Hole polaron of small radius in assemblies of hydrated mono-protonated meso-tetraphenylporphine dimers at 77 K

Polaron theory is often used for the study of electrons and holes mobility in semiconductors when longitudinal optical (LO) phonons are generated upon the charge carriers moving. The polaron theory was applied to explain long-wavelength absorptions observed nearby Soret band in the electronic spectra of assemblies of mono-protonated meso-tetraphenylporphine dimer (TPP₂H⁺) that are interpreted as LO-phonons originated due to proton movement. The energy of hole polaron is found to be 1.50 eV at 77 K. Energy of Franck–Condon transitions of LO-phonons generated by hole polaron moving through water confined in the assemblies with distortions of O–H bonds is 0.2653 eV (2138 cm⁻¹). A broad band around 2127 cm⁻¹ corresponding the same energy of O–H bonds vibrations is observed in IR spectra of the assemblies consisting of water and mainly of TPP₂H⁺ species in the solid state indicating the presence of similar distortions of the hydrogen bonds. The radius of protonic sphere of 0.202 Å, which was estimated as a polaron quasiparticle moving through the confined water at 77 K, is found in agreement with earlier evaluated one of 0.265 Å that was obtained for proton diffusion at 298 K in similar assemblies.     

Luminescence study of self-trapped excitons in CdMoO4

Luminescence properties of CdMoO₄ crystals have been investigated in a wide temperature range of T=5–300 K. The luminescence-excitation spectra are examined by using synchrotron radiation as a light source. A broad structureless emission band appears with a maximum at nearly 550 nm when excited with photons in the fundamental absorption region (<350 nm) at T=5 K. This luminescence is ascribed to a radiative transition from the triplet state of a self-trapped exciton (STE) located on a (MoO₄)^2? complex anion. Time-resolved luminescence spectra are also measured under the excitation with 266 nm light from a Nd:YAG laser. It is confirmed that triplet luminescence consists of three emission bands with different decay times. Such composite nature is explained in terms of a Jahn–Teller splitting of the triplet STE state. The triplet luminescence at 550 nm is found to be greatly polarized in the direction along the crystallographic c axis at low temperatures, but change the degree of polarization from positive to negative at T>180 K. This remarkable polarization is accounted for by introducing further symmetry lowering of tetrahedral (MoO₄)^2? ions due to a uniaxial crystal field, in addition to the Jahn–Teller distortion. Furthermore, weak luminescence from a singlet state locating above the triplet state is time-resolved just after the pulse excitation, with a polarization parallel to the c axis. The excited sublevels of STEs responsible for CdMoO₄ luminescence are assigned on the basis of these experimental results and a group-theoretical consideration.     

Magnetic tuning of exciton–photon resonance in II–VI microcavities

We demonstrate the effectiveness of the giant Zeeman effect in II–VI semimagnetic semiconductors to tune the exciton resonance of quantum wells onto the Fabry–Pérot resonance of a microcavity. A large oscillator strength of 3 × 10¹³cm⁻²per quantum well is deduced from the measured 10.6 meV vacuum Rabi splitting.     

Intrinsic luminescence in oriented BeO crystals under VUV and inner-shell excitation

Beryllium oxide (BeO) crystals were investigated by time-resolved low temperature VUV-spectroscopy at the SUPERLUMI station and BW3 beam line of HASYLAB (DESY, Hamburg). Photoluminescence spectra (3–10.5 eV), luminescence decay kinetics upon selective photoexcitation, as well as luminescence excitation (50–650 eV) and reflectivity (9–35 eV) spectra were measured and analyzed for oriented BeO crystals. It was shown that study of oriented crystals makes the traditional time-resolved spectroscopy method essentially more informative. Formation of the self-trapped exciton excited states of different multiplicity was found to sensitively depend on excitation energy and mutual orientation of the crystal's C optical axis and electric vector E of exciting polarized synchrotron radiation.     

Er–Pr doped tellurite glass nanocomposites for white light emitting diodes

In this paper, optical glass nanocomposites (nanoparticles sizes up to 100 nm) with composition TeO₂–WO₃–PbO–xEr₂O₃–yPr₆O₁₁ (x = 0.30 mol%, y = 0.70 mol%) embedded into polymer matrices was reported. The two types of polymers chosen for present study were: photopolymer oligoetheracryalte (OEA) and polymethylmethacrylate (PMMA), respectively. The incorporation of the titled nanoparticles into the polymer matrices is analyzed optically. The fluorescence spectra of the nanocomposites were compared with the fluorescence spectra of bulk glasses. Based on the comparison of Er^3 + and Pr^3 + ions' energy level schemes, possible energy transfer processes were identified. The prepared glasses are promising candidates for the white light emitting diodes applications.     

Picosecond molecular switch based on the influence of photogenerated electric fields on optical charge transfer transitions

A concept for a picosecond molecular switch is demonstrated using a photoinduced electron transfer reaction in a covalently linked, fixed distance donor–acceptor molecule D–A linked to a perylene-3,4-dicarboximide chromophore, C. The chromophore C possesses a strong charge transfer transition in its optical spectrum. Selective excitation of C within D–A–C using 530 nm, 130 fs laser pulses produces^1 * C, which undergoes singlet–singlet energy transfer to produce^1 * D, which in turn transfers an electron to A. If the D–A–C system is selectively excited with 416 nm, 130 fs laser pulses to produce D ⁺ – A ⁻ –C prior to excitation of C with 530 nm, 130 fs laser pulses, a 25% lower yield of^1 * C is generated. The intense local electric field produced by D ⁺ – A ⁻ causes a 15 nm electrochromic red shift of the charge transfer absorption of C. Thus, the absorption of C at 530 nm is significantly diminished by the presence of D ⁺ – A ⁻ . The need to use two laser pulses with different wavelengths to observe these effects, and the resulting picosecond time response makes it possible to consider applications of this concept in the design of molecular switches.     

High intensity photoluminescence of microcrystalline CsPbBr3 films: Evidence for enhanced stimulated emission at room temperature

Photoluminescence of microcrystalline CsPbBr₃ films grown from the amorphous phase shows stimulated emission not only at cryogenic temperature but also at room temperature, in great contrast to the case for bulk CsPbBr₃ single crystals, where no stimulated emission occurs even at 4.2 K. This is the first demonstration of room temperature stimulated emission from metal halide compounds.The stimulated emission is so strong that single-path-light-amplification stimulated emission across the film thickness is observed at relatively low threshold excitation intensities of ∼50 kW cm⁻² at 77 K and ∼100 kW cm⁻² at 295 K suggesting a large optical gain. The physical origin of the stimulated emission is assigned as due to free exciton-free exciton inelastic collision. The large-gain mechanism is attributable to giant oscillator strength effect characteristic of excitonic superradiance recently reported in this issue.     

Size dependence of ground-state energy of the excitons in spherical Y2O3

The exciton energies of rare earth oxides (Ln₂O₃) have rarely been calculated by the theory. Experimentally, the blue-shift of exciton energy in nanocrystals deviates from the traditional size confinement effect. Herein, the dependence of the ground-state energy of an exciton in Y₂O₃ spheres on particle radius was calculated by using a variational method. In the model, an exciton confined in a sphere surrounded by a dielectric continuum shell was considered. The ground-state energy of exciton comprises kinetic energy, coulomb energy, polarization energy and exciton–phonon interaction energy. The kinetic and coulomb energy were considered by the effective mass and the dielectric continuum and the exciton–phonon interaction energy was given by the intermediate coupling method. The numerical results demonstrate that the present model is roughly consistent with the experimental results. The confinement effect of the kinetic energy is dominant of the blue-shift of the exciton energy in the region of R < 5 nm, while confinement effect of the coulomb energy is dominant of the blue-shift of the exciton energy in the region of R > 5 nm. The polarization energy contributes largely to the exciton energy as the particle size is smaller than ~ 10 nm, while the exciton–phonon interaction energy takes only a little contribution in all the range.     

A waveguide high-pass filter system for measuring the spectrum of pulsed terahertz sources

We propose a system for measuring spectra of terahertz (THz) pulses, including single pulses, which is based on high-pass filters (HPFs). The system consists of channels for measuring amplitudes of pulses (initial pulses and those transmitted via HPFs with different cutoff frequencies) and an algorithm for processing of the obtained data. The pulse spectrum is restored by using the iteration method or the amplitude–frequency method. The iteration method of spectrum restoration is applicable in the range of THz pulse durations from 10⁻⁹ s to 10⁻⁷ s. The amplitude–frequency method is applicable to THz pulses with durations exceeding 10⁻⁸ s. The system for measuring of THz pulse spectra was simulated by using the characteristics of specially developed waveguide HPFs. The relative simulation error of determining the central frequency by the amplitude–frequency method is equal to 2 · 10⁻⁶ for THz pulse durations of 10⁻⁵ s and longer.     

A FT-IR spectroscopic study of ultrasound effect on aqueous imidazole based ionic liquids having different counter ions

Ultrasound (US) effect on 1-butyl-3-methyl-imidazolium (BMI) ionic liquids having different counter anions, BF₄⁻, PF₆⁻ and Cl⁻ in aqueous medium was studied by FT-IR spectroscopy. Their deconvolution spectra were used to analyze the change of hydrogen bond in the absence and presence of US exposure to the ionic liquid. The FT-IR spectra were measured in different water contents without and with US at 23 kHz. These results indicated that the counter anion species in the imidazole based the ionic liquids played an important role for water solvation, when the US was exposed. The US hardly changed hydrogen bonding in the aqueous BMI–PF₆, while the BMI–BF₄ and BMI–Cl showed obvious change in their FT-IR spectra. Especially for the BMI–Cl, significant change was observed by the US exposure in the range of 2.6 wt% to 20 wt% of water contents. The results showed that the US could break the hydrogen bond in the BMI–Cl ionic liquids. In the case of BMI–BF₄, the FT-IR band at 950–1152 cm⁻¹ was significantly intensified under US exposure, due to that the US influenced BF₄⁻-water interaction. But, it was observed that the ionic liquid having PF₆⁻ was very less changed in the US system.     

Nuclear polarization by optical pumping in InP:Fe above liquid nitrogen temperature

Hyperpolarized nuclear spins are observed in optically pumped iron-doped InP from 70 K to 140 K. ³¹P NMR was carried out at 9.28 T (159.8 MHz) during optical excitation with circularly polarized light, using a laser diode (λ∼830 nm) as a source. The enhancement of the nuclear spin polarization by optical pumping at 70 K is estimated to be about 34 for those nuclei in the region of the sample absorbing light. This enhancement decreases with increasing temperature. As the direction of the enhanced nuclear spin polarization is found parallel or antiparallel to the travelling direction of the σ⁺ or σ⁻, the contact hyperfine interaction is dominant compared to the dipolar hyperfine interaction.     

Optical and physical characteristics of In-doped ZnO nanorods

In this paper the effect of indium dopants on structure, optical, electrical and mechanical properties of ZnO nanorods are studied. The average surface potentials and the surface currents of ZnO:In nanorods were 0.25–0.84 mV and 2.2–200 MΩ-cm, respectively. The turn-on threshold field for the vertical ZnO nanorods was around 2–16 V μm⁻¹. Emission current densities of 3.3–911.4 mA cm⁻² were obtained for an electrical field of 60–160 V μm⁻¹. The photoluminescence (PL) spectrum measured at 15–300 K showed that the intensity of the peak at 2.06 eV increased with decreasing temperature, while the peak at 2.06 eV further red shifted and the peak at 3.39 eV blue shifted.     

The broadband NIR emission properties of Bi doped La2O3–Al2O3–SiO2 glass

Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ (in mole%) glasses were prepared by the traditional melting–quenching method. The spectroscopic properties and mechanism of NIR broadband emission in these glasses were investigated in this work. Three excitation wavelengths of 500, 700 and 800 nm were used to test emission spectra. The emission band under 500 nm excitation can be regarded as combination of emission bands under 700 and 800 nm excitation. 2.0 mole% is found to be the optimal Bi₂O₃ doping level in this glass. Under 500 nm excitation its emission peak, FWHM and lifetime of emission band are 1160 nm, 300 nm and 569 μs, respectively. The longest fluorescent lifetime reaches 620 μs under 700 nm excitation. The valence state of Bi in these glasses is suggested to be lower than +3 by X-ray photoelectron spectroscopy. With the help of energy matching, we infer that both Bi⁰ and Bi⁺ centers are responsible for the NIR fluorescence of Bi₂O₃ doped 65SiO₂–20Al₂O₃–15La₂O₃ glass.     

Optical nutation in a magnetized semiconductor quantum well structure

Using the semiclassical coherent radiation—semiconductor interaction model, optical nutation has been analysed in aGaAs / Al_xGa_1 − xAs quantum well structure (QWS) assumed to be immersed in a moderately strong magnetic field and irradiated by a not-too-strong near band gap resonant femtosecond pulsed Ti–sapphire laser. The finite potential well depth of the QWS and the Wannier–Mott excitonic structure of the crystal absorption edge is taken into account. The excitation intensity is assumed to be below the Mott transition where the various many-body effects have been neglected with adequate reasoning. Numerical analysis made for a GaAs quantum well of thickness  ∼  100 Åand the confining layers ofAl_xGa_1 − xAs withx =  0.3 at intensity I ≤  5  ×  10⁶Wcm ^− 2reveals that the real and imaginary parts of the transient complex-induced polarization are enhanced with an increase in the magnetic field and their ringing behaviour confirms the occurrence of optical nutation in the QWS.     

I–V characteristics of a methanol concentration sensor for direct methanol fuel cell (DMFC) by using catalyst electrode of Pt dots

In this work, the methanol sensors were fabricated by using Pt dot catalyst electrode and the level of electrochemical response was analyzed. This kind of sensors can be applicable to sensing the methanol concentration in real-time. When we measured the methanol sensor with 5 nm of Pt dot, we could get 2.00 × 10⁻⁶, 3.06 × 10⁻⁶ and 6.25 × 10⁻⁶ A of electric current value for the methanol concentration of 1, 2 and 3 mole, respectively. The measured voltage was 1 V. To optimize the sensitivity level of Pt dot catalyst electrode, the electrodes were made in H-grid shape. The distance between electrode branches was designed to be 80, 150 and 300 μm, respectively. When we measured the electric current–voltage characteristics of methanol sensor with 2 M of methanol, it was 3.06 × 10⁻⁶, 2.02 × 10⁻⁶ and 1.50 × 10⁻⁶ A, for 80, 150 and 200 μm, respectively. Thus it is suggested that more efficient response of methanol sensing is possible when the distance between electrodes is reduced.     

Fiber curvature sensor based on spherical-shape structures and long-period grating

A novel curvature sensor based on optical fiber Mach–Zehnder interferometer (MZI) is demonstrated. It consists of two spherical-shape structures and a long-period grating (LPG) in between. The experimental results show that the shift of the dip wavelength is almost linearly proportional to the change of curvature, and the curvature sensitivity are −22.144 nm/m⁻¹ in the measurement range of 5.33–6.93 m⁻¹, −28.225 nm/m⁻¹ in the range of 6.93–8.43 m⁻ and −15.68 nm/m⁻¹ in the range of 8.43–9.43 m⁻¹, respectively. And the maximum curvature error caused by temperature is only −0.003 m⁻¹/°C. The sensor exhibits the advantages of all-fiber structure, high mechanical strength, high curvature sensitivity and large measurement scales.     

Photoionization studies of the atmospherically important species N and OH at the Elettra synchrotron radiation source

In this paper angularly resolved photoelectron spectra (PES) and constant-ionic-state (CIS) spectra are presented for the atmospherically important species N and OH.The natural width Γ, line shape parameters q and ρ² and discrete oscillator strengths f have been measured for the members of the N*[2s2p³(⁵S), np] (⁴P) ← N(⁴S) autoionizing resonances for n = 5–10. The n = 5 parameters calculated in this work are in good agreement with the values obtained previously whereas for the resonances with n = 6–10 the values of these parameters are reported for the first time. The asymmetry parameter (β) for the first band of N atoms, the N⁺(³P) ← N(⁴S) ionization, has also been measured in the photon energy range of the above autoionizing resonances.For OH, CIS spectra have been recorded for the first photoelectron band corresponding to the ionization OH⁺(X³Σ⁻, v⁺ = 0) ← OH(X²Π, v″ = 0). In these spectra, rotationally partially resolved bands associated with OH*(a¹Δ3d, v′ = 0) ← OH(X²Π, v″ = 0) resonances have been observed. Suggestions for their assignment are made on the basis of their positions and band simulations which use rotational line strength calculations.     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

A time-resolved luminescence spectroscopy study of non-linear optical crystals K2Al2B2O7

We report the results of complex study of luminescence and dynamics of electronic excitations in K₂Al₂B₂O₇ (KABO) crystals obtained using low-temperature luminescence-optical vacuum ultraviolet spectroscopy with sub-nanosecond time resolution under selective photoexcitation with synchrotron radiation. The paper discusses the decay kinetics of photoluminescence (PL), the time-resolved PL emission spectra (1.2–6.2 eV), the time-resolved PL excitation spectra and the reflection spectra (3.7–21 eV) measured at 7 K. On the basis of the obtained results three absorption peaks at 4.7, 5.8 and 6.5 eV were detected and assigned to charge-transfer absorption from O^2? to Fe³⁺ ions; the intrinsic PL band at 3.28 eV was revealed and attributed to radiative annihilation of self-trapped excitons, the defect luminescence bands at 2.68 and 3.54 eV were separated; the strong PL band at 1.72 eV was revealed and attributed to a radiative transition in Fe³⁺ ion.     

Analysis of Tb3+- and melittin-binding with the C-terminal domain of centrin in Euplotes octocarinatus

Centrin is a low molecular mass (20 KDa) protein that belongs to the EF-hand superfamily. In this work, the interaction between the Tb³⁺-saturated C-terminal domain of Euplotes octocarinatus centrin (Tb₂-C-EoCen) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated using difference UV–vis spectra and the fluorescence spectra methods. In 100 mM N-2-hydroxy-ethylpiperazine-N-2-ethanesulfonic acid (Hepes) at pH 7.4, with the addition of Tb₂-C-EoCen, four new peaks were observed at 265 nm, 278 nm, 317 nm and 360 nm by absorptivity compared with blank solution of TNS. At the same time, the reaction could be measured by fluorescence spectra. The fluorescence emission of TNS was shifted from 480 nm to 445 nm in the presence of Tb₂-C-EoCen. Meanwhile, its fluorescence intensity was increased markedly. The 1:1 stoichiometric ratio of C-EoCen to TNS was confirmed by fluorescence titration curves. The conditional binding constants of TNS with C-EoCen and Tb₂-C-EoCen were calculated to be log K_{(C-EoCen-TNS)}=5.32±0.04  M^?1 and log K_{(Tb2-C-EoCen-TNS)}=5.58±0.12 M^?1, respectively. In addition, the protein of Tb₂-C-EoCen binding with melittin was also studied. Based on the fluorescence titration curves, the 1:1 stoichiometric ratio of Tb₂-C-EoCen to melittin was confirmed. And the conditional binding constant of C-EoCen with melittin was calculated to be log Ka′=6.79±0.17 M^?1.