Surface-enhanced emission from single semiconductor nanocrystals

The fluorescence behavior of single CdSe(ZnS) core-shell nanocrystal (NC) quantum dots is dramatically affected by electromagnetic interactions with a rough metal film. Observed changes include a fivefold increase in the observed fluorescence intensity of single NCs, a striking reduction in their fluorescence blinking behavior, complete conversion of the emission polarization to linear, and single NC exciton lifetimes that are >10(3) times faster. The enhanced excited state decay process for NCs coupled to rough metal substrates effectively competes with the Auger relaxation process, allowing us to observe both charged and neutral exciton emission from these NC quantum dots.     

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.     

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.     

Monitoring surface charge movement in single elongated semiconductor nanocrystals

We demonstrate a universal correlation between the spectral linewidth and position of the excitonic transition in the spectral jitter observed from single elongated colloidal quantum dots. Breaking the symmetry of electron and hole confinement as well as of the spatial directions for surface charge diffusion enables us to microscopically track meandering surface charges, providing a novel probe of the particle's nanoenvironment. Spectral diffusion exhibits only a weak temperature dependence, which allows us to uncover the single particle homogeneous linewidth of 50 meV at room temperature.     

Environment-dependent blinking of single semiconductor nanocrystals and statistical aging of ensembles

We compare decreasing fluorescence signals from ensembles with the blinking statistics of individual nanocrystals in various environments. For most substrates, the ensemble decay follows a power-law of time, the exponent being the difference of the power-law exponents of on- and off-time distributions. The decay exponent is also found to depend on substrate. We discuss possible mechanisms for this dependence, in conjunction with previously published models.     

Self-purification in semiconductor nanocrystals

Doping of nanocrystals is an important and very difficult task. "Self-purification" mechanisms are often claimed to make this task even more difficult, as the distance a defect or impurity must move to reach the surface of a nanocrystal is very small. We show that self-purification can be explained through energetic arguments and is an intrinsic property of defects in semiconductor nanocrystals. We find the formation energies of defects increases as the size of the nanocrystal decreases. We analyze the case of Mn-doped CdSe nanocrystals and compare our results to experimental findings.     

Photoluminescence polarization of semiconductor nanocrystals

We review the polarization properties of photoluminescence (PL) in nanocrystals (NCs) from both theoretical and experimental points of view. We show that, under linearly polarized excitation, NCs emit partly polarized light owing to their uniaxial structure or their anisotropic shape. In elongated NCs, the anisotropy may have two origins, the electronic confinement or the effect of depolarizing field created by the light-induced charges on the interfaces. Results of polarization studies in porous silicon are presented. They are explained by the shape of the Si NCs. Experiments in CdSe NCs reveal the fine structure of the excitonic levels and show evidence of the enhancement of the electron-hole exchange energy with decreasing NC size. Spin orientation in wurtzite-type NCs is achieved by optical pumping with circularly polarized light. The effect of a magnetic field on the degree of circular polarization and the mechanisms of spin relaxation are discussed. Results in large-size NCs are presented.     

Fluorescence decay time measurements in tetracene crystals excited with synchrotron radiation

Fluorescence decay times from tetracene single crystals excited at room temperature with synchrotron radiation have been recorded as a function of the excitation wavelength (in the 400–500 nm range). A non-exponential decay with two decay rates is observed. The analysis of our data shows that the first singlet exciton level of tetracene (single crystal) decays radiatively mainly through, as we call it, channel 1, with a lifetime of 0.200 ± 0.020 ns. About 10% of the emitted fluorescence transits through channel 2 with a lifetime of 1.7 ± 0.2 ns. These results do not agree with previously published decay data obtained when tetracene is excited by means of powerful lasers. Thus there is experimental evidence to believe that the decay properties of condensed materials can be very dependent on the excitation density. Because synchrotron radiation compared to lasers is a very weak source, and therefore secondary effects are minimized in our experimental conditions, the decay values reported in the present work are the true lifetimes of the tetracene single crystal.     

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.     

Photo-modification and synthesis of semiconductor nanocrystals

Both photo-oxidation and photosynthesis manifest a strong interaction between nanoparticles and photons due to the large surface area-to-volume ratio. The final sizes of the semiconductor nanocrystals are determined by the photon energy during these phenomena. The photosynthesis is demonstrated in a Si-rich oxide and is similar to thermal synthesis, which involves the decomposition of SiO_x into Si and SiO₂, that is well known and often employed to form Si or Ge nanocrystals embedded in SiO₂ by annealing SiO_x at high temperature. However, photosynthesis is much faster, and allows the low-temperature growth of Si nanocrystals and is found to be pronounced in the SiO nanopowder, which is made by thermal CVD using SiH₄ and O₂. The minimum laser power required for the photosynthesis in the SiO nanopowder is much lower than in the Si-rich oxide formed by the co-sputtering of Si and SiO₂. This is attributed to the weak bond strength of Si-Si and Si-O in the SiO nanopowder. Photosynthesis, which can control the size and position of Si nanocrystals, is a novel nanofabrication technique making the best use of the strong interaction between photons and nanoparticles.     

Capped semiconductor nanocrystals for device applications

For device purpose, our main aim is to synthesise material which is chemically and thermally stable, as well as enhancement in luminescence properties followed with matching lattice parameters. This can be achieved by precisely controlling the size of semiconductor nanocrystals which can create an opportunity for producing functional materials with new properties. Here we showed advantages of using both organic and inorganic capping agents. We reported two synthesis routes, one will lead to nanocomposites and other to Core/Shell nanostructures. Our mechanism consists of two stages: core nanoparticle formation and shell growth. Gibbs free energy of hydration of Zn+2 gives more clarity for shell growth over core rather than ion displacement from core. Colloidal films comprising of nanocrystalline CdS/ZnS were fabricated by the dip coating method. A blue shift in energy level at the nanoscale is demonstrated by optical absorption. Electron microscopy studies with an SEM and TEM show a particle size of 10 nm and diffraction patterns show a crystalline nature. Absence of lattice mismatching is one of the important parameter for device fabrication, which is confirmed by Raman spectroscopy. Overall reduction in optical absorption due to blue shift is expected to result in higher performance, especially in short-circuit currents in CdS/CdTe solar cells.     

Persistent hole burning in semiconductor nanocrystals

The persistent spectral hole burning (PSHB) phenomenon was found to occur in many kinds of nanocrystalline semiconductors, such as CdSe, CdS, CuCl, CuBr and CuI, embedded in crystals, glass or polymers. In inhomogeneously broadened exciton absorption spectra of these nanocrystals, the spectral hole and its associated structure were created by the narrow-band laser excitation and were conserved for more than several hours at 2 K. Hole depth grew in proportion to the logarithm of the burning fluence. Thermally-annealing and light-induced hole-filling phenomena were observed. The hole burning takes place by the tunneling process through potential barriers with broadly distributed barrier height and thickness. Unusual luminescence behaviors related to the PSHB phenomena were also observed. They are luminescence elongation with increase of the light exposure and hole burning in the luminescence spectrum. The observed PSHB phenomena are explained by the exciton localization and the succeeding ionization of nanocrystals. The energy of the photoionized nanocrystal is released from the original energy and the new energies depend on the spatial arrangement of the trapped carriers. Quantum confinement of carriers and resulting strong Coulomb interaction between confined carriers and trapped carriers are essential for the energy change. Possible applications of the PSHB phenomenon is discussed.     

Theory of multi-exciton states in semiconductor nanocrystals

In this article, the fundamental physics of multi-exciton states in semiconductor nano-crystals is reviewed focusing on the mesoscopic enhancement of the excitonic radiative decay rate and the excitonic optical nonlinearity and the mechanism of their saturation with increase of the nanocrystal size. In the case of the radiative decay rate the thermal excitation of excited exciton states having small oscillator strength within the homogeneous linewidth of the exciton ground state is essential in determining the saturation behavior. The weakly correlated exciton pair states are found to cause a cancellation effect in the third-order nonlinear optical susceptibility at the exciton resonance, providing the first consistent understanding of the experimentally observed saturation of the mesoscopic enhancement of the excitonic optical nonlinearity. The presence of the weakly correlated exciton pair states is confirmed convincingly from the good correspondence between theory and experiments on the induced absorption spectra from the exciton state in CuCl nanocrystals. Furthermore, ultrafast relaxation processes of biexcitons are discussed in conjunction with the observed very fast rise of the biexciton gain in nanocrystals. In prospect of future progress in research, the theoretical formulation to calculate the triexciton states as one of the multi-exciton states beyond the biexciton is presented for the first time including the electron-hole exchange interaction.     

Room-temperature exciton storage in elongated semiconductor nanocrystals

The excited state of colloidal nanoheterostructures consisting of a spherical CdSe nanocrystal with an epitaxially attached CdS rod can be perturbed effectively by electric fields. Field-induced fluorescence quenching coincides with a conversion of the excited state species from the bright exciton to a metastable trapped state (dark exciton) characterized by a power-law luminescence decay. The conversion is reversible so that up to 10% of quenched excitons recombine radiatively post turn-off of a 1 micro s field pulse, increasing the delayed luminescence by a factor of 80. Excitons can be stored for up to 10(5) times the natural lifetime, opening up applications in optical memory elements.     

Size-dependent spintronic properties of dilute magnetic semiconductor nanocrystals

The electronic structure and magnetic properties of Mn-doped Ge, GaAs, and ZnSe nanocrystals are investigated using real space ab initio pseudopotentials constructed within the local spin-density approximation. The ferromagnetic and half-metallicity trends found in the bulk are preserved in the nanocrystals. However, the Mn-related impurity states become much deeper in energy with decreasing nanocrystalline size, causing the ferromagnetic stabilization to be dominated by double exchange via localized holes rather than by a Zener-like mechanism.     

Vanishing of the Mott transition in semiconductor nanocrystals

The dynamics of the system of photoexcited electron–hole pairs in semiconductor nanocrystals of different size with increasing excitation intensity was experimentally studied by utilizing the luminescence spectra of semiconductor-doped glasses in order to elucidate the peculiarities of many-body effects in structures approaching the zero-dimensional limit. Vanishing of effects causing the Mott transition in bulk crystals was observed with decreasing nanocrystal radius, and a new type of transformation of excitons to unbound electron–hole pairs was shown to take place in nanocrystals where the energy shift for electrons and holes due to quantum confinement becomes comparable with the exciton binding energy.