Studies on the opto-electronic properties of III–V and II–VI group semiconductors from optical electronegativities

New empirical relations have been proposed to evaluate bond energies (E_s) in compound semiconductors, first from the knowledge of optical electronegativities of the constituent ions and secondly from the energy gap values. The validity of the two relations has been tested in the case of certain III–V and II–VI group semiconductors by comparing the calculated values of E_s, with those in the literature. From the computed values of E_s, refractive indices have been calculated. The Penn gap (E_p), Fermi energy (E_F) and S_o-parameter for these semiconductors have also been determined. The estimated values of these parameters are utilized to evaluate the electronic polarizabilities (α). The computed values of a compare excellently with the standard data.     

Diluted magnetic semiconductors based on II–VI compounds for photovoltaic detector applications

Infrared photovoltaic p−n junction detectors fabricated by using ternary and quaternary diluted magnetic semiconductors (also called semimagnetic semiconductors) are reviewed. The methods of material and detector preparation are described and the experimental results of the electrical and photoelectric measurements of the detectors are briefly discussed. Some singularities of both the materials and the technological techniques as well as their impact upon the properties of the detectors are analyzed.     

Recent developments in the optical spectroscopy of II–VI compound semiconductors

This review emphasises the information on the binding energies and the identities of electrically impurity and defect centres in II–VI semiconductors which may be obtained from optical spectra. Those shallow centres which may promote useful electrical conductivity are of particular interest. They contribute the richly structured near gap (edge) luminescence, containing weak to moderate phonon coupling and therefore very accessible information about the energy states of the different centres. It is shown that improved material and spectroscopic techniques have yielded considerable information about donors and, particularly shallow to moderately deep acceptors in ZnTe, a key II–VI semiconductor. Persistent impurities such as Li and Cu exert a greater influence on the properties of this semiconductor than formerly supposed. This influence is traced to other II–VI semiconductors, particularly ZnSe. Both the Cu_Zn and P_V acceptors appear to be much deeper in ZnSe than in ZnTe due to lattice relaxation, although evidence for a shallow P-related centre, probably a complex, is presented. Finally, some comments are made about the energy states of centres involving native defects in these compounds, particularly the V_Zn-donor associate centre, responsible for the self-activated luminescence.The author is grateful to D. Bensahel, R. N. Bhargava, S. G. Bishop, H. G. Grimmeiss, N. Magnea, J. E. Nicholls, J. Pautrat, D. J. Robbins, H. Tews and H. Venghaus for permission to use some of their data in this paper. He is also grateful to several of these and other colleagues. cited in the references for discussions of some of the problems described here.     

Luminescence of II–VI and III–V nanostructures

Photoluminescence of HgCdTe epitaxial films and nanostructures and electroluminescence of InAs(Sb,P) light-emitting diode (LED) nanoheterostructures were studied. For HgCdTe-based structures, the presence of compositional fluctuations, which localized charge carriers, was established. A model, which described the effect of the fluctuations on the rate of the radiative recombination, the shape of luminescence spectra and the position of their peaks, was shown to describe experimental photoluminescence data quite reasonably. For InAs(Sb,P) LED nanoheterostructures, at low temperatures (4.2–100 K) stimulated emission was observed. This effect disappeared with the temperature increasing due to the resonant ‘switch-on’ of the Auger process involving transition of a hole to the spin-orbit-splitted band. Influence of other Auger processes on the emissive properties of the nanoheterostructures was also observed. Prospects of employing II–VI and III–V nanostructures in light-emitting devices operating in the mid-infrared part of the spectrum are discussed.     

Electronic structure and optical properties of III–VI crystals

The polarized spectra of the full set of optical functions of GaS, GaSe, InSe, GaTe, InS, and TlSe crystals are determined in a wide range of fundamental-absorption energies. The ?₂ and -Im?^?1 spectra are decomposed into elementary components. The main parameters of the components were determined and the main features of the spectra and transition components are established. The results obtained are explained on the basis of the theoretical band calculations.     

Electrical and optical properties of a-SexTe100–x thin films

The dc electrical conductivity of as deposited thin films of a-Se_xTe_100?x (x=3, 6, 9 and 12) is measured as a function of temperature range from 298 to 383 K. It is observed that the dc conductivity increases exponentially with the increase in temperature in this glassy system. The value of activation energy calculated from the slope of ln σ_dc vs. 1000/T plot, is found to decrease on incorporation of dopant (Se) content in the Te system. On the basis of pre-exponetial factor (σ₀), it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges. The optical absorption measurements show an indirect optical band gap in this system and it decreases on increasing Se concentration. The optical constants (extinction coefficient (k) and refractive index (n)) do change significantly with the photon energy and also with the dopant Se concentration. The decrease in optical band gap may be due to the decrease in activation energy in the present system. It is also found that the real and imaginary parts of dielectric constants show a significant change with the photon energy as well as with the dopant concentration. With large absorption coefficients and compositional dependence of optical band gap and optical constants (n and k), these materials may be suitable for optical disk applications.     

Semiempirical assignment of the electron transitions in manganese(II)-doped II–VI compounds

The electron transitions in manganese(II)-doped II–VI compounds have been assigned by the Angular Overlap Model (AOM). The extracted AOM and electron repulsion parameters are applied to assess the covalency of the respective manganese-ligand bonds. A comparison with Crystal Field Theory (CFT) is made in order to demonstrate the advantages offered by the AOM. The Dq values for Mn(II) in CdS and CdSe were found by interpolation from the Dq vs R⁻⁵_ml relation.     

Influences of Co doping on the structural and optical properties of ZnO nanostructured

Pure and Co-doped ZnO nanostructured samples have been synthesized by a chemical route. We have studied the structural and optical properties of the samples by using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), field-emission transmission electron microscope (FETEM), energy-dispersive X-ray (EDX) analysis and UV–VIS spectroscopy. The XRD patterns show that all the samples are hexagonal wurtzite structures. Changes in crystallite size due to mechanical activation were also determined from X-ray measurements. These results were correlated with changes in particle size followed by SEM and TEM. The average crystallite sizes obtained from XRD were between 20 to 25 nm. The TEM images showed the average particle size of undoped ZnO nanostructure was about 20 nm whereas the smallest average grain size at 3% Co was about 15 nm. Optical parameters such as absorption coefficient (α), energy band gap (E _g ), the refractive index (n), and dielectric constants (σ) have been determined using different methods.     

Influence of Mn doping on structural and optical properties of ZnO nano thin films synthesized by sol–gel technique

Undoped and Mn-doped ZnO samples with different percentages of Mn content (1, 5 and 10?at%) were synthesized by a dip-coating sol?Cgel method. We have studied the structural, chemical and optical properties of the samples by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible spectroscopy. The XRD spectra show that all the samples are hexagonal wurtzite structures. We note that doping favors c-axis orientation along (002) planes. Up to 5?at% of Mn doping level, the c-axis lattice parameter shifts towards higher values with the increase of manganese content in the films. The expansion of the lattice constant of ZnO?CMn indicates that Mn is really doped into the ZnO. The SEM investigations of all samples revealed that the crystallites are of nanometer size. The surface quality of the ZnO?CMn film increases with Mn doping but no significant change of the grain size is observed from SEM images. The transmittance spectra show that the transparency of all the samples is greater than 85?%. We note, also, that a small doping (1?%) lowered the refractive index while the thickness of the layers and the gap increase. However, on raising the proportion of Mn beyond 5?%, practically the same values of index and gap as pure ZnO are found.     

Influence of Ag doping on structural and optical properties of ZnO thin films synthesized by the sol–gel technique

Thin films of Ag–ZnO samples deposited on glass substrates with a different percentage of Ag content (1, 2, and 3 at%) were synthesized, at room temperature, by a dip-coating sol-gel method. The obtained samples are hexagonal wurtzite structure. The average grain size of deposits is about 5 nm. Up to 3 at%, c-axis lattice parameter shifts toward a higher value, which indicates that silver atoms replace Zn atoms in the crystal lattice. As shown by the DRX spectra, growth rate in the (101) direction is favored by the presence of silver ions in the ZnO. The layers present a homogeneous crystallites distribution, as we can remark it on SEM micrographs and exhibit a very low roughness according to AFM images. The entire samples exhibit a transmission value greater than 80 %, in the visible region, while the maximum is obtained for those doped at 2 at%. Energy band varies between 3.15 eV and 3.25 eV. The wider gap obtained is that of the ZnO layer doped with 2 at%. It is worth noting a strong UV emission observed on PL spectrum, performed at very low temperature (liquid nitrogen temperature), for silver doped ZnO compared to that of pure ZnO.     

Shift of the photoemission threshold in III–V and II–VI semiconductors

The reasons why the photoemission threshold energy of semiconductors is lower than the ionization energy of constituent atoms have been investigated. It has been indicated that the previously proposed interpretation of this phenomenon based on the inclusion of an additional intra-atomic Coulomb interaction between the valence electrons is insufficient. It has been shown that the calculation of the electronic energy structure of semiconductors, in particular, of the photoemission threshold, requires taking into account a change in the localization region of the valence electrons when a free atom is embedded into a crystal. A way of taking this change into account in the tight-binding theory has been demonstrated. Corrections to the tight-binding Hamiltonian have been found. The photoemission thresholds of III–V and II–VI semiconductors have been calculated with the inclusion of these corrections. Comparison of the results with the experimental data has been performed.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

Infrared and Raman investigation of the charge–density-wave state in rare-earth tri-telluride compounds

We summarize our recent efforts in investigating the charge–density-wave (CDW) state of the rare-earth tri-tellurides RTe₃ by means of infrared and Raman techniques. We identify the CDW gap, as order parameter of the broken-symmetry ground state, as well as the collective mode of the CDW condensate.     

Theory of band gap bowing of disordered substitutional II–VI and III–V semiconductor alloys

For a wide class of technologically relevant compound III?CV and II?CVI semiconductor materials AC and BC mixed crystals (alloys) of the type A _x B_1?x C can be realized. As the electronic properties like the bulk band gap vary continuously with x, any band gap in between that of the pure AC and BC systems can be obtained by choosing the appropriate concentration x, granted that the respective ratio is miscible and thermodynamically stable. In most cases the band gap does not vary linearly with x, but a pronounced bowing behavior as a function of the concentration is observed. In this paper we show that the electronic properties of such A _x B_1?x C semiconductors and, in particular, the band gap bowing can well be described and understood starting from empirical tight-binding models for the pure AC and BC systems. The electronic properties of the A _x B_1?x C system can be described by choosing the tight-binding parameters of the AC or BC system with probabilities x and 1 ? x, respectively. We demonstrate this by exact diagonalization of finite but large supercells and by means of calculations within the established coherent potential approximation (CPA) We apply this treatment to the II?CVI system Cd _x Zn_1?x Se, to the III?CV system In _x Ga_1?x As and to the III-nitride system Ga _x Al_1?x N.     

Pressure-dependent dynamical properties of Zn-based II–VI semiconductors

The effect of pressure on optical phonons and polaron properties in ZnS, ZnSe, and ZnTe II–VI compound semiconductors has been investigated. The calculations are performed in the framework of ab initio pseudopotential approach based on the density functional perturbation theory. At zero pressure, a reasonable degree of agreement is generally found between our results and data available in the literature. It is found that when pressure is increased the phonon modes at Г in the Brillouin zone are shifted towards high energies. The pressure dependence of features such as Fröhlich coupling parameter, the Debye temperature of the longitudinal optical phonon frequency and the polaron effective mass showed that the polaron properties are sensitive to the pressure effect.     

Electrical,structural, and optical characterization of coal ash–PEO/PMMA blend composites

In the present work, indigenous coal ash taken from Sharigh, Balochistan, Pakistan was used to prepare polymer electrolyte films with PEO/PMMA/LiClO₄. Coal ash was first characterized by various techniques like Surface and Porosity Analysis, SEM/energy dispersive X-ray analysis (EDX), transmission electron microscopy, Fourier transform infrared (FTIR), and XRD. Chemical composition of ash was confirmed by EDX. Then, the utility of coal ash towards fabricating PEO/PMMA/LiClO₄/coal ash composites was studied in order to explore its use as an additive for polymeric blend composites. The ash incorporation into the polymeric blend composites was studied by X-ray diffraction and UV/Visible spectroscopy, while ionic conductivity measurements were undertaken by Impedance spectroscopy. Room temperature conductivity of polymeric blend composites was found to increase sharply with ash content and reached maximum at 3.3 wt.% of ash. Both direct and indirect band gap energies of polymeric blend decreased with coal ash incorporation. The decrease was at peak at 3.3 wt.% of ash. Coal ash has found to improve the performance of polymeric blends.     

Effect of annealing temperature on optical and electrochemical properties of chitosan–ZnO nanostructure

Chitosan–ZnO nanostructures were prepared by chemical precipitation method using different concentration of zinc chloride and sodium hydroxide solutions. Nanorod-shaped grains with hexagonal structure for samples annealed at 300 °C and porous structure with amorphous morphology for samples annealed at 600 °C were revealed in SEM analysis. X-ray diffraction patterns confirmed the hexagonal phase ZnO with crystallite size found to be in the range of ~24.15–34.83 nm. Blue shift of UV–Vis absorption shows formation of nanocrystals/nanorods of ZnO with marginal increase in band gap. Photoluminescence spectra show that blue–green emission band at 380–580 nm. The chitosan–ZnO nanostructures used on surface of a glassy carbon electrode gives the oxidation peak potential at ~0.6 V. The electrical conductivity of chitosan–ZnO composites were observed at 2.1?×?10^?5 to 2.85?×?10^?5?S/m. The nanorods with high surface area and nontoxicity nature of chitosan–ZnO nanostructures observed in samples annealed at 300 °C were suitable as a potential material for biosensing.     

Structural investigation on gamma-irradiated polyacrylamide hydrogels using small-angle neutron scattering and ultraviolet–visible spectroscopy

Small-angle neutron scattering (SANS) and ultraviolet (UV)–visible spectroscopic techniques are used to investigate the microstructural changes in polyacrylamide (PAAm) hydrogels on gamma irradiation. SANS measurements have revealed the presence of inhomogeneities in nanometre scale and reduction of their size with increase in dose. Analysis of SANS data also revealed the increase in the correlation length with increase in dose. The extinction coefficient obtained from the UV–visible spectroscopic studies exhibited λ^?β dependence between 500 and 700 nm and is understood to arise from the existence of scatterers (inhomogeneities) in submicron scale in PAAm hydrogels. The increase in value of exponent β with increase in dose indicates that the size of scatterers decrease with increase in dose.