semiconductors

Using an all-electron band structure approach, we have systematically calculated the natural band offsets between all group IV, III-V, and II-VI semiconductor compounds, taking into account the deformation potential of the core states. This revised approach removes assumptions regarding the reference level volume deformation and offers a more reliable prediction of the "natural" unstrained offsets. Comparison is made to experimental work, where a noticeable improvement is found compared to previous methodologies.

Strain relaxation and band-gap tunability in ternary InxGa1-xN nanowires

The alloy formation enthalpy and band structure of InGaN nanowires were studied by a combined approach of the valence-force field model, Monte Carlo simulation, and density-functional theory (DFT). For both random and ground-state structures of the coherent InGaN alloy, the nanowire configuration was found to be more favorable for the strain relaxation than the bulk alloy. We proposed an analytical formula for computing the band gap of any InGaN nanowires based on the results from the screened exchange hybrid DFT calculations, which in turn reveals a better band-gap tunability in ternary InGaN nanowires than the bulk alloy.

Longitudinal spin transport in diluted magnetic semiconductor superlattices: The effect of the giant Zeeman splitting

Longitudinal spin transport in diluted magnetic semiconductor superlattices is investigated theoretically. The longitudinal magnetoconductivity (MC) in such systems exhibits an oscillating behavior as function of an external magnetic field. In the weak magnetic-field region the giant Zeeman splitting plays a dominant role that leads to a large negative magnetoconductivity. In the strong magnetic-field region the MC exhibits deep dips with increasing magnetic field. The oscillating behavior is attributed to the interplay between the discrete Landau levels and the Fermi surface. The decrease of the MC at low magnetic field is caused by the s-d exchange interaction between the electron in the conduction band and the magnetic ions. The spin polarization increases rapidly with increasing magnetic field and the longitudinal current becomes spin polarized in strong magnetic field. The effect of spin-disorder scattering on MC is estimated numerically for low magnetic fields and found to be neglectible for our system.

Strong three-level resonant magnetopolaron effect due to the intersubband coupling in heavily modulation-doped GaAs/AlxGa1-xAs single quantum wells at high magnetic-fields

Electron cyclotron resonance CR) measurements have been carried out in magnetic fields up to 32 T to study electron-phonon interaction in two heavily modulation-delta -doped GaAs/Al0.3Ga0.7As single-quantum-well samples. No measurable resonant magnetopolaron effects were observed in either sample in the region of the GaAs longitudinal optical (LO) phonons. However, when the CR frequency is above LO phonon frequency, omega (LO)=E-LO/(h) over bar, at high magnetic fields (B>27 T), electron CR exhibits a strong avoided-level-crossing splitting for both samples at frequencies close to (omega (LO)+ (E-2-E-1)1 (h) over bar, where E-2, and E-1 are the energies of the bottoms of the second and the first subbands, respectively. The energy separation between the two branches is large with the minimum separation of 40 cm(-1) occurring at around 30.5 T. A detailed theoretical analysis, which includes a self-consistent calculation of the band structure and the effects of electron-phonon interaction on the CR, shows that this type of splitting is due to a three-level resonance between the second Landau level of the first electron subband and the lowest Landau level of the second subband plus one GaAs LO phonon. The absence of occupation effects in the final states and weak screening or this three-level process yields large energy separation even in the presence of high electron densities. Excellent agreement between the theory and the experimental results is obtained.

Electronic states of a two-dimensional electron system in a lateral superlattice and a perpendicular magnetic field

The electronic state of a two-dimensional electron system (2DES) in the presence of a perpendicular uniform magnetic field and a lateral superlattice (LS) is investigated theoretically. A comparative study is made between a LS induced by a spatial electrostatic potential modulation (referred to as a PMLS) and that induced by a spatial magnetic-field modulation (referred ro asa MMLS). By utilizing a finite-temperature self-consistent Hartree-Fock approximation scheme; the dependence of the electronic state on different system parameters (e.g., the modulation period, the modulation strength, the effective electron-electron interaction strength, the averaged electron density, and the system temperature) is studied in detail. The inclusion of exchange effect is found to bring qualitative changes to the electronic state of a PMLS, leading generally to a nonuniform spin splitting, and consequently the behavior of the electronic state becomes similar to that of a MMLS. The Landau-level coupling is taken into account, and is found to introduce some interesting features not observed before. It is also found that, even in the regime of intermediate modulation strength, the density dependence of the spin splitting of energy levels, either for a PMLS or a MMLS, can be qualitatively understood within the picture of a 2DES in a perpendicular magnetic field with the modulation viewed as a perturbation. [S0163-1829(97)02248-0].