Nonlinear absorption of a picosecond pulse in a-Si: H

The results of a nonlinear-absorption research in a film of a-Si: H are reported. The absorption is induced by a picosecond laser pulse with quantum energy only slightly exceeding the band gap width of the material. Picosecond pulses obtained by optical methane and hydrogen pumping and stimulated Raman scattering were used in experiments for resonance excitation of the sample. The total absorption is shown to be the sum of the free carrier absorption and absorption by holes trapped on local levels in the “tail” of the conduction band.     

Excitation spectra of self-activated luminescence in ZnSe crystals under pressure

A narrow excitation band observed for S-A luminescence in ZnSe crystal is attributed to free exciton absorption. Some overlap with a higher characteristic band of low intensity is considered for low temperature spectra.This band shifts under pressure toward higher energies with a coefficient dE/dP = (7.5±0.3) meV Kb^-1 at 300 K and (7.4±0.5) meV Kb^-1 at 85 K.The pressure shift of the excitation due to edge absorption is (7.0± 0.5) meV Kb^-1.     

Modulation of charge transfer rate in (N,N′-dimethylamino)benzonitrile liquid solutions

We studied the properties of the emission, absorption and excitation of dual fluorescence of (N,N′?dimethylamino)benzonitrile in a polar aprotic solvent acetonitrile under selective irradiation of solutions by light with different energies of quanta to elucidate mechanisms of dual fluorescence arising in this solvent at different temperatures in the range 274–313 K. In all cases, dual fluorescence of the solute in acetonitrile was observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has a weak effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favour of the intensity of the long-wavelength band at excitation in the range of the long-wavelength absorption band. An interesting and unusual fact is that solution heating is accompanied by essential growth of quantum yield of dual fluorescence at all wavelengths of the excitation. To explain the observed effects, the same dependences were measured and analysed for DMABN in neutral solvent n-hexane in the same conditions. We involve also the data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of DMABN rotational isomers with differing orientation of the dimethylamino group with respect to the benzonitrile. In the excited state, these have different charge-transfer rates, resulting in a modulation in the intensity ratio of the observed fluorescence bands with change excitation energy quanta on the red wing of the absorption band, doi: 10.1134/S0030400X12050219.     

Excitation of lowest electronic states of the uracil molecule by slow electrons

The excitation of lowest electronic states of the uracil molecule in the gas phase has been studied by electron energy loss spectroscopy. Along with excitation of lowest singlet states, excitation of two lowest triplet states at 3.75 and 4.76 eV (±0.05 eV) and vibrational excitation of the molecule in two resonant ranges (1?C2 and 3?C4 eV) have been observed for the first time. The peak of the excitation band related to the lowest singlet state (5.50 eV) is found to be blueshifted by 0.4 eV in comparison with the optical absorption spectroscopy data. The threshold excitation spectra have been measured for the first time, with detection of electrons inelastically scattered by an angle of 180°. These spectra exhibit clear separation of the 5.50-eV-wide band into two bands, which are due to the excitation of the triplet 1³ A?? and singlet 1¹ A?? states.     

Critical Dependence of the Excitonic Absorption in Cuprous Oxide on Experimental Parameters

We study the modification of the exciton absorption in cuprous oxide by the presence of free carriers excited through above band gap excitation. Without this pumping, the absorption spectrum below the band gap consists of the yellow exciton series with principal quantum numbers up to more than n = 20, depending on the temperature, changing over to an about constant, only slowly varying absorption above the gap. Careful injection of free carriers, starting from densities well below 1 μm^–3, leads to a reduction of the band gap through correlation effects. The excitons in the Rydberg regime above n = 10 remain unaffected until the band gap approaches them. Then they lose oscillator strength and ultimately vanish upon crossing with the band gap.     

Alloying induced shift between excitation and luminescence of the nitrogen bound exciton in GaPxAs1−x alloys

Photoluminescence and luminescence excitation spectra have been performed on epitaxial layers of nitrogen doped GaP_xAs_1?x alloys (x > 0.85). The main luminescence excitation band A appears above the photoluminescence band N_x. The composition dependence of this energy shift suggests an alloying energy shift. The origin of this new effect would be the thermalization of the bound exciton population to the lower energy states of the A absorption band which reflects the density of states broadening due to As-P disorder around N atoms     

Study of sequential two photon absorption and conduction band electrons absorption in ZnSe

Using the Z-scan technique and pump–probe technique with 130 fs laser pulses at 800 nm, we verify that an intraband one-photon absorption follows the interband two photon absorption. Particularly, we find that there is an intraband relaxation interspersed between these two absorption processes for some of the conduction band electrons but not all of them. In this study, we measure the interband two photon absorption coefficient and the absorptive cross sections associated with both excitation pathways within the conduction band. In addition, we estimate the time for relaxation of electrons within the conduction band to be 250 fs.     

Low-temperature time-resolved vacuum ultraviolet luminescent spectroscopy of KH2PO4 crystals with defects

Low-temperature photoluminescence (PL) of unactivated KDP crystals under selective synchrotron excitation is for the first time measured with subnanosecond time resolution. Time-resolved PL (2–6 eV) and PL excitation (4–35 eV) spectra, as well as PL kinetics, are measured at 7 K. From the acquired experimental data, luminescent bands related to intrinsic defects of the KDP lattice are identified; in particular, the long-wave band at 2.6 eV is assigned to L defects, and the band at 3.5–3.6 eV is attributed to D defects. An efficient energy transfer over the hydrogen sublattice is shown to take place in KDP at low temperatures. It results in the efficient excitation of L and D center photoluminescence in the fundamental absorption region, at electron transitions to the bottom levels of the conduction band, corresponding to the states of the hydrogen atom. The band gap E _g is evaluated to be 8.0–8.8 eV.     

Luminescence properties of Li6GdB3O9:Ce crystal fibers upon their excitation in the range of 4d → 4f core transitions

We have investigated UV luminescence with a subnanosecond time resolution of Li₆GdB₃O₉:Ce crystal fibers upon their ultrasoft X-ray selective excitation at 10 and 293 K in the range of 4d → 4f core transitions. We have revealed an intense fast-decaying subnanosecond luminescence component, which is caused by a high local density of electronic excitation and Auger core hole relaxation processes, and modulation of the luminescence excitation spectrum by an absorption band of the 4d–4f photoionization giant resonance in the energy range 135–160 eV.     

Solution synthesis of Y1−xBixVO4 for optical applications

Transparent luminescent Y_0.98?xBi_xEu_0.02VO₄ (0<x<1) ceramic films have been prepared using a polymeric route and heat-treatment at 550 °C. A solid solution of zircon-type Y_1?xBi_xVO₄ is obtained for x values below 0.5 whereas phase separation is observed above this limit. The absorption spectra of the films show a shift of the band edge towards high wavelength with the bismuth content, as theoretical calculi have predicted. Luminescence of the films under a UV excitation is typical of europium ion in the zircon structure. The poor correlation between absorption and excitation spectra at high bismuth content is coherent with desexcitation in localized states of valence band. However, the excitation wavelength could still be tuned from deep-UV to near-UV range by inserting bismuth in YVO₄.     

Effects of long-wavelength fluorescence excitation in N, N′-dimethylaminobenzonitrile liquid solutions

We have studied the properties of the emission, absorption, and excitation of dual fluorescence of N,N??-dimethylaminobenzonitrile in a set of solvents of different polarity under selective irradiation of solutions by light with different energies of quanta in the range of the long-wavelength absorption band. In all cases, dual fluorescence is observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has no effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favor of the intensity of the long-wavelength band, which belongs to the charge-transfer state. To explain the observed effects, we involve data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of these systems of rotational isomers that differ in the orientation of the dimethylamino group with respect to benzonitrile. In the excited state, these rotamers have different charge-transfer reaction rates, which leads to a change in the intensity ratio of the observed fluorescence bands upon using the selective excitation.     

Localized electronic excitations in nickel oxide

Valence-electron ionization and optical excitation energies of NiO have been calculated by the SCF?Xα cluster method and transition-state procedure. Ni 3d-like spin orbitals are localized above the O 2p band, leading to well defined peaks in the photoemission spectra. Ligand-to-metal charge-transfer excitations are responsible for strong optical absorption between 4 and 7eV.     

Stokes and anti-stokes excitation of the resonance emission band of crystal phosphors

Anti-Stokes laser excitation has been induced by one photon absorption transitions in the resonance band of the following crystal phosphors: a natural diamond crystal in which the line structure of the spectrum is quite important, a ZnS:Mn crystal in which the line spectrum is easily observed but its intensity is smaller than that of the wide band emission, and halo-complexes of manganese in which the zero phonon line can hardly be observed. In all cases the emitted spectrum has the same shape as while using Stokes excitation; the intensity depends on temperature by means of a Boltzmann factor. Such a result is easily accounted for by the theory; however, except perhaps in the case of diamond, experiment is not in agreement with the simple theoretical model which concludes that the activation energy W involved in the excitation process is equal to the difference E₀ - hv between the energy of the zero phonon line E₀ and the exciting laser energy hv.     

Direct observation of proton transfer from the excited <Emphasis Type="Italic">S</Emphasis><Subscript>2</Subscript> state in the 3-hydroxyflavone molecule

The spectra of dual fluorescence of 3-hydroxyflavone molecules excited by 44-ps pulses in the region of the S ₁ and S ₂ absorption bands are measured with a picosecond resolution. The dynamics of the spectra directly demonstrates the time development of the proton transfer from the carboxyl to the carbonyl group of the molecule. Upon excitation into the main absorption band, the transfer process occurs for about 210 ps. The excitation into the region of the S ₂ band results in a faster (～170 ps) process, and the relative contribution made to the total spectrum by the long-wavelength band, which belongs to the proton-transfer state, is higher in this case for all the time ranges of luminescence recording. The data obtained directly point to an additional channel of proton transfer via the S ₂ state. The probability of this process is estimated to be 0.84 × 10¹² s^?1.     

Electronic effects in multibridged cyclophanes as viewed by the indices of excitation

[2.2]Paracyclophane and its multibridged analogs containing 3 to 6 bridges [3(1,2,3), 3(1,2,4), 3(1,3,5), 4(1,2,3,4), 4(1,2,3,5), 4(1,2,4,5), 5 and 6] were characterized by the indices of excitation expressed as localization of excitation numbers and charge transfer numbers based on the analysis of the transition density matrix. The MO theory, in supermolecule approximation, was applied together with the PPP CI-1 method. The σ-π orbitals interactions between bridges and rings were also considered. With regard to the first UV absorption band at 33000 ± 1000 cm⁻¹, the relatively low transition energies for 3(1,3,5) and 4(1,2,4,5) resulted from the lowest degree of localization of excitation on the aromatic rings and the highest transannular interaction. For 3(1,2,3) and 4(1,2,3,4), the opposite conclusion was reached. The 3(1,3,5) cyclophane was distinguished not only by neglecting the linear correlation between the transition energies E(S₀→ S₂) and the localization numbers that are valid for other cyclophanes, but also by the stronger transannular interaction appearing in the 2¹A' state connected with the third absorption band.     

Optical properties of silylene-biphenylene copolymer films

We have measured absorption, photoluminescence, and photoluminescence excitation spectra, and the photoluminescence time response for films of silylene-biphenylene copolymer, ((C₆H₄)₂(Si(CH₃)₂)_m)_n with m=1,2,4, and 6. The excitation spectra clearly reveal that the lowest absorption band in each copolymer consists of two bands, i.e., a band at 4.7 eV and a band of which energy depends on m. Since the latter band is absent in the copolymer with m=1, the former band is attributed to the lowest π−π* transition in biphenylene subunits. The latter band is attributed to the lowest σ−σ* transition in the silylene subunits, considering its dependence on m. In contrast to the result for solution, the peak energy of photoluminescence band is independent of m. The band has a Stokes shift of more than 1 eV and a large band width of 0.5 eV. The time responses of photoluminescence intensity consist of more than two decay components and the intensity decays more slowly at smaller energy. The large Stokes shift is explained as due to excimer formation between biphenylene subunits. In order to explain the energy dependence of time responses, energy migration is discussed.     

Decay and polarization of luminescence pulses in the 336 nm emission band of KI-Tl

Model predictions for the impurity luminescence center in KI-Tl type crystals are found to agree with experimental results obtained by excitation of KI-Tl at 12K with polarized light pulses in the A and C impurity absorption band. On excitation in the C absorption band, as compared to the A band excitation, a noticeable initial population of the metastable M state has been observed.     

Intracenter transitions of iron-group ions in II–VI semiconductor matrices

A review is made of studies of intracenter optical transitions in 3d shells of iron-group divalent (magnetic) ions. Attention is focused on the emission spectra of Mn²⁺ ions in CdTe, ZnS, and ZnSe crystals. An analysis is made of the structure of intracenter absorption and luminescence and of the effect that the elemental matrix composition, magnetic-ion concentration, temperature, hydrostatic pressure, and structural phase transitions exert on the intracenter transitions. The mutual influence of two electronic excitation relaxation mechanisms, interband and intracenter, is considered. The specific features of the intracenter emission of magnetic ions embedded in two-dimensional systems and nanocrystals associated with a variation in sp-d exchange interaction and other factors are discussed. Data on the decay kinetics over the intracenter luminescence band profile are presented as a function of temperature, magnetic ion concentration, and excitation conditions. The saturation of the luminescence and the variation of its kinetic properties under strong optical excitation, which are caused by excitation migration and the cooperative effect, as well as the manifestation of a nonlinearity in intracenter absorption, are studied.     

Ultraviolet luminescence of Li6Gd(BO3)3: Ce crystals under selective excitation in the region of 4d → 4f transitions

The subnanosecond time-resolved ultraviolet luminescence of Li₆Gd(BO₃)₃: Ce crystals under selective excitation by ultrasoft X-rays in the region of the 4d??4f core transitions at temperatures of 7 and 293 K has been investigated for the first time. The performed investigation has revealed the following features: an intense fast component of the luminescence decay kinetics in the subnanosecond range due to the high local density of electronic excitations and the processes of Auger relaxation of the core hole; the modulation of the luminescence excitation spectrum by the ??giant resonance?? absorption band of the 4d-4f photoionization in the energy range 135?C160 eV; and a new broad luminescence band at an energy of 4.44 eV due to the direct radiative recombination between the genetically related electron in the states of the conduction band bottom and hole in the 4f ground state of the Ce³⁺ ion.     

Photoluminescence analyses of hydrogenated amorphous silicon nitride thin films

Silicon-rich hydrogenated amorphous silicon nitride (a-SiN_x:H) films were grown by plasma enhanced chemical vapor deposition (PECVD) with different r=NH₃/SiH₄ gas flow ratios. The optical absorption characteristics were analyzed by Fourier transform infrared (FTIR) and UV-visible transmittance spectroscopies. The recombination properties were investigated via photoluminescence (PL) measurements. As r was increased from 2 to 9, the PL emission color could be adjusted from red to blue with the emission intensity high enough to be perceived by naked eye at room temperature. The behaviors of the PL peak energy and the PL band broadness with respect to the optical constants were discussed in the frame of electron-phonon coupling and band tail recombination models. A semiquantitative analysis supported the band tail recombination model, where the recombination was found to be favored when the carriers thermalize to an energy level at which the band tail density of states (DOS) reduces to some fraction of the relevant band edge DOS. For the PL efficiency comparison of the samples with different nitrogen contents, the PL intensity was corrected for the absorbed intensity fraction of the incident PL excitation source. The resulted correlation between the PL efficiency and the subgap absorption tail width further supported the band tail recombination model.