Theoretical study of the migration of the hydrogen atom adsorbed on aluminum nanowire

We study the behavior of a hydrogen atom adsorbed on aluminum nanowire based on density functional theory. In this study, we focus on the electronic structure, potential energy surface (PES), and quantum mechanical effects on hydrogen and deuterium atoms. The activation energy of the diffusion of a hydrogen atom to the axis direction is derived as 0.19 eV from PES calculations. The probability density, which is calculated by including quantum effects, is localized on an aluminum top site in both cases of hydrogen and deuterium atoms of the ground state. In addition, some excited states are distributed between aluminum atoms on the surface of the nanowire. The energy difference between the ground state and these excited states are below 0.1 eV, which is much smaller than the activation energy of PES calculations. Thus using these excited states, hydrogen and deuterium atoms may move to the axial direction easily. We also discuss the electronic structure of the nanowire surface using quantum energy density defined by one of the authors.     

Quantum dot p-i-n structure in an electric field

Time-resolved photoluminescence (PL), steady-state PL, and electroluminescence (EL) techniques have been used to characterize the carrier relaxation processes and carrier escape mechanisms in self-assembled InAs/GaAs quantum dot (SAQD) p-i-n structures under reverse bias. The measurements were performed between 5 K and room temperature on a ring mesa sample as a function of bias. At 100 K, the PL decay time originating from the n  =  1 SAQD decreases with increasing reverse bias from ∼3 ns under flat band condition to∼ 400 ps for a bias of −3 V. The data can be explained by a simple model based on electron recombination in the quantum dots (QDs) or escape out of the dots. The escape can occur by one of three possible routes: direct tunneling out of the distribution of excited electronic levels, thermally assisted tunneling of ground state electrons through the upper excited electronic states or thermionic emission to the wetting layer.     

Photophysical parameters and laser performance of 3-(4′-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP): A new laser dye

The spectral properties such as singlet absorption, molar absorptivity, emission spectra, fluorescence quantum yield and excited state lifetime of 3-(4′-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP) have been determined in different solvents. DMAFP dye exhibits a large red shift in both electronic absorption and emission spectra as the solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation. A crystalline solid of DMAFP gives an excimer like emission at 566 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. The ground and excited state protonation constants of DMAFP are calculated and amounted to 1.71 and 8.3, respectively. DMAFP acts as a good laser dye upon pumping with nitrogen laser (λ_ex=337.1 nm) in chloroform, methylene chloride and dioxane and gives laser emission in the range 460–590 nm. The laser parameters such as the tuning range, gain coefficient (α), emission cross section (σ_e) and half-life energy (E_1/2) are calculated. The photoreactivity and net photochemical quantum yield of DMAFP in chloromethane solvents are also studied.     

Fourier Transform Infrared spectrum of the OCD bending mode in methanol-D1

The infrared (IR) spectra corresponding to OCD bending vibration of asymmetrically deuterated methanol species CH₂DOH have been recorded with a Fourier Transform Spectrometer. The spectrum shows a typical structure of a parallel a-type band. This is expected because the bending vibration mainly executed parallel to the symmetry axis The Q-branch lines are grouped closely around 896 cm⁻¹ and the P- and R-Branches show complex structure. Nonetheless it was possible to assign a-type P- and R-branch lines up to K value of 8 and J value up to about 20 in most cases. The Q-branch lines for higher K values can be followed to about J = 15, the presence of which confirmed the assignments. The observations suggest that in the OCD bend some energy levels are highly interacted by highly excited torsional state from the ground torsional state. A full catalogue is presented along with the effective molecular parameters. An intensity anomaly was also observed in the transitions. So far it has been possible to assign only transitions between e₀ ← e₀ states. Plausible explanations of intensity anomaly are presented. Lastly, a number of optically pumped far infrared (FIR) laser lines have been assigned either to exact or tentative quantum states. These assignments should prove valuable for production of new FIR laser lines.     

Accumulation layer and interface effects in doped nonabrupt GaAs/AlxGa1 − xAs single quantum wells

The electron energy levels in doped nonabrupt GaAs/Al_xGa_1 − xAs single quantum wells 100 Å wide are calculated. Interface widths varying from zero to four GaAs unit cells are taken into account, as well as band bendings of 0–90 meV. It is shown that interface effects on the energy levels are important and sensitive to the level of doping. When interfaces of only two GaAs unit cells and a band bending of 40 meV are considered, the ground-state (first excited state) energy level shifts toward energies as high as 4 meV (20 meV).     

A study of an exciton in a quantum dot with Woods–Saxon potential

A theoretical study of an exciton confined in a quantum dot with the Woods–Saxon potential is presented. The great advantage of our methodology is that it enables confinement regimes by varying two parameters in the model potential. Calculations are made by using the method of the numerical diagonalization of the Hamiltonian matrix within the effective-mass approximation. The binding energies of the ground (L=0$L=0$) and first excited (L=1$L=1$) states are obtained as functions of the dot radius. Based on the computed energies and wave functions, the linear, the third-order nonlinear and the total optical absorption coefficients have been examined between the ground and the first excited states. The results are presented as a function of the incident photon energy for the different values of the dot radius and the barrier slope. It is found that the binding energy and the optical properties of the excitons in a quantum dot are strongly affected by the dot radius and the barrier slope of the confinement potential.     

Defects related emission and nanosecond optical power limiting in CuS quantum dots

We report optical and nonlinear optical properties of CuS quantum dots and nanoparticles prepared through a nontoxic, green, one-pot synthesis method. The presence of surface states and defects in the quantum dots are evident from the luminescent behavior and enhanced nonlinear optical properties measured using the open aperture Z-scan, employing 5 ns laser pulses at 532 nm. The quantum dots exhibit large effective third order nonlinear optical coefficients with a relatively lower optical limiting threshold of 2.3 J cm⁻², and the optical nonlinearity arises largely from absorption saturation and excited state absorption. Results suggest that these materials are potential candidates for designing efficient optical limiters with applications in laser safety devices.     

Confinement-enhanced dots-in-a-well QDIPs with operating temperature over 200 K

LWIR InAs/Al_0.3Ga_0.7As/In_0.15Ga_0.85As confinement-enhanced DWELL (CE-DWELL) QDIPs with operation temperatures higher than 200 K are reported. A thin Al_0.3Ga_0.7As barrier layer was inserted above the InAs QDs to improve the confinement of QD states in the In_0.15Ga_0.85As DWELL structure and the device performance. The better confinement of the electronic states increases the oscillator strength of the infrared absorption. The higher excited state energy also improves the escape probability of the photoelectrons. Compared with the conventional DWELL QDIPs, the quantum efficiency increases for more than 20 times and the detectivity is an order of magnitude higher at 77 K. With better device parameters of CE-DWELL, it is possible to achieve high quantum efficiency, high operating temperature and long wavelength detection at the same time.     

Quantum dot nanostructures for multi-band infrared detection

A dual-band (two-color) tunneling-quantum dot infrared photodetector (T-QDIP) structure, which provides wavelength selectivity using bias voltage polarity, is reported. In this T-QDIP, photoexcitation takes place in InGaAs QDs and the excited carriers tunnel through an AlGaAs/InGaAs/AlGaAs double-barrier by means of resonant tunneling when the bias voltage required to line up the QD excited state and the double-barrier state is applied. Two double-barriers incorporated on the top and bottom sides of the QDs provide tunneling conditions for the second and the first excited state in the QDs (one double-barrier for each QD excited state) under forward and reverse bias, respectively. This field dependent tunneling for excited carriers in the T-QDIP is the basis for the operating wavelength selection. Experimental results showed that the T-QDIP exhibits three response peaks at ～4.5 (or 4.9), 9.5, and 16.9 μm and selection of either the 9.5 or the 16.9 μm peak is obtained by the bias polarity. The peak detectivity (at 9.5 and 16.9 μm) of this detector is in the range of 1.0–6.0 × 10¹² Jones at 50 K. This detector does not provide a zero spectral crosstalk due to the peak at 4.5 μm not being bias-selectable. To overcome this, a quantum dot super-lattice infrared photodetector (SL-QDIP), which provides complete bias-selectability of the response peaks, is presented. The active region consists of two quantum dot super-lattices separated by a graded barrier, enabling photocurrent generation only in one super-lattice for a given bias polarity. According to theoretical predictions, a combined response due to three peaks at 2.9, 3.7, and 4.2 μm is expected for reverse bias, while a combined response of three peaks at 5.1, 7.8, and 10.5 μm is expected for forward bias.     

Stark effect in diffused quantum wells

We study the longitudinal Stark effect in diffused AlGaAs/GaAs quantum wells grown along the [1,0,0] direction. The energies of the ground electron and hole states and the first excited hole state are calculated for different diffusion lengths and electric field strengths. The energies of the main optical transitions and their Stark shifts are found. The intensities of the transitions are considered in terms of the bound states spatial distributions. The calculations are carried out within the semi-empirical sp³s ^* tight-binding model including spin and the surface Green function matching method. We compare our results with those obtained by means of other theoretical methods.     

Very high resolution far infrared synchrotron radiation spectrum of methanol-D1 (CH2DOH) in the first three torsional-vibrational modes

In our effort to systematically study the far infrared (FIR) spectra of asymmetrically mono deuterated methanol (CH₂DOH) and thereby obtain the transition wavenumbers with better and better accuracy (Mukhopadhyay, 2016a,b), the complete Fourier transform (FT) spectra from FIR to infrared (IR) vibrational bands (in the range 50–1190 cm⁻¹) have been re-recorded using the Synchrotron Radiation Source at the Canadian Light Sources in Saskatchewan, Canada. The resolution of the spectrum is unprecedented, reaching beyond the Doppler limited resolution as low as about 0.0008 cm⁻¹ with a signal to noise (S/N) ratio is many fold better than that can be obtained by commercially available FT spectrometer using thermal sources (e.g., Globar). Spectra were also recorded beyond 1190 cm⁻¹ to about 5000 cm⁻¹ at a somewhat lower resolution of 0.002–0.004 cm⁻¹. In this report the analysis of the b-type and c-type torsional - rotational spectra in the ground vibrational state corresponding to gauche- (e₁/o₁) to gauche- (e₁/o₁) and gauche- (e₁/o₁) to trans- (e₀) states in the ground vibrational state are reported and an atlas of the wavenumber for about 2500 FIR assigned absorption lines has been prepared. The transitions within a given sub-band are analyzed using state dependent expansion parameters and the Q-branch origins. The data from previous results (Mukhopadhyay, 2016a,b) along with the present work allowed a global analysis yielding a complete set of molecular parameters. The state dependent molecular parameters reproduce the experimental wavenumbers within experimental uncertainty. In addition, the sensitivity of the spectrum allowed observation of forbidden transitions previously unobserved and helped reassignment of rotational angular momentum quantum numbers of some ΔK = ±1, Q-branch transitions in highly excited states recently reported in the literature. To our knowledge the wavenumbers reported in the present work are the most accurate so far reported in the literature and represent the highest resolution spectra for this molecular species.     

Luminescence properties of InAs quantum dots formed by a modified self-assembled method

The luminescence properties of self-assembled InAs quantum dots (QDs) on GaAs (1 0 0) substrates grown by molecular beam epitaxy have been investigated using temperature-dependent photoluminescence (PL) and time-resolved PL (TRPL). InAs QDs were grown using an In-interruption growth technique, in which the indium flux was periodically interrupted. InAs QDs grown using In-interruption showed reduced PL linewidth, redshifted PL emission energy, increased energy level spacing between the ground state and the first excited state, and reduced decay time, indicating an improvement in the size distribution and size/shape of QDs.     

Electronic energy alignment at the PbSe quantum dots/ZnO(101̅0) interface

A number of solar energy conversion strategies depend on exciton dissociation across interfaces between semiconductor quantum dots (QDs) and other electron or hole conducting materials. A critical factor governing exciton dissociation and charge transfer in these systems is the alignment of electronic energy levels across the interface. We probe interfacial electronic energy alignment in a model system, sub-monolayer films of PbSe QDs adsorbed on single crystal ZnO(101?0) surfaces using ultraviolet photoemission spectroscopy. We establish electronic energy alignment as a function of quantum dot size and surface chemistry. We find that replacing insulating oleic-acid capping molecules on the QDs by the short hydrazine or ethanedithiol molecules results in pinning of the valence band maximum (VBM) of QDs to ZnO substrate states, independent of QD size. This is in contrast to similar measurements on TiO₂(110) where the alignment of the PbSe QD VBM to that of the TiO₂ substrate depends on QD size. We interpret these findings as indicative of strong electronic coupling of QDs with the ZnO surface but less with the TiO₂ surface. Based on the measured energy alignment, we predict that electron injection from the 1s_e level in photo-excited PbSe QDs to ZnO can occur with small QDs (diameter ? = 3.4 nm), but energetically unfavorably for larger dots (? = 6.7 nm). In the latter, hot electrons above the 1s_e level are necessary for interfacial electron injection.     

Supersymmetric quantum-well shape optimization for intersubband bound–continuum second harmonic generation

A method is described for the optimized design of quantum-well structures, with respect to maximizing the second-order susceptibilities relevant for second harmonic generation. The possibility is explored of obtaining resonantly enhanced nonlinear optical susceptibilities in quantum wells with two bound states and a continuum resonance state as the dominant third state. The method relies on applying the isospectral (energy structure preserving) transformations to an initial Hamiltonian in order to generate a parameter-controlled family of Hamiltonians. By changing the values of control parameters one changes the potential shape and thus the values of matrix elements relevant to susceptibility to be maximized. The method was used for the design of Al_xGa_1 − xAs -based QWs. The results indicate the possibility of employing continuum states in resonant second harmonic generation at higher photon energies,ℏω =  200–300 meV.     

Magnetic field effects on THz quantum cascade laser: A comparative analysis of three and four quantum well based active region design

We consider the influence of additional carrier confinement, achieved by application of strong perpendicular magnetic field, on inter Landau levels electron relaxation rates and the optical gain, of two different GaAs quantum cascade laser structures operating in the terahertz spectral range. Breaking of the in-plane energy dispersion and the formation of discrete energy levels is an efficient mechanism for eventual quenching of optical phonon emission and obtaining very long electronic lifetime in the relevant laser state. We employ our detailed model for calculating the electron relaxation rates (due to interface roughness and electron–longitudinal optical phonon scattering), and solve a full set of rate equations to evaluate the carrier distribution over Landau levels. The numerical simulations are performed for three- and four-well (per period) based structures that operate at 3.9 THz and 1.9 THz, respectively, both implemented in GaAs/Al_0.15Ga_0.85As. Numerical results are presented for magnetic field values from 1.5 T up to 20 T, while the band nonparabolicity is accounted for.     

Integral and local density of states of InAs quantum dots in GaAs/AlGaAs heterostructure observed by ballistic electron emission spectroscopy near one-electron ground state

Density of states is studied by a ballistic electron emission microscopy/spectroscopy on self-assembled InAs quantum dots embedded in GaAs/AlGaAs heterostructure prepared by metal–organic vapor phase epitaxy. An example of integral quantum dot density of states which is proportional to superposition of a derivative of ballistic current–voltage characteristics measured at every pixel (1.05 nm×1.05 nm) of quantum dot is presented. For the two lowest observed energy levels of quantum dot (the maxima in density of states) the density of states is mapped and correlated with the shape of quantum dot. It was found that prepared quantum dots have a few peaks on their flatter top and a split of the lowest energy level can be observed. This effect can be explained by inhomogeneous (nonuniform) stress distribution in the examined quantum dot.     

Optical absorption and refraction index change of a confined exciton in a spherical quantum dot nanostructure

Electronic energies of an exciton confined in a strained Zn_1−x Cd _x Se/ZnSe quantum dot have been computed as a function of dot radius with various Cd content. Calculations have been performed using Bessel function as an orthonormal basis for different confinement potentials of barrier height considering the internal electric field induced by the spontaneous and piezoelectric polarizations. The optical absorption coefficients and the refractive index changes between the ground state (L = 0) and the first excited state (L = 1) are investigated. It is found that the optical properties in the strained ZnCdSe/ZnSe quantum dot are strongly affected by the confinement potentials and the dot radii. The intensity of the total absorption spectra increases for the transition between higher levels. The obtained optical nonlinearity brings out the fact that it should be considered in calculating the optical properties in low dimensional semiconductors especially in quantum dots.     

Optical investigation of strain-balanced superlattices

A series of strain-balanced GaInAs/AlInAs superlattices were investigated using optical spectroscopy. Three sets of excitonic Landau levels could be resolved in magneto-absorption spectra enabling estimates to be made for the reduced effective masses of the first and second electron to heavy hole (0.040±0.001m_eand 0.034 ± 0.002m_e) and the first electron to light hole (0.053 ±  0.002m_e) excitons. Enhancement in the light hole in-plane effective mass, relative to the heavy hole, is shown to result from the tensile strain in the quantum wells. Temperature-dependent photoluminescence measurements of these samples show evidence of thermal excitation of carriers between the first light and heavy hole states. The activation energy of this process compares well with the separation of the first heavy and light holes confined levels found from low-temperature absorption measurements in two structures with energy splitting of ∼40 meV and <10 meV respectively.     

Observation of charge transfer process for optical emission of rare-earth dopant using electric probing technique

Charge propagation dynamics for the excitation and de-excitation of samarium doped titanium dioxide (TiO₂:Sm) were observed by an electric measurement technique, namely, the phase response of complex impedance to step-function UV irradiation. The probing frequency for the impedance measurement was widely changed, and a critical frequency that emphasizes a specific charge propagation path was found. Above the critical frequency of 1 kHz the transitions from the photo-excited state to ground state progressed via a rapid, and a slow charge propagation path. Through a comparison of the frequency responses obtained under continuous UV light (photo-excited state) and in the dark (ground state), the rapid path was assigned to charge recombination in a defect-dopant complex in TiO₂:Sm, which is consistent with the persistence of luminescence observed in conventional optical measurements. The slow path that is not associated with the optical transition was explained by a dissipation of excited charges. Similar path consistent with the charge dissipation explanation was confirmed below the critical frequency <1 kHz.     

Electronic structure and optical properties of BaMoO4 powders

Barium molybdate (BaMoO₄) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 °C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet–visible (UV–vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm⁻¹, which is associated to the Mo–O antisymmetric stretching vibrations into the [MoO₄] clusters. UV–vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap.