Single carbon nanotubes probed by photoluminescence excitation spectroscopy: the role of phonon-assisted transitions

We study light absorption mechanisms in semiconducting carbon nanotubes using low-temperature, single-nanotube photoluminescence excitation spectroscopy. In addition to purely electronic transitions, we observe several strong phonon-assisted bands due to excitation of one or more phonon modes together with the first electronic state. In contrast with a small width of emission lines (sub-meV to a few meV), most of the photoluminescence excitation features have significant linewidths of tens of meV. All of these observations indicate very strong electron-phonon coupling that allows efficient excitation of electronic states via phonon-assisted processes and leads to ultrafast intraband relaxation due to inelastic electron-phonon scattering.     

Study of optical transitions in an individual ZnO tetrapod using two-photon photoluminescence excitation spectrum

Two-photon excited photoluminescence (PL) measurements have been carried out on an individual ZnO tetrapod at low temperature (8 K) using femtosecond laser pulses in the wavelength range of 714–850 nm. Simultaneously PL and second-harmonic generation were observed. The integrated PL intensity excitation spectrum at different two-photon excitation frequencies has eight peaks, which are in good correspondence to the exciton-phonon complexes L_1b , L_1a , and the free exciton lines B _n=3, A _n=3, B _n=2, A _n=2, B _n=1, and A _n=1 seen in ZnO film. This technique can be used to measure the optical transitions in individual nanostructures, which is very difficult to achieve using the traditional transmission/reflection method.     

Ultrafast laser spectroscopy of semiconductor nanocrystals

A large amount of work has been worldwide directed to understand the properties of semiconductor nanostructures. Ultrafast lasers with pulsewidths of a few femtoseconds allowed the investigation of the dynamics of elementary excitations in semiconductor structures on ultrashort time scales. Recent progress in technology made it possible to fabricate semiconductor nanocrystals (i.e. crystals of nanometer dimensions) of well-defined properties. The purpose of this paper is to review the understanding of carrier relaxation and recombination processes in semiconductor nanocrystals as studied by ultrafast laser spectroscopy. The up-to-date techniques of ultrafast laser spectroscopy as well as the fabrication of semiconductor nanocrystals are discussed in some detail.     

Power-law statistics of intermittent photoluminescence in single semiconductor nanocrystals

A physical model is proposed for a single CdSe nanocrystal coated with a ZnS shell which can explain the power-law statistics of its experimentally observed intermittent photoluminescence. If the localized electron-hole pairs (excitons) form in the nanocrystal, this suggestion alone will suffice to explain why the on-time distribution follows the law close to t ^?1.5 found experimentally.     

Stark spectroscopy of excited-state transitions in a conjugated polymer

Stark spectroscopy, which is well established for probing transitions between the ground and excited states of many material classes, is extended to transitions between transient excited states. To this end, it is combined with femtosecond pump-probe spectroscopy on a conjugated polymer with appropriately introduced traps which harvest excitation energy and build up a sufficient excited state population. The results indicate a significant difference in the effective dipole moments between two short lived excited states.     

Theory of radiative and nonradiative transitions for semiconductor nanocrystals

Existing calculations on the radiative and nonradiative transitions in semiconductor crystallites are reviewed with particular emphasis on indirect band-gap materials like silicon for which the quantum confinement effects are more spectacular. It is shown that the crystallite gaps and radiative recombination rates can be predicted with fair accuracy. Effects related to atomic relaxation in the excited state (Stokes shift) are calculated and it is shown that small enough crystallites lead to self-trapped excitons which provide another source of luminescence, much less dependent on size effects. Nonradiative processes are then examined: intrinsic, due to Auger recombination, and extrinsic, due to dangling bond surface states. Both are found to play an essential role in the interpretation of experimental data. Finally, dielectric screening is studied, justifying the use of a reduced internal dielectric constant and providing an estimate of the Coulomb shift due to charging effects.     

Synthesis and time-resolved photoluminescence spectroscopy of capped CdS nanocrystals

Here, we report the synthesis of colloidal CdS nanoparticles by capping with starch, phenol and pyridine. We also study the photophysical properties of CdS nanoparticles by steady state and time-resolved photoluminescence spectroscopy. The experimental results show that the relaxation of the excited state of CdS nanoparticles is composed of two different components. Our analysis suggests that the fast and slow components decay times of these capped CdS nanocrystals are due to trapping of carriers in surface state and e–h radiative recombination processes, respectively.     

Polarized photoluminescence excitation spectroscopy of single-walled carbon nanotubes

The polarized photoluminescence excitation spectra of twenty-five single-walled carbon nanotube species are reported. For light polarized along the nanotube axis, the main absorption resonance at E22 shows sidebands attributed to phonon assisted absorption. Sidebands to E11 have a diameter dependent energy and are assigned to excited excitonic states. Along with longitudinal excitations, several transverse excitations are identified. The transverse E12 resonance has a specific family pattern with energy close to E22. Comparison with theory provides an estimate of the strength of the Coulomb interaction.     

Wurtzite and zinc-blende CdSe based core/shell semiconductor nanocrystals: Structure, morphology and photoluminescence

We report comparative study of core/shell nanocrystals based on wurtzite and novel zinc-blende CdSe core. Both wurtzite and zinc-blende CdSe are coated with CdS shell or CdS/ZnS multishell under identical synthetic parameters. Crystal structure analysis finds that CdS shell is wurtzite on either wurtzite or zinc-blende CdSe cores. Morphology and photoluminescence studies exhibit that for zinc-blende CdSe based samples, the shell growth is in fine epitaxy and the obtained core/shell nanocrystals show high quantum yield both before and after surface modification process; while wurtzite CdSe based samples have irregular shape indicating inhomogeneous shell growth, and are with lower quantum yield. Furthermore, in the photoluminescence spectra exited with UV radiation, wurtzite CdSe based samples show side peaks of independently nucleated nanocrystals from the shell material; while samples with zinc-blende CdSe cores are potent in restricting these byproducts, which may attribute to the highly effective arrestment of precursor ions onto the zinc-blende CdSe surface. These features manifest that zinc-blende CdSe is more talented than conventional wurtzite CdSe in achieving core/shell nanocrystals with higher qualities.     

Superlinear photoluminescence in silicon nanocrystals: The role of excitation wavelength

We study the influence of the wavelength of picosecond excitation pulses on the properties of photoluminescence (PL) in a series of samples of silicon nanocrystals prepared by ion implantation into silica matrix. We observed a gradual change in the behaviour of the PL fast component (spectral shape, decay times, pump-intensity dependence) when tuning the excitation wavelength from 355 to 532 nm. We interpret the results in terms of an interplay between the PL originating from volume states of nanocrystals containing two photoexcited carrier pairs, and the PL due to the silicon oxide states. We discuss also the role of the implant fluence on the PL properties of samples.     

Characterization of semiconductor core-shell nanoparticles by resonant Raman scattering and photoluminescence spectroscopy

Colloidal CdSe nanoparticles (NPs), passivated with CdS and ZnS, were characterized by resonant Raman scattering and photoluminescence (PL). The effect of the passivating shell, its volume and formation procedure on optical and vibrational spectra is discussed. Analyzing the Raman peaks due to optical phonons inside the core and those related to the core-shell interface allows some understanding of the relation between the core-shell structure and its PL properties to be achieved. In particular, a compositional intermixing at the core/shell interface of the NPs was deduced from the Raman spectra, which can noticeably affect their PL intensity.     

Exotic and excited-state meson spectroscopy and radiative transitions from lattice QCD

We discuss recent progress in extracting the excited meson spectrum and radiative transition form factors from lattice QCD.We mention results in the charmonium sector,including the first lattice QCD calculation of radiative transition rates involving excited charmonium states,highlighting results for high spin and exotic states.We present recent results on a highly excited isovector meson spectrum from dynamical anisotropic lattices.Using carefully constructed operators we show how the continuum spin of extracted states can be reliably identified and confidently extract excited states,states with exotic quantum numbers and states of high spin.This spectrum includes the first spin-four state extracted from lattice QCD.We conclude with some comments on future prospects.     

Exotic and excited-state meson spectroscopy and radiative transitions from lattice QCD

We discuss recent progress in extracting the excited meson spectrum and radiative transition form factors from lattice QCD.We mention results in the charmonium sector,including the first lattice QCD calculation of radiative transition rates involving excited charmonium states,highlighting results for high spin and exotic states.We present recent results on a highly excited isovector meson spectrum from dynamical anisotropic lattices.Using carefully constructed operators we show how the continuum spin of extracted states can be reliably identified and confidently extract excited states,states with exotic quantum numbers and states of high spin.This spectrum includes the first spin-four state extracted from lattice QCD.We conclude with some comments on future prospects.     

Observation of size-dependent thermalization in CdSe nanocrystals using time-resolved photoluminescence spectroscopy

We report heat dissipation times in semiconductor nanocrystals of CdSe. Specifically, a previously unresolved, subnanosecond decay component in the low-temperature photoluminescence decay dynamics exhibits longer decay lifetimes (tens to hundreds of picoseconds) for larger nanocrystals as well as a size-independent, ~25-meV spectral shift. We attribute the fast relaxation to transient phonon-mediated relaxation arising from nonequilibrium acoustic phonons. Following acoustic phonon dissipation, the dark exciton state recombines more slowly via LO-phonon assistance resulting in the observed spectral shift. The measured relaxation time scales agree with classical calculations of thermal diffusion, indicating that interfacial thermal conductivity does not limit thermal transport in these semiconductor nanocrystal dispersions.     

Modulation,photoluminescence, and Raman spectroscopy of semiconductor heterostructures

Using illustrative examples from the investigations of the author and his collaborators, it is shown that (1) piezo-modulated reflectivity (2) photoluminescence and (3) Raman spectroscopy can be effectively used in the study of collective and localized excitations in semiconductor heterostructures. Results on epilayers of Cd_1−xMn_xTe:In and ZnSe and quantum well structures of GaAs/Al_xGa_1−xAs; Cd_1−xMn_xTe/Cd_1−yMn_yTe; Cd_1−xMn_xTe/CdTe; Cd_1−xMn_xTe:In/CdTe are discussed.     

Optical spectroscopy of lanthanides doped in wide band-gap semiconductor nanocrystals

Currently, tripositive lanthanide (Ln³⁺) ions doped wide band-gap semiconductor nanocrystals (NCs) have been the focus of research interest due to their distinct optical properties and potential applications in optical devices and luminescent biolabels. Because of the low absorptions of parity-forbidden 4f-4f transitions for Ln³⁺, it is highly anticipated that the luminescence of Ln³⁺ ions embedded in wide band-gap NC lattices can be sensitized efficiently via exciton recombination in the host. For this purpose, the successful incorporation of Ln³⁺ into the lattices of semiconductor NCs is of utmost importance, which still remains intractable via conventional wet chemical methods. Here, the most recent progress in the optical spectroscopy of Ln³⁺ ions doped wide band-gap semiconductor NCs is discussed. Much attention was focused on the optical properties including electronic structures, luminescence dynamics, energy transfer as well as the up-conversion emissions of Ln³⁺ ions in ZnO, TiO₂, SnO₂ and In₂O₃ NCs that were synthesized in our laboratory using wet chemical methods.     

Erbium photoluminescence excitation spectroscopy in Si: Er epitaxial structures

Excitation spectra of erbium photoluminescence in Si: Er epitaxial structures are studied within a broad pump wavelength range (λ_ex = 780–1500 nm). All the structures studied reveal a fairly strong erbium photoluminescence signal at photon energies substantially smaller than the silicon band-gap width (λ = 1060 nm) with no exciton generation. A possible mechanism of erbium ion excitation in silicon without exciton involvement is discussed.     

Two-photon spectroscopy and microscopy of II–VI semiconductor nanocrystals

We review our recent nonlinear spectroscopies of nanocrystals and synthetic efforts to improve their luminescence properties. A two-photon spectroscopic study of CdSe nanocrystals as a function of size is presented and compared with predictions from the effective mass model with spherical confinement. We also detail our efforts at improving the luminescence properties of nanocrystals which have culminated in a 50% fluorescence quantum yield for inorganic capping of some sizes of CdSe nanocrystals. Finally, we present the application of two-photon microscopy to resolve fluorescence from single nanocrystals at room temperature and cryogenic temperatures.     

Fluorescence spectroscopy of semiconductor CdTe nanocrystals: preparation effect on photostability

We report on continuous-wave and time-resolved fluorescence spectroscopy studies of CdTe water-soluble nanocrystals at room temperature. For nanocrystals spread directly on the substrate we observe large variation both in fluorescence maximum energy and fluorescence lifetime. We attribute this to the influence of the surface of the nanocrystals on the stability of excitations in the nanocrystals. As the fluorescence lifetime of the nanocrystals is monitored, we find it increases with time from 6 to 18 ns and then saturates. Placing the nanocrystals in a polymer matrix remarkably improves the photostability and all the above-mentioned effects are diminished. Upon mixing the nanocrystals with gold spherical nanoparticles we observe a decrease of the fluorescence intensity due to efficient energy transfer to the nanoparticles.     

Photo-induced phase transitions probed by X-ray absorption spectroscopy: Fe(II) spin crossover complex

Photo-induced phase transitions in spin-crossover complex [Fe(II)(2-pic)₃]Cl₂EtOH were investigated by X-ray absorption spectroscopy (XAS) technique. In situ XAS results showed that the metal-ligand (Fe–N) bond distance expands by ca. 0.20 Å upon photo-induced (S=0→S=2) spin conversion. We find that nearly octahedral (O_h) symmetry of FeN₆ coordination remains in the photo-induced high spin state. The next-nearest neighbor Fe–C radial distribution shows a subtle change due to local distortions of ligand molecules. Inhomogeneous distribution of strains may disturb cooperative photo-induced phase transitions removing centers of inversion symmetry.