Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

On the two dimensional effective electron mass in quantum wells, inversion layers and NIPI superlattices of Kane type semiconductors in the presence of strong light waves: Simplified theory and relative comparison

An attempt is made to study the two dimensional (2D) effective electron mass (EEM) in quantum wells (Qws), inversion layers (ILs) and NIPI superlattices of Kane type semiconductors in the presence of strong external photoexcitation on the basis of a newly formulated electron dispersion laws within the framework of k.p. formalism. It has been found, taking InAs and InSb as examples, that the EEM in Qws, ILs and superlattices increases with increasing concentration, light intensity and wavelength of the incident light waves, respectively and the numerical magnitudes in each case is band structure dependent. The EEM in ILs is quantum number dependent exhibiting quantum jumps for specified values of the surface electric field and in NIPI superlattices; the same is the function of Fermi energy and the subband index characterizing such 2D structures. The appearance of the humps of the respective curves is due to the redistribution of the electrons among the quantized energy levels when the quantum numbers corresponding to the highest occupied level changes from one fixed value to the others. Although the EEM varies in various manners with all the variables as evident from all the curves, the rates of variations totally depend on the specific dispersion relation of the particular 2D structure. Under certain limiting conditions, all the results as derived in this paper get transformed into well known formulas of the EEM and the electron statistics in the absence of external photo-excitation and thus confirming the compatibility test. The results of this paper find three applications in the field of microstructures. (C) 2011 Elsevier Ltd. All rights reserved.

Pressure transitions and electron transport behaviour of crystalline Se-Te alloys

Pressure transitions of Se-Te alloys have been studied over the entire range of compositions. Conductivities have also been measured as a function of temperature and alloy composition. Transition pressures, activation barriers and isothermal conductivities exhibit distinct changes of slope in their variation as a function of composition at about 8 at % of Te. Transition pressures change slope at not, vert, similar 35% Te also. An attempt has been made to explain these observations on the basis of the size effect of Te which, in turn, affects the electron energy dispersions in the band structure.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

An ab-initio study of the proton affinity of conjugated schiff-base and related nitrogen compounds: an analysis of the triggering site of bacteriorhodopsin

The chemical groups which take part in the proton transfer reaction in bacteriorhodopsin have been studied by ab initio quantum chemical methods. The various factors such as conjugation with a linear system, electron delocalization of the guanidine type, cis-trans isomerism, geometry distortion and hydrogen bonding with charged groups can influence the properties of a given chemical group. Several systems are studied at 4-31G and STO-3G levels. Some of the Schiff-base analogues and guanidine type molecules are characterized by their molecular orbital diagrams, energy levels and the nature of charge distribution. Also, the effects of the above-mentioned factors on proton affinity are studied. It is hoped that the values thus obtained can be helpful in evaluating various structural models for proton transfer.

Systematic Organic UV Photoelectron Spectroscopy

Photoelectron spectroscopy (PES) provides valuable information on the ionization energies of atoms and molecules. The ionization energy (IE) is given by the relation.hv = IE + T where hv is t h e energy of the radiation and T i s the kinetic energy of the electron. The IEs are directly related to the orbital energies (Koopmans' theorem). By employing UV radiation (HeI. 21.2 eV. or HeII. 40.8 eV). extensive data on the ionization of valence electrons in organic molecules have been obtained in recent years. These studies of UV photoelectron spectroscopy. originated by Turner, have provided a direct probe into the energy levels of organic molecules. Molecular orbital calculations of various degrees of sophistication are generally employed to make assignments of the PES bands. Analysis of the vibrational structure of PES bands has not only provided structural information on the molecular ions, but has also been of value in band assignments. Dewar and co-workers [1, 2) presented summaries of available PES data on organic molecules in 1969 and 1970. Turner et al. [3] published a handbook of Hel spectra of organic molecules in 1970. Since then, a few books [4-7] discussing the principles and applications of UV photoelectron spectroscopy have appeared of which special mention should be made of the recent article by Heilbronner and Maier [7]. There has, however, been no comprehensive review of the vast amount of data on the UV-PES of organic molecules published in the literature since 1970.

Preparation, Characterization And Properties Of C-60 And C-70 - Spectroscopy, Structure, Anions, Interaction With Electron-Donors And Superconductivity

Preparation and characterization of the fullerenes, C60 and C70, are described in detail, including the design of the generators fabricated locally. The characterization techniques employed are UV-visible, IR, Raman and C-13 NMR spectroscopies, scanning as well as transmission electron microscopy and mass spectrometry. The electron energy level diagram of C60 as well as the one-electron reductions of C60 and C70 leading to various anions are discussed. Electronic absorption spectra of C60- and C60(2-) are reported. Phase transitions from the plastic to the crystalline states of C60 and C70 are examined. Based on a C-13 NMR study in a mixture of nematic liquid crystals, it has been demonstrated that C60 retains its extraordinary symmetry in solution phase as well. Interaction of C60 and C70 with strong electron-donor molecules has been investigated employing cyclic voltammetry. Superconductivity of K(x)C60 has been studied by non-resonant microwave absorption; Na(x)C60 as well as K(c)C70 are shown to be non-superconducting. Doping C60 with iodine does not make it superconducting. Interaction of C60 with SbCl5 and liquid Br2 gives rise to halogenated products.

Quantum Dots and Nanoroads of Graphene Embedded in Hexagonal Boron Nitride

The quest for novel two-dimensional materials has led to the discovery of hybrids where graphene and hexagonal boron nitride (h-BN) occur as phase-separated domains. Using first-principles calculations, we study the energetics and electronic and magnetic properties of such hybrids in detail. The formation energy of quantum dot inclusions (consisting of n carbon atoms) varies as 1/root n, owing to the interface. The electronic gap between the occupied and unoccupied energy levels of quantum dots is also inversely proportional to the length scale, 1/root n-a feature of confined Dirac fermions. For zigzag nanoroads, a combination of the intrinsic electric field caused by the polarity of the h-BN matrix and spin polarization at the edges results in half-metallicity; a band gap opens up under the externally applied ``compensating'' electric field. For armchair nanoroads, the electron confinement opens the gap, different among three subfamilies due to different bond length relaxations at the interfaces, and decreasing with the width.

Simple theoretical analysis of the Fowler-Nordheim field emission from microstructures and quantum wires of optoelectronic materials

We present a simplified theoretical formulation of the Fowler-Nordheim field emission (FNFE) under magnetic quantization and also in quantum wires of optoelectronic materials on the basis of a newly formulated electron dispersion law in the presence of strong electric field within the framework of k.p formalism taking InAs, InSb, GaAs, Hg(1-x)Cd(x)Te and In(1-x)Ga(x) As(y)P(1-y) lattice matched to InP as examples. The FNFE exhibits oscillations with inverse quantizing magnetic field and electron concentration due to SdH effect and increases with increasing electric field. For quantum wires the FNFE increases with increasing film thickness due to the existence van-Hove singularity and the magnitude of the quantum jumps are not of same height indicating the signature of the band structure of the material concerned. The appearance of the humps of the respective curves is due to the redistribution of the electrons among the quantized energy levels when the quantum numbers corresponding to the highest occupied level changes from one fixed value to the others. Although the field current varies in various manners with all the variables in all the limiting cases as evident from all the curves, the rates of variations are totally band-structure dependent. Under certain limiting conditions, all the results as derived in this paper get transformed in to well known Fowler-Nordheim formula. (C) 2011 Elsevier Ltd. All rights reserved.

Efficient generation and guiding of megaampere relativistic electron current by silicon nanowires

We demonstrate 30 times enhanced flux of relativistic electrons by a silicon nanowire coated target excited by 30 fs, 800 nm laser pulses at an intensity of 3 x 10(18) W cm(-2). A measurement of the megaampere electron current via induced megagauss magnetic field supports the enhancement feature observed in the electron energy spectrum. The relativistic electrons generated at the front of nanowire coated surface are shown to travel efficiently over 500 mu m in the insulating substrate. The enhanced hot electron temperature is explained using a simple model and is supported by recent simulations. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729010]

Design and synthesis of new low band gap organic semiconductors for photovoltaic applications

Donor-acceptor (D-A) conjugated polymers have attracted a good deal of attention in recent years. In D-A systems, the introduction of electron withdrawing groups reduces E-g by lowering the LUMO levels whereas, the introduction of electron donating groups reduces E-g by raising the HOMO levels. Also, conjugated polymers with desired HOMO and LUMO energy levels could be obtained by the proper selection of donor and acceptor units. Because of this reason, D-A conjugated polymers are emerging as promising materials particularly for polymer light emitting diodes (PLEDs) and polymer solar cells (PSCs). We report the design and synthesis of four new narrow band gap donor-acceptor (D-A) conjugated polymers, PTCNN, PTCNF, PTCNV and PTCNO, containing electron donating 3,4-didodecyloxythiophene and electron accepting cyanovinylene units. The effects of further addition of electron donating and electron withdrawing groups to the repeating unit of a D-A conjugated polymer (PTCNN) on its optical and electrochemical properties are discussed. The studies revealed that the nature of D and A units as well as the extent of alternate D-A structure influences the optical and the electrochemical properties of the polymers. All the polymers are thermally stable up to a temperature of 300 degrees C under nitrogen atmosphere. The electrochemical studies revealed that the polymers possess low-lying HOMO energy levels and low-lying LUMO energy levels. In the UV-Vis absorption study, the polymer films displayed broad absorption in the wavelength region of 400-700 nm. The polymers exhibited low optical band gaps in the range 1.70 - 1.77 eV.

Narrow band gap conjugated polymer for improving the photovoltaic performance of P3HT:PCBM ternary blend bulk heterojunction solar cells

A new D-A structured conjugated polymer (PBDO-T-TDP) based on electron-rich benzo 1,2-b:4,5-b'] difuran (BDO) containing conjugated alkylthiophene side chains with an electron-deficient diketopyrrolopyrrole (DPP) derivative is designed and synthesized. The polymer shows a narrow band gap with broad UV-Visible absorption spectra, which is in contrast to that of the P3HT:PCBM binary blend. Furthermore, its energy levels can meet the energetic requirement of the cascaded energy levels of P3HT and PCBM. Therefore, PBDO-T-TDP is used as a sensitizer in P3HT: PCBM based BHJ solar cells and its effect on their photovoltaic properties was investigated by blending them together at various weight ratios. It is observed that the resulting ternary blend system exhibited a significant improvement in the device performance (similar to 3.10%) as compared with their binary ones (similar to 2.15%). Such an enhancement in the ternary blend system is ascribed to their balanced hole and electron mobility along with uniform distribution of PBDO-T-TDP in the blend system, as revealed by organic field effect transistors and AFM studies.

Theoretical Insights to Niobium-Doped Monolayer MoS2-Gold Contact

We report a first principles study of the electronic properties for a contact formed between Nb-doped monolayer MoS2 and gold for different doping concentrations. We first focus on the shift of energy levels in band structure and the density of states with respect to the Fermi level for a geometrically optimized 5 x 5 MoS2 supercell for both pristine and Nb-doped structures. The doping is achieved by substituting Mo atoms with Nb atoms at random positions. It is observed that for an experimentally reported sheet hole doping concentration of (rho(2D)) 1.8 x 10(14) cm(-2), the pristine MoS2 converts to degenerate p-type semiconductor. Next, we interface this supercell with six layers of < 111 > cleaved surface of gold to investigate the contact nature of MoS2-Au system. By careful examination of projected band structure, projected density of states, effective potential and charge density difference, we demonstrate that the Schottky barrier nature observed for pure MoS2-Au contact can be converted from n-type to p-type by efficient Nb doping.

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.