Semiempirical tight-binding modelling of III-N-based heterostructures

In this work, we present a second nearest neighbour sp³s^* semi-empirical tight-binding theory to calculate the electronic band structure of heterostructures based on group III-N binary semiconductors and their ternaries. The model Hamiltonian includes the second nearest neighbour (2nn) interactions, the spin–orbit splitting and the nonlinear variations of the atomic energy levels and the bond length with ternary mole fraction. Using this sp³s^* tight-binding approach, we investigated the electronic band structure of Al_1−xGa_xN/GaN and In_1−xGa_xN/GaN heterostructures as a function of composition and interface strain for the entire composition range (0≤x≤1). There is an excellent agreement between the model predictions and experiment for the principal bandgaps at Γ, L and X symmetry points of the Brillouin zone for AlN, GaN and InN binaries and Al_1−xGa_xN and In_1−xGa_xN ternaries. The model predicts that the composition effects on the valence band offsets is linear, but on the conduction band offsets is nonlinear and large when the interface strain and deformation potential is large.     

Structural and optical properties of Ba(Ti1−x,Nix)O3 thin films prepared by sol–gel process

Ba(Ti_1−x,Ni_x)O₃ thin films were prepared on fused quartz substrates by a sol–gel process. X-ray diffraction and Raman scattering measurements showed that the films are of pseudo-cubic perovskite structure with random orientation and the change of lattice constant caused by Ni-doping with different concentrations is very small. Optical transmittance spectra indicated that Ni-doping has an obvious effect on the energy band structure. The energy gap of Ba(Ti_1−x,Ni_x)O₃ decreased linearly with the increase of Ni concentration. It indicates that the adjusting of band gap can be achieved by controlling the Ni-doping content accurately in Ba(Ti_1−x,Ni_x)O₃ thin films. This has potential application in devices based on ferroelectric thin films.     

Pressure studies of conduction-band N-pair-state mixing in dilute GaAs1−xNx alloys

High-pressure photoluminescence (PL) experiments (at 9 K) are reported for GaAs_1−xN_x/GaAs quantum wells having N compositions (x=0.0025, 0.004) in the dilute regime where the GaAs_1−xN_x alloy conduction band (CB) evolves rapidly by incorporation of N-pair states. Under increasing pressure, the PL spectra exhibit several new N-pair features that derive from CB-resonant states at 1 atm. Two of these features appear strongly at sub-band-gap energies for P29 kbar in the x=0.0025 sample, but are absent for all pressures in the x=0.004 sample. Several competing PL assignments due to bound-exciton recombination at NN_i pairs (i=1–4 is the anion separation) are considered in light of prior findings for N-doped (10¹⁷ cm⁻³) GaAs. The absence of certain PL features in the x=0.004 sample shows that N-pair states mix into the CB-continuum via a selective process, and this selectivity offers an important test for band-structure calculations in dilute GaAs_1−xN_x alloys.     

Comparison of the band alignment of strained and strain-compensated GaInNAs QWs on GaAs and InP substrates

We present a comparison of the band alignment of the Ga_1−xIn_xN_yAs_1−y active layers on GaAs and InP substrates in the case of conventionally strained and strain-compensated quantum wells. Our calculated results present that the band alignment of the tensile-strained Ga_1−xIn_xN_yAs_1−y quantum wells on InP substrates is better than than that of the compressively strained Ga_1−xIn_xN_yAs_1−y quantum wells on GaAs substrates and both substrates provide deeper conduction wells. Therefore, tensile-strained Ga_1−xIn_xN_yAs_1−y quantum wells with In concentrations of x0.53 on InP substrates can be used safely from the band alignment point of view when TM polarisation is required. Our calculated results also confirm that strain compensation can be used to balance the strain in the well material and it improves especially the band alignment of dilute nitride Ga_1−xIn_xN_yAs_1−y active layers on GaAs substrates. Our calculations enlighten the intrinsic superiority of N-based lasers and offer the conventionally strained and strain-compensated Ga_1−xIn_xN_yAs_1−y laser system on GaAs and InP substrates as ideal candidates for high temperature operation.     

Band offset calculations applied to III–V nitride quantum well device engineering

Band offset calculations for zinc-blende pseudomorphically strained Al_1−xGa_xN/Al_1−yGa_yN and In_xGa_1−xN/In_yGa_1−yN interfaces have been performed on the basis of the model solid theory combined with ab initio calculations. From the results obtained, we have calculated, separately, the valence and conduction band discontinuities of In_xGa_1−xN/GaN and GaN/Al_1−xGa_xN as a function of the indium and gallium contents respectively. Using the latter results, we have extended our study to simulate band discontinuities for strained Ga_1−xIn_xN/relaxed Al_1−yGa_yN heterointerfaces. Information derived from this investigation will be useful for the design of lattice mismatched heterostructures in modeling optoelectronic devices emitting at ultraviolet to near infrared wavelengths.     

Electron–hole symmetry and spin–orbit splitting in IV–VI asymmetric quantum wells

It is shown that, due to the electron–hole symmetry of the fundamental gap of the lead–salts (PbTe, PbSe and PbS), the Rashba spin splitting in their flat band asymmetric quantum wells is much reduced with the usual equal conduction and valence band-offsets. Different from the III–V case, we find that the important structure inversion asymmetry for the Rashba splitting in IV–VI quantum wells with different left and right barriers is not a material property (i.e., barrier height, effective mass or band gap) but results from the band alignment. This is shown by specific envelope function calculations of the spin-dependent subband structure of Pb_1−xEu_xTe/PbTe/Pb_1−yEu_yTe asymmetric quantum wells (x≠y), based on a simple but accurate four-band kp model for the bulk band structure near the gap, which takes into account band anisotropy, nonparabolicity and multi-valley effects.     

Electrical properties of perovskite-type La(Cr1−xMnx)O3+δ

Perovskite-type La(Cr_1−xMn_x)O_3+δ (0.0x1.0) was synthesized using a sol–gel process. The crystal structure of La(Cr_1−xMn_x)O_3+δ changes from orthorhombic to rhombohedral at x=0.6. The Mn⁴⁺ ion content increases monotonically in the range 0.2x1.0. The magnetic measurement of La(Cr_1−xMn_x)O_3+δ indicates that a Mn³⁺ ion is a high-spin state with (d)³(dγ)¹. The variation of the average (Cr, Mn)-O distance is explained by ionic radii of the Cr³⁺, the Mn³⁺, the Mn⁴⁺ ions. Since the log σT–1/T curve is linear and the Seebeck coefficient (α) is independent of temperature, it is considered that La(Cr_1−xMn_x)O_3+δ is a p-type semiconductor and exhibits the hopping conductivity.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Photo- and electroluminescence of sulfide and silicate phosphors embedded in synthetic opal

The sulfide (ZnS:Mn, Zn_xCd_1−xS:Mn, Zn_xCd_1−xS:Ag) and silicate (Zn₂SiO₄:Mn) phosphors were synthesized directly inside the pores of synthetic opal by chemical bath deposition. These composites are perfect three-dimensional photonic crystals, which produce effective photo- and electroluminescence at room temperature. The emission spectra are considerably modified by the photonic crystal structure to become anisotropic in accordance with the photonic band gap angular dispersion.     

Quantum properties of two-dimensional electron gas in the inversion layer of Hg1−xCdxTe bicyrstals

The electronic and magnetotransport properties of conduction electrons in the grain boundary interface of p-type Hg_1−xCd_xTe bicrystals are investigated. The results clearly demonstrate the existence of a two-dimensional degenerate n-type inversion layer in the vicinity of the grain boundary. Hydrostatic pressure up to 10³ MPa is used to characterize the properties of the two-dimensional electron gas in the inversion layer. At atmospheric pressure three series of quantum oscillations are revealled, indicating that tthree electric subbands are occupied. From quantum oscilations of the magnetoresistivity the characteristics parameters of the electric subbands (subband populations n_si, subband energies E_F−E_i, effective electron masses m^*_ci) and their pressure dependences are established. A strong decrease of the carrier concentration in the inversion layer and of the corresponding subband population is observed when pressure is applied A simple theoretical model based on the triangular-well approximation and taking into account the pressure dependence of the energy band structure of Hg_1−xCd_xTe is use to calculate the energy band diagram of the quantum well and the pressure dependence of the subband parameters.     

Analysis of the 2ν3 band of CD3F at 5.06 μm recorded under high resolution

The 2ν₃(A₁) band of ¹²CD₃F near 5.06 μm has been recorded with a resolution of 20–24 × 10⁻³ cm⁻¹. The value of the parameter (α^B − α^A) for this band was found to be very small and, therefore, the K structure of the R(J) and P(J) manifolds was unresolved for J < 15 and only partially resolved for larger J values. The band was analyzed using standard techniques and values for the following constants determined: ν₀ = 1977.178(3) cm⁻¹, B″ = 0.68216(9) cm⁻¹, D″_J = 1.10(30) × 10⁻⁶ cm⁻¹, α^B = (B″ − B′) = 3.086(7) × 10⁻³ cm⁻¹, and β^J = (D″_J − D′_J) = −3.24(11) × 10⁻⁷ cm⁻¹. A value of α^A = (A″ − A′) = 2.90(5) × 10⁻³ cm⁻¹ has been obtained through band contour simulations of the R(J) and P(J) multiplets.     

The 2ν8 Band of CH3CN

The overtone band 2ν⁰₈ of CH₃CN around 720 cm⁻¹ has been measured on a Bruker Fourier transform spectrometer at a resolution of 0.003 cm⁻¹. Only the parallel band was observed, but due to the l(2, 2) resonance, ΔK = −2 lines leading to the v₈ = 2, l₈ = −2 levels with K = 1-3 could be seen. More information for the l₈ = ±2 component of the vibrational state v₈ = 2 was evaluated from the hot band 2ν^±2₈ - ν^±1₈. Altogether more than 1000 lines were assigned. In the fit pure rotational lines from literature were also combined. Among the results the anomalous A₀ - A′ values 4.6722(13) × 10⁻³ cm⁻¹ for the 2ν⁰₈ band and 7.0324(32) × 10⁻³ cm⁻¹ for the 2ν^±2₈ band are striking.     

Study of correlation effects on stability of many-body complexes in III–V nitride quantum dots

The aim of this work is to analyze theoretically the correlation energies, for neutral, positive and negative excitons and bi-excitons in the III–V nitride In_xGa_1−xN/GaN quantum dot; where x=17.5% denotes the indium concentration. So, we propose a model consistent with experimental observations that is small In_xGa_1−xN truncated pyramids with circular base lying on wetting layer, both buried into GaN matrix. The correlation energies of many-body complexes X, X⁻, X⁺ and XX are investigated as a function of the quantum dot radius r_c and the intrinsic electric field.     

Photoluminescence characterization of air exposed AlGaAs surface and passivated ex situ by ultrathin silicon interface control layer

Using the photoluminescence surface state spectroscopy (PLS³) technique, attempts were made to determine the surface state density (N_ss) distribution on Al_xGa_1−xAs (x≈0.3) surfaces passivated by the Si interface control layer (ICL) technique. Air-exposed AlGaAs epitaxial wafers which are technologically important for fabrication of various devices were passivated ex situ by forming a SiO₂/Si₃N₄/Si ICL/AlGaAs structure after the HCl treatment and their photoluminescence behavior was investigated in detail. The result of the PLS³ analysis indicated that Si ICL-based passivation reduces the minimum interface state density value down to 10¹⁰ cm⁻² eV⁻¹ range. Some indication was also obtained that further improvements are possible by using electron cyclotron resonance (ECR)-enhanced N₂ plasma for Si₃N₄/Si ICL interface formation.     

Power factor enhancement in Pr-substituted alloys prepared by high-pressure sintering

Bi₈₅Sb_15−xPr_x (x=0,1,2,3) alloys with partial substitution of Pr for Sb were synthesized by mechanical alloying followed by high-pressure sintering. The crystal structure was characterized by X-ray diffraction. The electrical conductivity and Seebeck coefficient were measured in the temperature range of 80–300 K. The results show that the electrical conductivity and Seebeck coefficient of Pr-substituted samples are both larger than those of the reference sample, Bi₈₅Sb₁₅, in the whole measurement temperature range. The power factor of Bi₈₅Sb₁₃Pr₂ reaches a maximum value of 3.83×10⁻³ W K⁻² m⁻¹ at 235 K, which is about four times larger than that of the reference sample, Bi₈₅Sb₁₅, at the same temperature.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Far-infrared dielectric functions and phonon spectra of alloys determined by spectroscopic ellipsometry

We have used spectroscopic ellipsometry to determine the complex dielectric function of a series of ternary Be_xZn_1−xTe thin films grown by molecular beam epitaxy. The II–VI semiconductor alloys were grown on InP substrates that had an InGaAs buffer layer. After the growth, X-ray diffraction experiments were performed in order to determine the alloy concentration. A standard inversion technique was used to obtain the dielectric functions from the measured ellipsometric spectra, obtained between 2000 nm (5000 cm⁻¹) and 40,000 nm (250 cm⁻¹). By modelling the dielectric function as a collection of oscillators, representing longitudinal and transverse optical phonons of the Be_xZn_1−xTe lattice, we were able to recover the phonon spectra for this alloy system. It is argued that the additional phonon modes that are obtained from ellipsometry are best understood from the recently-proposed percolation model.     

Energy band gaps for the GaxIn1−xAsyP1−y alloys lattice matched to different substrates

A pseudopotential formalism within the virtual crystal approximation in which the effects of composition disorder are involved is applied to the Ga_xIn_1−xAs_yP_1−y quaternary alloys in conditions of lattice matching to GaAs, InP and ZnSe substrates so as to predict their energy band gaps. Very good agreement is obtained between the calculated values and the available experimental data for the alloy lattice matched to InP and GaAs. The alloy is found to be a direct-gap semiconductor for all y compositions whatever the lattice matching to the substrates of interest. The (Γ→Γ) band-gap ranges and the ionicity character are found to depend considerably on the particular lattice-matched substrates suggesting therefore that, for an appropriate choice of y and the substrate, Ga_xIn_1−xAs_yP_1−y could provide more diverse opportunities to obtain desired band gaps, which opens up the possibility of discovering new electronic devices with special features and properties.     

The rotational-vibrational spectra of HNCS and DNCS : An analysis of the high resolution spectra

Ro-vibrational spectra of HNCS and DNCS have been obtained in the spectral range 300–4000 cm⁻¹ with a practical resolution limit of 0.06 cm⁻¹ in the region 350–1200 cm⁻¹ and 0.15 cm⁻¹ in the region 1200–4000 cm⁻¹. The observed fine structure permitted definitive assignments for some of the ^PQ_K, ^QQ_K, and ^RQ_K branches in both molecules, and yielded sets of rotational constants in substantial agreement with those obtained from recent microwave and far-infrared studies. Precise estimates of the band origins have been obtained and there is evidence of second-order Coriolis coupling between the three bending modes in each molecule. The isolation of the out-of-plane bending modes has lead to a re-assignment of ν₃, ν₄, ν₅, and ν₆ for each molecule. The band origins, uncorrected for Coriolis interaction, are for HNCS and DNCS, respectively. v₁:3538.6 ±0.3, 2644.5±0.5cm⁻¹;v₂:1989.0 ±0.3, 1944.3±0.5cm⁻¹;v₃:857.0 ±0.6, 851.0±0.1cm⁻¹;v₄:615.0 ±0.5, 549.1±0.2cm⁻¹;v₅:469.2 ±0.1, 365.8 ±0.2cm⁻¹;v₆:539.2 ±0.5, 481.0±0.1cm⁻¹;     

Electrical conductivity of Ag/Na ion-exchanged titanosilicate glasses

The Ag₂O–TiO₂–SiO₂ glasses were prepared by Ag⁺/Na⁺ ion-exchange method from Na₂O–TiO₂–SiO₂ glasses at 380–450 °C below their glass transition temperatures (T_g), and their electrical conductivities were investigated as functions of TiO₂ content and the ion-exchange ratio (Ag/(Ag+Na)). In a series of glasses 20R₂O·xTiO₂·(80−x)SiO₂ with x=10, 20, 30 and 40 in mol%, the electrical conductivities at 200 °C of the fully ion-exchanged glasses of R=Ag were in the order of 10⁻⁵ or 10⁻⁴ S cm⁻¹ and were 1 or 2 orders of magnitude higher than those of the initial glasses of R=Na. The glass of x=30 exhibited the highest increase of conductivity from 3.8×10⁻⁷ to 1.3×10⁻⁴ S cm⁻¹ at 200 °C by Ag⁺/Na⁺ ion exchange among them. When the ion-exchange ratio was changed in 20R₂O·30TiO₂·50SiO₂ system, the electrical conductivity at 200 °C exhibited a minimum value of 7.6×10⁻⁸ S cm⁻¹ around Ag/(Ag+Na)=0.3 and increased steeply in the region of Ag/(Ag+Na)=0.5–1.0. When the ion-exchange temperature was changed from 450 to 400 °C, the conductivity of the ion-exchanged glass of x=30 decreased. The infrared spectroscopy measurement revealed that the ion-exchange temperature of 450 °C induced a structural change in the glass of x=30. The T_g of the fully ion-exchanged glass of x=30 was 498 °C. It was suggested that the incorporated silver ions changed the average coordination number of titanium ions to form higher ion-conducting pathway and resulted in high conductivity in the titanosilicate glasses.