Effect of Structural Modification on the Quantum-Size Effect in II-VI Semiconducting Nanocrystals

The electronic structure of group II-VI semiconductors in the stable wurtzite form is analyzed using state-of-the-art ab initio approaches to extract a simple and chemically transparent tight-binding model. This model can be used to understand the variation in the bandgap with size, for nanoclusters of these compounds. Results complement similar information already available for same systems in the zinc blende structure. A comparison with all available experimental data on quantum size effects in group II-VI semiconductor nanoclusters establishes a remarkable agreement between theory and experiment in both structure types, thereby verifying the predictive ability of our approach. The significant dependence of the quantum size effect on the structure type suggests that the experimental bandgap change at a given size compared to the bulk bandgap, may be used to indicate the structural form of the nanoclusters, particularly in the small size limit, where broadening of diffraction features often make it difficult to unambiguously determine the structure.

Doping Transition Metal (Mn or Cu) Ions in Semiconductor Nanocrystals

Following growth doping strategy and using dopant oxides nanocrystals as dopant sources, we report here two different transition-metal ions doped in a variety of group II-VI semiconductor nanocrystals. Using manganese oxide and copper oxide nanocrystals as corresponding dopant sources, intense photoluminescence emission over a wide range of wavelength has been observed for different host nanocrystals. Interestingly, this single doping strategy is successful in providing such highly emissive nanocrystals considered here, in contrast with the literature reports that would suggest synthesis strategies to be highly specific to the particular dopant, host, or both. We investigate and discuss the possible mechanism of the doping process, supporting the migration of dopant ions from dopant oxide nanocrystals to host nanocrystals as the most likely scenario.

Einstein Relation in n-Channel Inversion Layers of Nonlinear Optical, Optoelectronic and Related Materials: Simplified Theory, Relative Comparison and Suggestion for an Experimental Determination

In this paper, we study the Einstein relation for the diffusivity to mobility ratio (DMR) in n-channel inversion layers of non-linear optical materials on the basis of a newly formulated electron dispersion relation by considering their special properties within the frame work of k.p formalism. The results for the n-channel inversion layers of III-V, ternary and quaternary materials form a special case of our generalized analysis. The DMR for n-channel inversion layers of II-VI, IV-VI and stressed materials has been investigated by formulating the respective 2D electron dispersion laws. It has been found, taking n-channel inversion layers of CdGeAs2, Cd(3)AS(2), InAs, InSb, Hg1-xCdxTe, In1-xGaxAsyP1-y lattice matched to InP, CdS, PbTe, PbSnTe, Pb1-xSnxSe and stressed InSb as examples, that the DMR increases with the increasing surface electric field with different numerical values and the nature of the variations are totally band structure dependent. The well-known expression of the DMR for wide gap materials has been obtained as a special case under certain limiting conditions and this compatibility is an indirect test for our generalized formalism. Besides, an experimental method of determining the 2D DMR for n-channel inversion layers having arbitrary dispersion laws has been suggested.

Einstein relation in n-i-p-i and microstructures of nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestions for an experimental determination

We investigate the Einstein relation for the diffusivity-mobility ratio (DMR) for n-i-p-i and the microstructures of nonlinear optical compounds on the basis of a newly formulated electron dispersion law. The corresponding results for III-V, ternary and quaternary materials form a special case of our generalized analysis. The respective DMRs for II-VI, IV-VI and stressed materials have been studied. It has been found that taking CdGeAs2, Cd3As2, InAs, InSb, Hg1−xCdxTe, In1−xGaxAsyP1−y lattices matched to InP, CdS, PbTe, PbSnTe and Pb1−xSnxSe and stressed InSb as examples that the DMR increases with increasing electron concentration in various manners with different numerical magnitudes which reflect the different signatures of the n-i-p-i systems and the corresponding microstructures. We have suggested an experimental method of determining the DMR in this case and the present simplified analysis is in agreement with the suggested relationship. In addition, our results find three applications in the field of quantum effect devices.

Simple theoretical analysis of the Einstein's photoemission from quantum confined superlattices

In this paper, we study the Einstein's photoemission from III-V, II-VI, IV-VI and HgTe/CdTe quantum well superlattices (QWSLs) with graded interfaces and quantum well effective mass superlattices in the presence of a quantizing magnetic field on the basis of newly formulated dispersion relations in the respective cases. Besides, the same has been studied from the afore-mentioned quantum dot superlattices and it appears that the photoemission oscillates with increasing carrier degeneracy and quantizing magnetic field in different manners. In addition, the photoemission oscillates with film thickness and increasing photon energy in quantum steps together with the fact that the solution of the Boltzmann transport equation will introduce new physical ideas and new experimental findings under different external conditions. The influence of band structure is apparent from all the figures and we have suggested three applications of the analyses of this paper in the fields of superlattices and microstructures.

Thermoelectric power in ultrathin films, quantum wires and carbon nanotubes under classically large magnetic field: Simplified theory and relative comparison

We study the thermoelectric power under classically large magnetic field (TPM) in ultrathin films (UFs), quantum wires (QWs) of non-linear optical materials on the basis of a newly formulated electron dispersion law considering the anisotropies of the effective electron masses, the spin-orbit splitting constants and the presence of the crystal field splitting within the framework of k.p formalism. The results of quantum confined III-V compounds form the special cases of our generalized analysis. The TPM has also been studied for quantum confined II-VI, stressed materials, bismuth and carbon nanotubes (CNs) on the basis of respective dispersion relations. It is found taking quantum confined CdGeAs2, InAs, InSb, CdS, stressed n-InSb and Bi that the TPM increases with increasing film thickness and decreasing electron statistics exhibiting quantized nature for all types of quantum confinement. The TPM in CNs exhibits oscillatory dependence with increasing carrier concentration and the signature of the entirely different types of quantum systems are evident from the plots. Besides, under certain special conditions, all the results for all the materials gets simplified to the well-known expression of the TPM for non-degenerate materials having parabolic energy bands, leading to the compatibility test. (C) 2009 Elsevier B.V. All rights reserved.

Thermoelectric Power Under Strong Magnetic Field in Quantum Dots and Quantized Superlattices: Simplified Theory and Relative Comparison

In this paper, we study the thermoelectric power under strong magnetic field (TPSM) in quantum dots (QDs) of nonlinear optical, III-V, II-VI, GaP, Ge, Te, Graphite, PtSb2, zerogap, Lead Germanium Telluride, GaSb, stressed materials, Bismuth, IV-VI, II-V, Zinc and Cadmium diphosphides, Bi2Te3 and Antimony respectively. The TPSM in III-V, II-VI, IV-VI, HgTe/CdTe quantum well superlattices with graded interfaces and effective mass superlattices of the same materials together with the quantum dots of aforementioned superlattices have also been investigated in this context on the basis of respective carrier dispersion laws. It has been found that the TPSM for the said quantum dots oscillates with increasing thickness and decreases with increasing electron concentration in various manners and oscillates with film thickness, inverse quantizing magnetic field and impurity concentration for all types of superlattices with two entirely different signatures of quantization as appropriate in respective cases of the aforementioned quantized structures. The well known expression of the TPSM for wide-gap materials has been obtained as special case for our generalized analysis under certain limiting condition, and this compatibility is an indirect test of our generalized formalism. Besides, we have suggested the experimental method of determining the carrier contribution to elastic constants for nanostructured materials having arbitrary dispersion laws.

The Photoemission from Quantum Wells, Wires and Carbon Nanotubes:Simplified Theory and Relative Comparison

We investigate the photoemission from quantum wells (QWs) in ultrathin films (UFs) and quantum well wires (QWWs) of non-linear optical materials on the basis of a newly formulated electron dispersion law considering the anisotropies of the effective electron masses, the spin-orbit splitting constants and the presence of the crystal field splitting within the framework of k.p formalism. The results of quantum confined Ill-V compounds form the special cases of our generalized analysis. The photoemission has also been studied for quantum confined II-VI, n-GaP, n-Ge, PtSb2, stressed materials and Bismuth on the basis of respective dispersion relations. It has been found taking quantum confined CdGeAS(2), InAs, InSb, CdS, GaP, Ge, PtSb2, stressed n-InSb and B1 that the photoemission exhibits quantized variations with the incident photon energy, changing electron concentration and film thickness, respectively, for all types of quantum confinement. The photoemission from CNs exhibits oscillatory dependence with increasing normalized electron degeneracy and the signature of the entirely different types of quantum systems are evident from the plots. Besides, under certain special conditions, all the results for all the materials gets simplified to the well-known expression of photoemission from non-degenerate semiconductors and parabolic energy bands, leading to the compatibility test.

Influence of crossed electric and quantizing magnetic fields on the Einstein relation in nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity-to-mobility ratio (DMR) under crossed fields' configuration in nonlinear optical materials on the basis of a newly formulated electron dispersion law by incorporating the crystal field in the Hamiltonian and including the anisotropies of the effective electron mass and the spin-orbit splitting constants within the framework of kp formalisms. The corresponding results for III-V, ternary and quaternary compounds form a special case of our generalized analysis. The DMR has also been investigated for II-VI and stressed materials on the basis of various appropriate dispersion relations. We have considered n-CdGeAs2, n-Hg1-xCdxTe, n-In1-xGaxAsyP1-y lattice matched to InP, p-CdS and stressed n-InSb materials as examples. The DMR also increases with increasing electric field and the natures of oscillations are totally band structure dependent with different numerical values. It has been observed that the DMR exhibits oscillatory dependences with inverse quantizing magnetic field and carrier degeneracy due to the Subhnikov-de Haas effect. An experimental method of determining the DMR for degenerate materials in the present case has been suggested. (C) 2010 Elsevier B.V. All rights reserved.

Use of Polyazaheterocycles in the Assembly of New Cadmium Sulfate Frameworks: Synthesis, Structure, and Properties

The reaction of cadmium sulfate in the presence of polyazaheterocyclic organic molecules gave rise to a variety of new cadmium sulfate phases in water containing solvothermal reaction. The compounds have two- (I) and three-dimensionally (II-VI) extended structures. All the compounds have structures built up by the connectivity involving the cadmium octahedra and the sulfate tetrahedra in which the heterocyclic organic molecules act as the ligand. The linkages between the Cd2+ and (SO4)2- ions form one- (II), two- (I, III, and IV), and three- (V and VI) dimensionally extended cadmium sulfate phases. The connectivity between Cd2+ ion and the heterocyclic ligand also gives rise to one- and two-dimensional structures. The inter-connectivity between the two units gives rise to the observed structures. The presence of Cd-O-Cd chains and Cd-O-Cd layers in some of the structures is noteworthy. The adsorption/desorption studies suggest that the cadmium sulfate phases adsorb/desorb anionic dyes selectively in the presence of water/ethanol, respectively. The photocatalytic degradation studies on cationic dyes under UV-irradiation indicate modest activity. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicate good catalytic behavior. The various properties exhibited by the cadmium sulfate phases suggest that these compounds are versatile. All the compounds were characterized by powder X-ray diffraction, thermogravimetric analysis, infrared (IR) and UV-visible studies.

On the two-dimensional thermoelectric power in quantum wells of non-parabolic materials under magnetic quantization

We present a simplified theoretical formulation of the thermoelectric power (TP) under magnetic quantization in quantum wells (QWs) of nonlinear optical materials on the basis of a newly formulated magneto-dispersion law. We consider the anisotropies in the effective electron masses and the spin-orbit constants within the framework of k.p formalism by incorporating the influence of the crystal field splitting. The corresponding results for III-V materials form a special case of our generalized analysis under certain limiting conditions. The TP in QWs of Bismuth, II-VI, IV-VI and stressed materials has been studied by formulating appropriate electron magneto-dispersion laws. We also address the fact that the TP exhibits composite oscillations with a varying quantizing magnetic field in QWs of n-Cd3As2, n-CdGeAs2, n-InSb, p-CdS, stressed InSb, PbTe and Bismuth. This reflects the combined signatures of magnetic and spatial quantizations of the carriers in such structures. The TP also decreases with increasing electron statistics and under the condition of non-degeneracy, all the results as derived in this paper get transformed into the well-known classical equation of TP and thus confirming the compatibility test. We have also suggested an experimental method of determining the elastic constants in such systems with arbitrary carrier energy spectra from the known value of the TP. (C) 2010 Elsevier Ltd. All rights reserved.

Photoelectron spectroscopic study of CdS nanocrystallites

Nanocrystallites of semiconductors, especially those belonging to II-VI and III-V groups, show size-dependent optical and electrical properties. In this paper we report on x-ray photoemission results of CdS nanocrystallites of two different sizes and compare these results with bulk CdS. The S 2p and 2s core levels of the nanocrystallites reveal three different types of sulfur, unlike bulk CdS, which shows only one kind of sulfur species. Details of the spectroscopic results provide estimates of the size of the nanocrystallites, while also indicating the origin of the stability of such small clusters. [S0163-1829(99)03811-4].

Novel Mn-doped chalcopyrites

Heavily Mn-doped II-VI-V-2 semiconductors, such as CdGeP2 and ZnGeP2 have been prepared by depositing Mn on single crystalline substrate at nearly 400 T in an ultra high vacuum chamber. Well-defined ferromagnetic hysteresis with a saturation behavior appears in the magnetization curve up to above room temperature. The chemical states of the ZDGeP(2):Mn interface has been clarified by a careful in situ photoemission spectroscopy. The as-prepared surface consists of Ge-rich, metallic Mn compound. In and below the sub-surface region, dilute divalent Mn species as precursors of the DMS phase exist. No MnP phase was observed at any stage of the depth profile. Theoretical band-calculation suggests that the system with vacancies (Cd, V-c, Mn)GeP2 or a non-stoichiometric (Cd, Ge, Mn)GeP2 are ferromagnetic and energetically stable although ferromagnetism is not stable in a stoichiometric compound (Cd, Mn)GeP2. (C) 2003 Elsevier Ltd. All rights reserved.

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Oxidation of aqueous sulphur dioxide catalysed by poly-4-vinylpyridine-Cu(II) complex .2. Combined homogeneous and heterogeneous phase oxidation

Aqueous phase oxidation of sulphur dioxide at low concentrations catalysed by a PVP-Cu complex in the solid phase and dissolved Cu(II) in the liquid phase is studied in a rotating catalyst basket reactor (RCBR). The equilibrium adsorption of Cu(II) and S(VI) on PVP particles is found to be of the Langmuir-type. The diffusional effects of S(IV) species in PVP-Cu resin are found to be insignificant whereas that of product S(VI) are found to be significant. The intraparticle diffusivity of S(VI) is obtained from independent tracer experiments. In the oxidation reaction HSO3- is the reactive species. Both the S(IV) species in the solution, namely SO2(aq) and HSO3- get adsorbed onto the active PVP-Cu sites of the catalyst, but only HSO3- undergoes oxidation. A kinetic mechanism is proposed based on this feature which shows that SO2(aq) has a deactivating effect on the catalyst. A rate model is developed for the three-phase reaction system incorporating these factors along with the effect of concentration of H2SO4 on the solubility of SO2 in the dilute aqueous solutions of Cu(II). Transient oxidation experiments are conducted at different conditions of concentration of SO2 and O-2 in the gas phase and catalyst concentration, and the rate parameters are estimated from the data. The observed and calculated profiles are in very good agreement. This confirms the deactivating effect of nonreactive SO2(aq) on the heterogeneous catalysis.