Nonlinear optical properties and phase-relaxation processes in single-walled carbon nanotubes

We have investigated third-order nonlinear optical properties of bundled and isolated semiconducting single-walled carbon nanotubes (SWNTs) by means of Z-scan method, pump-probe method, and two-beam time-resolved degenerate four-wave mixing (DFWM) method. The figures of merit Im χ⁽³⁾/α in both bundled and isolated SWNTs samples were found to be enhanced with increasing tube diameter. The measured Im χ⁽³⁾/α value in the bundled SWNTs was an order of magnitude smaller than that in the isolated SWNTs. Both population relaxation time T₁ and phase-relaxation time T₂ for bundled samples were smaller than those in the isolated samples. These experimental results can be explained by an increase in nonradiative recombination rate and phase-relaxation rate in the bundled sample. The phase-relaxation time T₂ is considered to have a significant role in the enhancement of Im χ⁽³⁾/α.     

Structural dependence of exciton in carbon nanotubes

The binding energies and sizes of excitons, and energy splitting of the bright-dark excitons in single-walled carbon nanotubes have been calculated using the nonorthogonal tight-binding model, supplemented by the long-range Coulomb interaction. It is found that the binding energies and the sizes of excitons not only depend on tube's diameter d, but also its chirality. However, the splitting of the bright-dark excitons mostly depends on 1/d². Our obtained results show that the curvature effect is very important for the exciton excitations in the SWNTs, especially in the smaller diameter ones.     

Stimulated self-trapped exciton emission in CsI:Pb

Defects of the type of V_K and Pb⁺ centres were created in CsI:Pb under the 4.03 eV XeCl laser line irradiation at 10 K. After irradiation, the self-trapped and localized exciton emission excited by the same XeCl laser line was observed as a result of the recombination of electrons, optically released from Pb⁺, with the V_K centres. A strongly superlinear dependence of the emission intensity on the excitation intensity was found for the 3.65 eV emission of the self-trapped exciton. A much weaker superlinearity was observed for the visible localized exciton emission. Optical amplification of the exciton emission was considered as the most probable reason of the observed phenomenon. At 10 K, optical gain G=3.74 was calculated for the self-trapped exciton emission.     

Interference of resonance luminescence of exciton polaritons in CuGaS2 crystals

The nonmodulated and wavelength-modulated reflection spectra of CuGaS₂ crystals for the polarization EIIc of 10 K are studied. The states n = 1, 2 and 3 of the excitons Γ₄ (A-excitons) and n = 1, n = 2 of B- and C-excitons are found. The nonmodulated absorption spectra for the polarization E⊥c at 10 K have been studied. The states n = 1, 2 and 3 of Γ₅ excitons are found. The main parameters of the A (Γ₄, Γ₅) and B, C exciton series at the energies of the longitudinal and transverse excitons Γ₄ for the states n = 1 and n = 2, the effective masses of electrons and holes are determined. The photoluminescence peaks were observed at n = 3 and n = 4 of the excitons Γ₅ in the luminescence spectra excited by the line 4880 Å of Ar⁺ laser. In the luminescence spectra the interference is found.     

Strongly enhanced free-exciton luminescence in microcrystalline CsPbCl3 films produced via the amorphous phase

High-quality CsPbCl₃ films composed of crystallites with narrow size distributions are achieved for various size levels, from microcrystalline to polycrystalline, by a novel heat-treatment method applied to the same amorphous films. Their photoluminescence is dominated by free-exciton emission at every size level without showing trapped-exciton emission in great contrast to the case for single crystals. The microcrystalline state shows more than an order of magnitude stronger free-exciton emission than the polycrystalline state, and exhibits intense stimulated emission under high-power excitation.     

Terahertz signatures of the exciton formation dynamics in non-resonantly excited semiconductors

A microscopic theory for the induced terahertz (THz) absorption of semiconductors is applied to study the time-dependent system response after non-resonant optical excitation. The formation of excitonic populations from an interacting electron-hole plasma is analyzed and the characteristic THz signatures are computed. Good qualitative agreement with recent experiments is obtained.     

Polaronic exciton in quantum wells wires and nanotubes

We investigate the effect of the longitudinal-optical phonon field on the binding energies of excitons in quantum wells, well-wires and nanotubes based on ionic semiconductors. We take into account the exciton-phonon interaction by using the Aldrich-Bajaj effective potential for Wannier excitons in a polarizable medium. We extend the fractional-dimensional method developed previously for neutral and negatively charged donors to calculate the exciton binding energies in these heterostructures. In this method, the exciton wave function is taken as a product of the ground state functions of the electron polaron and hole polaron with a correlation function that depends only on the electron-hole separation. Starting from the variational principle we derive a one-dimensional differential equation, which is solved numerically by using the trigonometric sweep method. We find that the potential that takes into account polaronic effects always give rise to larger exciton binding energies than those obtained using a Coulomb potential screened by a static dielectric constant. This enhancement of the binding energy is more considerable in quantum wires and nanotubes than in quantum wells. Our results for quantum wells are in a good agreement with previous variational calculations. Also, we present novel curves of the exciton binding energies as a function of the wire and nanotubes radii for different models of the confinement potential.     

Exciton-phonon coupling strength in single wall carbon nanotubes

The coupling strength of the exciton and different phonons, including the radial breathing mode (RBM), longitudinal (LO) and transverse (TO) optical phonons, are calculated for different diameter single wall carbon nanotubes (SWNTs) in the framework of tight-binding model. It is found that the exciton-phonon coupling strength with the LO mode or RBM shows a clear (2n+m)-family behavior due to the trigonal warping effect, but it with the TO mode remains to be zero. In the same SWNT, the E₂₂ exciton-phonon coupling strength is found to be slightly smaller than that of E₁₁ exciton. Finally, the exciton-RBM-phonon coupling strengths for several SWNTs are found to be in good agreement with the recent experimental data [Phys. Rev. Lett. 98, 037405 (2007)].     

Nonresonant two-photon generation of excitonic matter in a CuCl pellet

A pressed CuCl pellet is optically excited at 2 K using an excitation energy in the range from 1892 to 2843 meV, which is far below the bandgap. The steady-state population dynamics unambiguously indicates an unusual two-photon generation of ground-state excitons. At high-excitation levels, the observed spectra exhibit rich spectral features arising from electron-hole plasma and electron-hole droplets formation. This nonresonant two-photon excitation is presumably assisted by impurity bands due to grain boundaries and surfaces in this random semiconductor.     

Photoluminescence spectra of nitrogen implanted GaSe crystals

GaSe single crystals were N-implanted along c-axis with ion beams of 10¹⁴ and 10¹⁶ ions/cm² doses having energy values of 60 and 100 keV. The photoluminescence (PL) spectra of undoped and N-implanted GaSe crystals were measured at different temperatures. The PL intensity was observed to decrease with increasing implantation dose while the FWHM of the exciton peaks increased. In heavily doped crystals, due to the interaction with the radiation induced disorders, the wave vector selection rules are satisfied and an indirect exciton PL band is observed 36 meV below the direct exciton states.     

Excitonic absorption spectra and ultrafast dephasing dynamics in arbitrary carbon nanotubes

We illustrate the potential of the density matrix theory for investigation of optical properties of arbitrary single‐walled carbon nanotubes (CNTs). We have performed microscopic calculations of excitonic absorption spectra for CNTs of different chiral angles and diameters. The obtained results are in good agreement with experiments, in particular the excitonic binding energies match well both experiments and ab initio calculations. Furthermore, we show the strength of our approach by presenting calculations of the ultrafast Coulomb driven non‐equilibrium dynamics in CNTs. We find excitation induced dephasing on the picosecond time scale depending on the excitation strength. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical response of small-diameter semiconducting carbon nanotubes under exciton-surface-plasmon coupling

We analyze the optical response of small-diameter (?1 nm) semiconducting carbon nanotubes under the exciton-surface-plasmon coupling. Calculated optical absorption lineshapes exhibit the significant line (Rabi) splitting ∼0.1-0.3 eV as the exciton energy is tuned to the nearest interband surface plasmon resonance of the nanotube so that the mixed strongly coupled surface plasmon-exciton excitations are formed. We discuss possible ways to bring the exciton in resonance with the surface plasmon. The exciton-plasmon Rabi splitting effect we predict here for an individual carbon nanotube is close in its magnitude to that previously reported for hybrid plasmonic nanostructures artificially fabricated of organic semiconductors deposited on metallic films. We believe this effect may be used for the development of carbon nanotube based tunable optoelectronic device applications in areas such as nanophotonics and cavity quantum electrodynamics.     

Proposal of structures possessing high exciton concentration

The possibility of achievement of high exciton concentrations is analyzed. It is shown that high concentrations can be achieved in a three-layer thin molecular film due to the autoreduction processes taking place in it. Shortly, the appearance of high concentrations is the consequence of boundary conditions in film and of the magnitude of matrix elements of dipol-dipol interactions. The autoreduction takes place in the cases when matrix elements characterizing exciton transfer are less than statistical matrix elements. Based on numerical analysis, it was found that optical quanta concentrations of a three-layer film can achieve values of about 5×10⁻². The structures possessing so high concentration do not exist in nature, thus they have to be synthesised. For the current state of nanotechnology, it is not a problem. Fortunately achieving high concentrations requires only certain ratios of relevant characteristics of the film with a two-level exciton scheme, but not their single values.     

Detecting spatially localized excitons in InGaN quantum well structures with a micro-photoluminescence technique

Spatially localized excitons are observed in InGaN quantum well structures at 4 K by using a micro-photoluminescence (PL) technique. By combining PL and nano-lithographic techniques, we are able to detect PL signals with a 0.2 μm spatial resolution. A sharp PL line (linewidth of <0.4 meV) is clearly obtained, which originates from a single localized exciton induced by a quantum dot like a local potential minimum position. Sharp PL spectra detected in three QWs with different indium compositions confirm that there are exciton localization effects in quantum wells in the blue-green (about 2.60 eV, 477 nm) to purple (about 3.05 eV, 406 nm) regions.     

Dependence of the heavy-hole exciton reduced mass on quantum-well size in InGaAs/GaAs heterostructures

We present low temperature photoluminescence investigations of the exciton ground state of In_0.14Ga_0.86As/GaAs quantum wells (QW) in the presence of pulsed magnetic fields up to 50 T. The exciton in-plane reduced mass and the heavy-hole in-plane mass are determined from the best fit of theoretical calculations to the magnetic field dependence of PL peaks. When the QW thickness decreases, their masses increases due to valence-band mixing effect.     

Preparation and luminescent properties of europium-doped yttria fibers by electrospinning

Sub-micrometer-sized fibers of europium-doped yttria (Y₂O₃:Eu³⁺) were prepared by electrospinning followed by high-temperature calcinations for the first time. The fibers were with diameters of 200-400 nm and lengths of several 10 μm and cubic in phase. The spectral properties of the Y₂O₃:Eu³⁺ fibers were studied, in contrast with those of bulk powders. The results indicated that in the present Y₂O₃:Eu³⁺ fibers the excited charge transfer band had slightly blue shift in comparison with that in the bulk due to weaker covalence of Eu-O bonds. In addition, both of the lifetimes of the ⁵D₁ and ⁵D₀ states in the fibers became shorter than that in the bulk due to improved nonradiative transition rates.     

Raman spectroscopy of pentyl‐functionalized carbon nanotubes

We present Raman scattering on carbon nanotubes functionalized with pentyl groups. Studies of the intermediate frequency region and the C–H bond stretching signal along with the D mode show evidence of the addition reaction by Raman spectroscopy. From the resonance profiles of the radial breathing mode (RBM) we assign the chiral indices of the tubes and study the influence of the functionalization on the transition energies, shift and intensity of the RBM signal. The largest effect we observe is on the Raman intensity of the radial breathing mode. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Poly(N-vinyl carbazole)-grafted multiwalled carbon nanotubes: Synthesis via direct free radical reaction and optical limiting properties

In this work, samples of poly(N-vinyl carbazole) (PVK)-grafted multiwalled carbon nanotubes (MWCNTs) were synthesized via free radical reaction. The ready-made PVK was allowed to react directly with MWCNTs at 70 °C in the presence of azo-bis-isobutyronitrile (AIBN). The purified deep grey products, which can dissolve in common organic solvents such as chloroform and 1,2-dichlorobenzene (DCB), were then characterized by FTIR spectra, TEM, TGA, elemental analysis, XPS, UV-vis spectra and Raman spectra. It was confirmed that PVK chains were grafted onto the surface of the carbon nanotubes (CNTs). The optical limiting properties of these PVK-grafted MWCNTs samples were investigated by open-aperture z-scan method. All of the samples of PVK-modified carbon nanotubes in chloroform showed optical limiting behavior better than that of C₆₀ in toluene.     

A new blue-emitting phosphor, SrZnO2:Pb, synthesized by the adipic acid templated sol-gel route

A new blue-emitting phosphor, Sr_1−xPb_xZnO₂, was prepared by a novel adipic acid templated sol-gel route. Photoluminescence and crystalline properties were investigated as functions of calcination temperatures and the Pb²⁺ doping levels. It was found that under UV excitation with a wavelength of 283 or 317 nm, the phosphors gave emission from 374 to 615 nm with a peak centered at 451 nm. This broad-band was composed of UV and the visible range was attributed to an impurity-trapped exciton-type emission. The maximum emission intensity of the Sr_1−xPb_xZnO₂ phosphors occurred at a Pb concentration of x=0.01. The decay time was observed to be ∼33 ms for the compound doped with 1 mol% Pb prepared at 1000 °C. Diffuse reflectance spectra revealed the characteristic absorption peaks and the bandgap energy of SrZnO₂ was found to be 3.4 eV. SEM analysis indicated that phosphor particles have an irregularly rounded morphology and the average particle size was found to be approximately 1 μm.     

Nano-star formation in Al-doped ZnO thin film deposited by dip-dry method and its characterization using atomic force microscopy, electron probe microscopy, photoluminescence and laser Raman spectroscopy

Zinc oxide doped with Al (AZO) thin films were prepared on borosilicate glass substrates by dip and dry technique using sodium zincate bath. Effects of doping on the structural and optical properties of ZnO film were investigated by XRD, EPMA, AFM, optical transmittance, PL and Raman spectroscopy. The band gap for ZnO:Al (5.0 at. wt.%) film was found to be 3.29 eV compared with 3.25 eV band gap for pure ZnO film. Doping with Al introduces aggregation of crystallites to form micro-size clusters affecting the smoothness of the film surface. Al³⁺ ion was found to promote chemisorption of oxygen into the film, which in turn affects the roughness of the sample. Six photoluminescence bands were observed at 390, 419, 449, 480, 525 and 574 nm in the emission spectra. Excitation spectra of ZnO film showed bands at 200, 217, 232 and 328 nm, whereas bands at 200, 235, 257 and 267 nm were observed for ZnO:Al film. On the basis of transitions from conduction band or deep donors (CB, Zn_i or V_OZn_i) to valence band and/or deep acceptor states (VB, V_Zn or O_i or O_Zn), a tentative model has been proposed to explain the PL spectra. Doping with Al³⁺ ions reduced the polar character of the film. This has been confirmed from laser Raman studies.