High-excitation photoluminescence studies of CdS1−x Se x quantum dots

Linear absorption and excitation dependent luminescence measurements on CdSSe quantum dots in glass are reported. The new aspects of the spectra are: (i) Stokes shift of linear emission versus absorption and (ii) appearance of new structures in the high energy wing of the luminescence peak under high excitation, which are interpreted as consequences of Coloumb effects, important for dot radii around the exciton Bohr radius.     

Acoustical phonon assisted two-photon excitation of excitonic molecules and resonant raman scattering in evaporated CuCl films

In evaporated CuCl films, Chase et al. have concluded the Bose-Einstein condensation of excitonic molecules for the origin of a sharp emission line which has been ascribed so far to the resonant Raman line in single crystals. A trace of the similar works on evaporated samples confirms that the sharp line shifts its energy with the change of the excitation photon energy; indicating the Raman character. When the excitation photon energy exceeds the resonant energy the Raman line shows broadening, and a new emission band appears which can be ascribed to the radiative annihilation of excitonic molecules generated by the two-photon absorption and one acoustical phonon emission.     

How does the substrate affect the Raman and excited state spectra of a carbon nanotube?

We study the optical properties of a single, semiconducting single-walled carbon nanotube (CNT) that is partially suspended across a trench and partially supported by a SiO₂-substrate. By tuning the laser excitation energy across the E ₃₃ excitonic resonance of the suspended CNT segment, the scattering intensities of the principal Raman transitions, the radial breathing mode (RBM), the D mode and the G mode show strong resonance enhancement of up to three orders of magnitude. In the supported part of the CNT, despite a loss of Raman scattering intensity of up to two orders of magnitude, we recover the E ₃₃ excitonic resonance suffering a substrate-induced red shift of 50 meV. The peak intensity ratio between G band and D band is highly sensitive to the presence of the substrate and varies by one order of magnitude, demonstrating the much higher defect density in the supported CNT segments. By comparing the E ₃₃ resonance spectra measured by Raman excitation spectroscopy and photoluminescence (PL) excitation spectroscopy in the suspended CNT segment, we observe that the peak energy in the PL excitation spectrum is red-shifted by 40 meV. This shift is associated with the energy difference between the localized exciton dominating the PL excitation spectrum and the free exciton giving rise to the Raman excitation spectrum. High-resolution Raman spectra reveal substrate-induced symmetry breaking, as evidenced by the appearance of additional peaks in the strongly broadened Raman G band. Laser-induced line shifts of RBM and G band measured on the suspended CNT segment are both linear as a function of the laser excitation power. Stokes/anti-Stokes measurements, however, reveal an increase of the G phonon population while the RBM phonon population is rather independent of the laser excitation power.     

Luminescent characterization of CaAl2S4:Eu powder

The photoluminescent (PL) emission and excitation behaviour of green-emitting CaAl₂S₄:Eu²⁺ powder phosphor is reported in detail. CaAl₂S₄:Eu²⁺ emission provides good CIE colour coordinates (x=0.141; y=0.721) for the green component in display applications. Powder with a dopant concentration of 8.5 mol% shows the highest luminescence efficiency. Temperature dependence of the radiative properties, such as luminescence intensity and decay time, was investigated. In particular, the Stokes shift, the mean phonon energy, the redshift, the energy of the f→d and d→f transition and the crystal field splitting of the CaAl₂S₄:Eu²⁺ emission were determined. The thermal quenching of the emission was examined.     

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.     

Evidence for non-thermal excitation of energy levels in active biological systems

The ratio R of the intensities of anti Stokes and Stokes Raman shift lines of 124 cm^-1 and of 118 cm^-1 of active E. coli B was measured. For an oscillating system in therm equilibrium R ≈ 0.55 is expected whereas we find R ≈ 1.0. This shows that this system is excited strongly above thermal excitation in agreement with a previous theoretical conjecture [2–5].     

Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

Time resolved luminescence of CdS at high excitation

We report a study at low temperature of the time resolved luminescence of CdS, excited by two photon absorption. Concerning the so called EHP-LO and P bands, we confirm our results previously obtained on CdSe[1, 2]. (a) At high excitation a broad band (peak position at λ > 495 nm) occurs due to radiative recombination in an electron hole plasma, assisted by the emission of one LO phonon. (b) The simultaneous kinetics of the P line (λ ? 490.5 nm) and A-LO line (λ ? 492.5 nm) are conflicting with the interpretation of the P line as resulting of radiative exciton-exciton collisions. We interpret the P line as due to biexciton recombination.We have studied the luminescence in the (I₂-I₁) region (486nm < λ < 490nm) at low excitation. We observe clearly the following, (a) A broad band (488 nm < λ < 490.5 nm) which corresponds to the gain observed in previous experiments of pulse and probe spectroscopy and interpreted as direct recombination in an electron hole liquid (EHL). (b) After the disappearance of the EHL band, one single line (M_D), which shifts continuously towards the I₂ position during the time resolved kinetics. We suggest it to be connected with the high excitation effect on donor impurities (bound polyexcitons).     

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.     

Phonon-assisted polar exciton–transitions in self-organized InAs/GaAs quantum dots

Phonon-assisted exciton transitions are investigated for self-organized InAs/GaAs quantum dots (QDs) using selectively excited photoluminescence (PL) and PL excitation spectroscopy. The results unambiguously demonstrate intrinsic recombination in the coherent InAs/GaAs QDs and the absence of a Stokes shift between ground state absorption and emission. Phonon-sidebands corresponding to a phonon energy of 34 meV are resolved and Huang–Rhys parameters of 0.015 and 0.08 are found for phonon-assisted emission and absorption, respectively, which are about one order of magnitude larger than in bulk InAs. Calculations of the exciton–LO–phonon interaction based on an adiabatic approximation and realistic wave functions for ideal pyramidal InAs/GaAs QDs show this enhanced polar coupling to result from the particular confinement and the strain-induced piezoelectric potential in such strained low-symmetry QDs.     

Localized excitons and energy transfer in ZnxCd1−xS solid solutions

A new photoluminescence (PL) line I_L in Zn_xCd_1?xS solid solutions (x? 0.15) has been studied. Two main features of the I_L line, i.e. (1) concentration dependence of Stokes shift with respect to n = 1A absorption (reflection) peak (2) gradual high-energy shift at rising temperature, are due to localized exciton states (LES) produced by potential fluctuations and to spectral diffusion by phonon assisted tunneling between LES.     

Influence of solvents on the amplified spontaneous emission characteristics of LD-423

Influence of the solvent environments, pumping pulse energies and concentrations on the spectral properties of 1,2,3,8-tetrahydro-1,2,3,3,5-pentamethyl-7H-pyrrolo[3,2-g]quinolin-7-one (LD-423) have been investigated. The photophysical characteristics such as absorption, fluorescence spectra, Stokes’ shift, fluorescence quantum yield, absorption, emission cross sections, extinction coefficient and amplified spontaneous emission (ASE) were measured. Here, LD-423 showed two ASE in a certain organic solution under pulsed laser excitation (Nd: YAG λ_ex?=?355 nm). One of these peaks corresponds to the fluorescence, while the other peak is an anomalous peak which does not have a corresponding fluorescence peak. This abnormal ASE peak can be ascribed to the fact that the excited molecules are connected in the excited state and the solvent acts as a link between them.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

Acoustical phonon anomaly in the Raman spectra of intermediate valent TmSe1−xTex and TmxSe

In the Raman spectra of intermediate valent TmSe_1?xTe_x the same anomaly within the acoustical phonon band at 60 cm^?1 is found as in Tm_xSe. The connection of this anomaly with the valence mixing is confirmed. In a one-dimensional model calculation it is shown that a renormalized LA dispersion curve can produce the observed anomalous peak in the phonon DOS. As an alternative interpretation the possibility of a low energy electronic excitation at 60 cm^?1 is discussed.     

Temperature dependence of luminescence from ZnS0.11Se0.89 random and ordered alloys

Temperature dependence of the luminescence spectra was investigated for a ZnS_0.11Se_0.89 random alloy and a (ZnSe)₁/(ZnS_0.22Se_0.78)₁ ordered alloy with equivalent mean sulfur compositions. The luminescence peak for the random alloy as a function of temperature shows anomalous behavior, while that for the ordered alloy exhibits normal behavior. From the temperature dependence of luminescence intensity for the random alloy, the quenching process can be understood with additional thermal activation energy besides exciton dissociation energy. Through the analysis of the temperature variation of the luminescence line width, the exciton-optical phonon coupling constant is found to be reduced in the random alloy. The results of this study demonstrate that exciton is localized by the potential fluctuation in the random alloy and that the potential fluctuation is significantly constrained in the ordered alloy.     

Temporal dependence of the dipole moment of long-wavelength forms of n-dimethylaminobenzonitrile

The temporal dependences μ_e(t) of the dipole moment of n-dimethylaminobenzonitrile excited to different states by quanta with different energies are evaluated based on the experimental correlation functions of the shift of instantaneous spectra. It is found that, upon excitation into the maximum of absorption, the relaxation changes of the spectra are accompanied by an increase in the dipole moment from 9 D in the Franck-Condon state to 16 D in the stationary state. At the same time, the excitation of luminescence at the red absorption edge by radiation at 403 nm leads to a decrease in the range of variation of the dipole moment. In this case, the initial value of the dipole moment amounts to 14 D and, during the lifetime of the excited state, it increases to 17 D. This indicates that the nature of the radiation excited at the wavelength 403 nm is directly related to internal charge transfer states of n-dimethylaminobenzonitrile.     

The nature of the predominant acceptors in high quality zinc telluride

We report very sharp bound exciton luminescence spectra in high quality melt-grown very lightly compensated ZnTe, p-type with N_A-N_D in the low 10⁺¹⁵ cm^-3. Bound exciton localisation energies at seven shallow neutral acceptors with E_A between ~55 and ~150 meV are very insensitive to E_A. Optical absorption and dye laser luminescence excitation spectroscopy were necessary to obtain a full separation of the transitions due to different acceptors, together with a study of certain ‘two-hole’ luminescence satellites in which the acceptor is left in a series of orbital states after bound exciton decay. Two shallow acceptors are P_Te and As_Te, a third possibly Li_Zn while a fourth, relatively prominent in our best undoped crystals, may be a complex. A deeper, 150 meV acceptor, frequently reported in the ZnTe literature and electrically dominant in most of our undoped crystals has the Zeeman character of a point defect. We present clear evidence from our spectra that this energy does not represent the binding of a single hole at a doubly ionized cation vacancy, a popular attribution since 1963. This acceptor may be covered by another impurity, possibly Cu_Zn. We also report bound phonon effects, lifetime broadening of excited bound exciton states and observe a single unidentified donor with E_D ~18.5 meV. This energy is determined using selective dye laser excitation at the weak neutral donor bound exciton line and from the onset of valence band to ionized donor photo-absorption.