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The coherent spin dynamics of electrons in CdSe nanocrystals embedded in a glass matrix with diameters from 3.3 up to 6.1 nm are investigated by time-resolved Faraday ellipticity at room and cryogenic temperatures. Only one Larmor precession frequency is detected, which corresponds to the larger of the two precession frequencies and thus

The electronic and hole states in quantum dots (QD) of cubic II–VI semiconductors with a spheroidal shape and uniaxial anisotropy have been studied theoretically. The smooth potential energy profiles simulated by the Gauss function in all three spatial directions are considered. The energy level lowering and the energy splitting of the hole state from the valence band top Γ8 by momentum 3/2 into the states with projections ±3/2, ±1/2 on the anisotropy axis are analyzed. The QD anisotropies of three types are considered: the QD size anisotropy, the QD potential barrier anisotropy, and the combined anisotropy. In the first case, flattened quantum dots, in which the characteristic size in the structure plane is larger than the size along the anisotropy axis, are considered. In the second case, QDs, in which the potential barrier height in the plane is lower than that along the anisotropy axis, are considered. In the third case, flattened quantum dots with the anisotropy of the size and the potential barrier are considered. The conditions of the charge carrier localization inside QD have been found, and the influence of the form and composition anisotropies on the energies of exciton transitions in the structures with CdxZn1 – xSe quantum dots are discussed.

A theory of electron spin-flip Raman scattering (SFRS) is presented that describes the Raman spectral signals shifted by both single and twice the electron Zeeman energy under nearly resonant excitation of the heavy hole excitons in semiconductor nanoplatelets. We analyze the spin structure of photoexcited intermediate states, derive compound matrix elements of the spin-flip scattering and obtain polarization properties of the one- and two-electron SFRS common for all the intermediate states. We show that, in the resonant scattering process under consideration, the complexes "exciton plus localized resident electrons" play the role of main intermediate states rather than tightly bound trion states. It is demonstrated that, in addition to the direct photoexcitation (and similar photorecombination) channel, there is another indirect channel contributing to the SFRS process. In the indirect channel, the photohole forms the exciton state with the resident electron removed from the localization site while the photoelectron becomes localized on this site. The theoretical results are compared with recent experimental findings for ensembles of CdSe nanoplatelets., 17 pages, 3 figures, submitted

The recombination dynamics and spin polarization of excitons in CdSe nanocrystals synthesized in a glass matrix are investigated using polarized photoluminescence in high magnetic fields up to 30 Tesla. The dynamics are accelerated by increasing temperature and magnetic field, confirming the dark exciton nature of low-temperature photoluminescence (PL). The circularly polarized PL in magnetic fields reveals several unusual appearances: (i) a spectral dependence of the polarization degree, (ii) its low saturation value, and (iii) a stronger intensity of the Zeeman component which is higher in energy. The latter feature is the most surprising being in contradiction with the thermal population of the exciton spin sublevels. The same contradiction was previously observed in the ensemble of wet-chemically synthesized CdSe nanocrystals but was not understood. We present a theory which explains all the observed features and shows that the inverted ordering of the circularly polarized PL maxima from the ensemble of nanocrystals is a result of competition between the zero phonon (ZPL) and one optical phonon-assisted (1PL) emission of the dark excitons. The essential aspects of the theoretical model are different polarization properties of the dark exciton emission via ZPL and 1PL recombination channels and the inhomogeneous broadening of the PL spectrum from the ensemble of nanocrystals exceeding the optical phonon energy.

Using time-resolved photoluminescence (PL) spectroscopy, we establish the presence of the Forster energy transfer mechanism between two arrays of epitaxial CdSe/ZnSe quantum dots (QDs) of different sizes. The mechanism operates through dipole–dipole interaction between ground excitonic states of the smaller QDs and excited states of the larger QDs. The dependence of energy transfer efficiency on the width of barrier separating the QD insets is shown to be in line with the Forster mechanism. The temperature dependence of the PL decay times and PL intensity suggests the involvement of dark excitons in the energy transfer process.

In the limit of strong quantum confinement the lower energy states of excitons and biexcitons in spheroidal quantum dots of semiconductors with a fourfold degenerate vertex of the valence band, which are active in the dipole approximation at one- and two-photon excitation, have been considered. The comparative analysis of the order of energy levels of the hole in the potentials of the infinitely deep quantum well and a three-dimensional harmonic oscillator taking into account the axial anisotropy of the quantum dot (QD) shape is carried out. It is shown that the anisotropy of the QD shape can lead to the opposite sign of splitting with respect to angular momentum projection ±3/2, ±1/2 for spatially odd (1P3/2) and even (1S3/2) levels of the hole. At the same time, in the case of the potential of an infinitely deep quantum well, an inversion of the order of 1S3/2 and 1P3/2 levels can be observed at values of the ratio of the effective masses of the light and heavy holes β = mlh/mhh ≈ 0.14. The type of the trial wave functions of the hole for the state 1P3/2 in the potential of an isotropic three-dimensional harmonic oscillator depending on β is proposed. The dependence of the binding energy of excitons in the considered potentials on β is presented and the possibility of formation of various biexcitonic states is considered.

We present a review of spin-dependent properties of excitons in semiconductor colloidal nanocrystals. The photoluminescences (PL) properties of neutral and charged excitons (trions) are compared. The mechanisms and the polarization of radiative recombination of a “dark” (spin-forbidden) exciton that determines the low-temperature PL of colloidal nanocrystals are discussed in detail. The radiative recombination of a dark exciton becomes possible as a result of simultaneous flips of the surface spin and electron spin in a dark exciton that leads to admixture of bright exciton states. This recombination mechanism is effective in the case of a disordered state of the spin system and is suppressed if the polaron ferromagnetic state forms. The conditions and various mechanisms of formation of the spin polaron state and possibilities of its experimental detection are discussed. The experimental and theoretical studies of magnetic field-induced circular polarization of PL in ensembles of colloidal nanocrystals are reviewed.

The biexciton binding energy in spherical CdSe/ZnSe quantum dots is calculated variationally in the framework of kp-perturbation theory. Smooth and abrupt confining potentials with the same localization area of carriers are compared for two limiting cases of light hole to heavy hole mass ratio β = m lh /m hh : β = 1 and β = 0. Accounting for correlations between carriers results in their polarized configuration and significantly increases the biexciton binding energy in comparison with the first order perturbation theory. For β = 0 in smooth confining potentials there are three nearby biexciton states separated by small energy gap between 1S3/2 and 1P3/2 hole states.

We present theoretical aspects of the exchange interaction between the ground optically-forbidden “dark” exciton state and surface dangling bonds in colloidal CdSe spherical nanocrystals and nanoplatelets. The influence of the dangling bond spins on the radiative recombination and spin splitting of the dark exciton is shown. Processes of optically-driven and external magnetic field-driven formation of the dangling bond magnetic polaron (DBMP) are considered. Thermodynamic and dynamic polarization mechanisms of the DBMP formation within these two processes and corresponding critical temperatures are compared. Experimental manifestations of the DBMP formation in CdSe nanocrystals and nanoplatelets are discussed.

We review our studies on spin-dependent phenomena in various colloidal nanocrystals (quantum dots, dot-in-rod, and nanoplatelets). Several magneto-optical techniques are used in high magnetic fields: magnetic-field-induced polarization of neutral and charged excitons, spin-flip Raman scattering, and pump-probe Faraday rotation. We focus on spin properties and spin dynamics of neutral and charged excitons in order to identify them and measure g-factors and spin relaxation times. Pump-probe time-resolved Faraday rotation experiments with additional prepump allow us to measure coherent spin dynamics of carriers in CdS NCs at room temperature, and to study interplay between the negative and positive photocharging processes. We discuss the role of the dangling bond spins for recombination of the dark excitons and for formation of the dangling bond magnetic polaron.

International audience; We address spin properties and spin dynamics of carriers and charged excitons in CdSe/CdS colloidal nanoplatelets with thick shells. Magneto-optical studies are performed by time-resolved and polarization-resolved photoluminescence, spin-flip Raman scattering and picosecond pump-probe Faraday rotation in magnetic fields up to 30 T. We show that at low temperatures the nanoplatelets are negatively charged so that their photoluminescence is dominated by radiative recombination of negatively charged excitons (trions). Electron g-factor of 1.68 is measured, and heavy-hole g-factor varying with increasing magnetic field from -0.4 to -0.7 is evaluated. Hole g-factors for two-dimensional structures are calculated for various hole confining potentials for cubic- and wurtzite lattice in CdSe core. These calculations are extended for various quantum dots and nanoplatelets based on II-VI semiconductors. We developed a magneto-optical technique for the quantitative evaluation of the nanoplatelets orientation in ensemble.

We present a comparative study of the influence of the form of a localization potential on the binding energy of the biexciton in spherically symmetric quantum dots based on II–VI compounds. The proposed criterion for the comparison of potentials of different forms—the box potential, the harmonic oscillator, and the Gaussian potential—is based on the identical localization of charge carriers of the same sign in these potentials. Calculations of the biexciton binding energy have been performed using the variational method within the framework of the kp-perturbation theory taking into account additional polarization terms in the wave functions of the electron and hole subsystems, as well as the complex structure of the valence band. The obtained results have demonstrated that the presence of a smoothly varying finite-height potential in Cd(Zn)Se/ZnSe quantum dots can lead to a more efficient localization in the case of the biexciton in comparison with the exciton, which is of interest for the implementation of fast-acting quantum light emitters.

Non-magnetic colloidal nanostructures can demonstrate magnetic properties typical for diluted magnetic semiconductors because the spins of dangling bonds at their surface can act as the localized spins of magnetic ions. Here we report the observation of dangling-bond magnetic polarons (DBMPs) in 2.8-nm diameter CdSe colloidal nanocrystals (NCs). The DBMP binding energy of 7 meV is measured from the spectral shift of the emission lines under selective laser excitation. The polaron formation at low temperatures occurs by optical orientation of the dangling-bond spins (DBSs) that result from dangling-bond-assisted radiative recombination of spin-forbidden dark excitons. Modelling of the temperature dependence of the DBMP-binding energy and emission intensity shows that the DBMP is composed of a dark exciton and about 60 DBSs. The exchange integral of one DBS with the electron confined in the NC is ∼0.12 meV. Nonmagnetic colloidal nanocrystals demonstrate magnetic properties due to spins of dangling bonds at their surface resulting in formation of dangling-bond magnetic polarons.

International audience; The surface of nominally diamagnetic colloidal CdSe nanoplatelets can demonstrate para-magnetism owing to the uncompensated spins of dangling bonds (DBSs). We reveal that by optical spectroscopy in high magnetic fields up to 15 Tesla using the exciton spin as probe of the surface magnetism. The strongly nonlinear magnetic field dependence of the circular polarization of the exciton emission is determined by the DBS and exciton spin polarization as well as by the spin-dependent recombination of dark excitons. The sign of the exciton-DBS exchange interaction can be adjusted by the nanoplatelet growth conditions. The surface of colloidal nanocrystals (NCs) greatly controls their optical and electronic properties making the surface chemistry critically important in nanocrystal research and applications. 1-3 Undercoordinated surface atoms with excess electrons, which in colloidal synthesis are often metal cations, either rearrange themselves by surface reconstruction or adsorb surfactant ligands. 4,5 The ligands are used to control the colloidal synthesis, increase the NC solubility, screen the NCs from environment, and stabilize their surface by saturating dangling bonds of the surface atoms. 6,7 They influence surface trap states and thereby control photoluminescence quantum yield. 8-11 Not every dangling bond can be passivated due to steric hindrance, as the ligand diameter typically exceeds the lattice constant of NC material and due to poor interaction of a facet with the ligands. An electron transfer from the d-shell of a surface atom to the ligand can provide surface magnetism. 12-14 Also the spins of unpassivated dangling bonds can contribute to it. The spins of surface atoms act similar to spins of magnetic impurities in diluted magnetic semiconductors, 15-17 and may influence crucially the optical, electronic and magnetic properties of colloidal NCs. 18,19 Nominally diamagnetic NCs may demonstrate paramagnetic behavior and giant magneto-optical effects. Here, we study the surface spins in colloidal quasi-two-dimensional nanoplatelets (NPLs) based on CdSe semiconductor. These emerging nanostructures have an atomically controlled thickness of a few monolayers, providing remarkable optical properties with narrow emission lines of neutral and charged excitons. 20,21 The interaction of confined excitons with the dangling-bond spins (DBSs) provides a nanoscopic tool for monitoring surface magnetism. In particular, the exciton spin polarization in magnetic field and the radiative recombination of dark excitons are strongly modified due to the exchange interaction with DBSs. We use high magnetic fields up to 15 T to measure the degree of circular polarization (DCP) of exciton photoluminescence and the exciton spin and recombination dynamics at cryogenic temperatures. In contract to a pure diamagnetic behavior, we find a strongly nonmonotonic magnetic field dependence of DCP, which sign changes for NPLs synthesized in air or argon atmosphere. This allows us to identify two mechanisms resulting from the exciton interaction with the surface spins. The first one is an additional Zeeman splitting of the exciton states, which is similar to the giant Zeeman splitting effect in diluted magnetic arXiv:1909.13700v1 [cond-mat.mes-hall]

We show theoretically that spins of dangling bonds (DBSs) at the surface of colloidal nanostructures can be responsible for the dark exciton radiative recombination governing low temperature photoluminecence. The DBS-assisted dark exciton recombination is efficient when all spins are randomly oriented. The DBS polarization caused by external magnetic field or by the formation of the dangling bond magnetic polaron (DBMP) at low temperatures suppresses the DBS-assisted recombination. The temperature or magnetic field control on the DBS-polarization allows to detect experimentally the presence of DBS and DBS-assisted recombination in CdSe nanocrystals and 2D nanoplatelets.

We use a time-resolved technique with three laser pulses (pump, orientation and probe) to study the photocharging dynamics with picosecond resolution on a long timescale ranging from ps to ms in CdS colloidal quantum dots. The detection is based on measuring the coherent spin dynamics of electrons, allowing us to distinguish the type of carrier in the dot core (electron or hole). We find that although initially negative photocharging happens because of fast hole trapping on surface states, eventually it evolves to positive photocharging due to electron trapping and hole detrapping. The positive photocharging lasts up to hundreds of microseconds at room temperature.

Magnetotransmission (MT) at magnetic fields up to 29 T was used to study the electronic structure of $\mathrm{CuInS}{\mathrm{e}}_{2}$ in thin polycrystalline films. The zero field absorption spectra exhibited resolved A, B, and C free excitons. Quantum oscillations, due to diamagnetic excitons comprising electrons and holes from Landau levels quantized in the conduction and valence band, respectively, appeared in the MT spectra at fields over 5 T. Spectral energies of Landau levels and binding energies of the corresponding diamagnetic excitons, theoretically calculated assuming a quasicubic approximation of the $\mathrm{CuInS}{\mathrm{e}}_{2}$ tetragonal lattice structure, helped to identify the character of the experimentally observed diamagnetic excitons. Spectral energies of diamagnetic excitons in the MT spectra with different circular polarizations were used to determine the electron and light hole effective masses, whereas heavy hole masses as well as the \ensuremath{\gamma} and ${\ensuremath{\gamma}}_{1}$ Luttinger parameters, ${E}_{p}$ Kane energy, and F parameter of the influence of remote bands, as well as their polaron values, were calculated using the Luttinger theory.

CdSe colloidal nanoplatelets are studied by spin-flip Raman scattering in magnetic fields up to 5 T. We find pronounced Raman lines shifted from the excitation laser energy by an electron Zeeman splitting. Their polarization selection rules correspond to those expected for scattering mediated by excitons interacting with resident electrons. Surprisingly, Raman signals shifted by twice the electron Zeeman splitting are also observed. The theoretical analysis and experimental dependencies show that the mechanism responsible for the double flip involves two resident electrons interacting with a photoexcited exciton. Effects related to various orientations of the nanoplatelets in the ensemble and different orientations of the magnetic field are analyzed.

Forster resonance energy transfer in inhomogeneous dense arrays of epitaxial CdSe/ZnSe quantum dots is demonstrated by time- and space-resolved photoluminescence spectroscopy. The specific feature of this process is the dipole–dipole interaction between the ground exciton levels of small quantum dots and the excited levels of large dots. This interaction brings efficient energy collection and spectral selection of a limited number of emitters. Results of theoretical modeling of optical transitions in spheroidal quantum dots with a Gaussian potential profile agree with the observed features of optical spectra induced by the change of the dominant energy transfer mechanism.

We report on Forster resonance energy transfer in the dense arrays of epitaxial quantum dots (QDs), formed by fractional monolayer CdSe insertions within a ZnSe matrix. In such arrays comprising the QDs of different sizes, the energy transfer can take place between the ground levels of small QDs and the excited levels of large radiating QDs, when these states are in resonance. This mechanism provides directional excitation of a limited number of the large QDs possessing the excited levels. It reveals itself by the shrinkage of photoluminescence (PL) bands and the appearance of the narrow single excitonic lines in micro-PL spectra. The strong shortening of characteristic PL decay times in the energy-donating QDs is observed when the distance between them and the energy-accepting QDs decreases. Photoluminescence excitation spectroscopy demonstrates the switching of the dominant energy transfer mechanism at the energy predicted by theoretical modeling of the excitonic levels in the QD arrays. Our results pave the way for engineering of the architecture of excitonic levels in the QD arrays to realize efficient nano-emitters.

authoren We demonstrate that the selection of a limited number of single excitonic lines from a dense array of epitaxial quantum dots (QDs) can be realized spectrally via resonant energy transfer from a huge number of small QDs toward a limited set of large nano-islands through their excited levels. Optical and transmission electron microscopy studies support this mechanism. Theoretical modeling describes the architecture of quantum levels in the array of CdSe/ZnSe QDs, which enables such a spectral selection. Schematic of resonant energy transfer between QDs shown together with a plan-view TEM image of a QD array.

We theoretically study nonradiative and radiative energy transfer between two localized quantum emitters, a donor (initially excited) and an acceptor (receiving the excitation). The rates of nonradiative and radiative processes are calculated depending on the spatial and spectral separation between the donor and acceptor states and for different donor and acceptor lifetimes for typical parameters of semiconductor quantum dots. We find that the donor lifetime can be significantly modified only due to the nonradiative Forster energy transfer process at donor–acceptor separations of approximately 10 nm (depending on the acceptor radiative lifetime) and for the energy detuning not larger than 1–2 meV. The efficiency of the nonradiative Forster energy transfer process under these conditions is close to unity and decreases rapidly with an increase in the donor–acceptor distance or energy detuning. At large donor–acceptor separations greater than 40 nm, the radiative corrections to the donor lifetime are comparable with nonradiative ones but are relatively weak.

We review the effects caused by a large difference in the dielectric constants of a semiconductor and its surrounding in colloidal semiconductor nanostructures (NSs) with various shapes, e.g., nanocrystals, nanorods, and nanoplatelets. The difference increases the electron–hole interaction and consequently the exciton binding energy and its oscillator transition strength. On the other hand, this difference reduces the electric field of a photon penetrating the NS (the phenomenon is called the local field effect) and reduces the photon coupling to an exciton. We show that the polarization properties of the individual colloidal NSs as well as of their randomly oriented ensemble are determined both by the anisotropy of the local field effect and by the symmetry of the exciton states participating in optical transitions. The calculations explain the temperature and time dependences of the degree of linear polarization measured in an ensemble of CdSe nanocrystals.

In this paper, we theoretically analyze the recombination and spin dynamics of excitons in an inhomogeneous ensemble of colloidal nanocrystals, which consists of several subensembles with different lifetimes and degrees of circular polarization of exciton photoluminescence (DCP). Each subensemble is described within a three-level model of interacting exciton states, including two excited states and a ground state. Various ratios of parameters, leading to a nontrivial time-dependent DCP and a difference in the integral and equilibrium DCP characteristics, are considered. It is shown that the presence of subensembles with different polarizations and lifetimes results in nonmonotonic dependence and a change in the sign of the DCP in magnetic field and as a function of time can occur. The theoretical model was implemented to describe the time dependences of the DCP in ensembles of colloidal CdSe nanoplatelets synthesized in the air and argon atmosphere.

Micro-photoluminescence studies of MoS2 nanotubes have shown that both direct and indirect excitonic transitions contribute to the emission spectra despite the fact that dozens of monolayers are inside their walls and, therefore, only indirect exciton emission would be expected. In addition, the intensity of the indirect exciton band increases with temperature in contrast to the direct exciton band, the intensity of which decreases. The same effects are observed for MoS2 flakes. To describe these phenomena, we propose a theoretical model that considers the balance between exciton transitions taking into account the spin-forbidden exciton states.

We report on a comprehensive experimental and theoretical study of optical third harmonic generation (THG) on the exciton-polariton resonances in the zinc-blende semiconductors GaAs, CdTe, and ZnSe subject to an external magnetic field, representing a topic that had remained unexplored so far. In these crystals, crystallographic THG is allowed in the electric-dipole approximation, so that no strong magnetic-field-induced changes of the THG are expected. Therefore, it comes as a total surprise that we observe a drastic enhancement of the THG intensity by a factor of fifty for the $1s$-exciton-polariton in GaAs in magnetic fields up to 10 T. In contrast, the corresponding enhancement is moderate for CdTe and almost neglectful for ZnSe. In order to explain this strong variation, we develop a microscopic theory accounting for the optical harmonics generation on exciton-polaritons and analyze the THG mechanisms induced by the magnetic field. The calculations show that the increase of THG intensity is dominated by the magnetic field enhancement of the exciton oscillator strength which is particularly strong for GaAs in the studied range of field strengths. The much weaker increase of THG intensity in CdTe and ZnSe is explained by the considerably larger exciton binding energies, leading to a weaker modification of their oscillator strengths by the magnetic field., 16 pages, 13 figures

We predict theoretically that nonmagnetic CdSe nanocrystals may possess macroscopic magnetic moments due to the formation of dangling-bond magnetic polarons (DBMPs). A DBMP is created in optically pumped nanocrystals by dynamic polarization of dangling bond spins (DBSs) at the nanocrystal surface during radiative recombination of the ground state "dark" exciton assisted by a spin-flip of the DBS. The formation of DBMPs suppresses the radiative recombination of the dark exciton and leads to a temperature-dependent contribution to the Stokes shift of the photoluminescence. This model consistently explains the experimentally observed low-temperature photoluminescence features of nonmagnetic CdSe nanocrystals as manifestations of their spin-related magnetic properties.

Nonlinear optical phenomena are widely used for the study of semiconductor materials. The paper presents an overview of experimental and theoretical studies of excitons by the method of optical second and third harmonics generation in various bulk semiconductors (GaAs, CdTe, ZnSe, ZnO, Cu$_2$O, (Cd,Mn)Te, EuTe, EuSe), and low-dimensional heterostructures ZnSe/BeTe. Particular attention is paid to the role of external electric and magnetic fields that modify the exciton states and induce new mechanisms of optical harmonics generation. Microscopic mechanisms of harmonics generation based on the Stark effect, the spin and orbital Zeeman effects, and on the magneto-Stark effect specific for excitons moving in an external magnetic field are considered. This approach makes it possible to study the properties of excitons and to obtain new information on their energy and spin structure that is not available when the excitons are investigated by linear optical spectroscopy. As a result of these studies, a large amount of information was obtained, which allows us to conclude on the establishing of a new field of research - exciton spectroscopy by the method of optical harmonics generation., Comment: 35 pages, 13 figures, to be published in Solid State Physics Journal (St. Petersburg, Russia as translation of Fizika Tverdogo Tela)

International audience; We study the band-edge exciton fine structure and in particular its bright-dark splitting in colloidal semiconductor nanocrystals by four different optical methods based on fluorescence line narrowing and time-resolved measurements at various temperatures down to 2 K. We demonstrate that all these methods provide consistent splitting values and discuss their advances and limitations. Colloidal CdSe nanoplatelets with thicknesses of 3, 4 and 5 monolayers are chosen for experimental demonstrations. The bright-dark splitting of excitons varies from 3.2 to 6.0 meV and is inversely proportional to the nanoplatelet thickness. Good agreement between experimental and theoretically calculated size dependence of the bright-dark exciton slitting is achieved. The recom-bination rates of the bright and dark excitons and the bright to dark relaxation rate are measured by time-resolved techniques.

We analyze theoretically physical mechanisms responsible for the radiative recombination of the ground optically passive (``dark'') exciton (DE), which dominates in photoluminescence (PL) of colloidal nanocrystals (NCs) at low temperatures. The DE becomes optically active due to its mixing with the bright excitons caused by an external magnetic field, dangling-bond spins or by acoustic and optical phonons. These activation mechanisms mix the DE with different bright excitons and, consequently, lead to different PL polarization properties, because they are determined by dipole orientations of the bright excitons, which the DE is coupled with. We show that the PL polarization properties of prolate and oblate shape NCs are different due to different activation mechanisms responsible for the DE recombination.

A theoretical study of the positive and negative trion channels in the nonradiative Auger recombination of band-edge biexcitons (BXs) in CdSe/CdS core/shell nanocrystals (NCs) is presented. The theory takes into account the BX fine-structure produced by NC asymmetry and hole−hole exchange interaction. The calculations show that growth of CdS shell upon CdSe core suppresses the rate of the Auger recombination via negative trion channel, while the more efficient Auger recombination via positive trion channel shows much weaker dependence on the shell thickness. The demonstrated oscillatory dependence of the BX Auger rate on the core and shell sizes is explained qualitatively in terms of overlap of the ground and excited carrier wave functions. The calculations show that raise of temperature accelerates the Auger recombination in CdSe/CdS NCs due to reduction of the bulk energy gaps of CdSe and CdS.

We report on the theoretical study of the hole states in II-IV quantum dots of a spherical and ellipsoidal shape, described by a smooth potential confinement profiles, that can be modelled by a Gaussian functions in all three dimensions. The universal dependencies of the hole energy, $g$-factor and localization length on a quantum dot barrier height, as well as the ratio of effective masses of the light and heavy holes are presented for the spherical quantum dots. The splitting of the four-fold degenerate ground state into two doublets is derived for anisotropic (oblate or prolate) quantum dots. Variational calculations are combined with numerical ones in the framework of the Luttinger Hamiltonian. Constructed trial functions are optimized by comparison with the numerical results. The effective hole $g$-factor is found to be independent on the quantum dot size and barrier height and is approximated by simple universal expression depending only on the effective mass parameters. The results can be used for interpreting and analyzing experimental spectra measured in various structures with the quantum dots of different semiconductor materials., 13 pages, 8 figures

An electric field applied to a semiconductor reduces its crystal symmetry and modifies its electronic structure which is expected to result in changes of the linear and nonlinear response to optical excitation. In GaAs, we observe experimentally strong electric field effects on the optical second (SHG) and third (THG) harmonic generation. The SHG signal for the laser-light $k$ vector parallel to the [001] crystal axis is symmetry forbidden in the electric-dipole approximation, but can be induced by an applied electric field in the vicinity of the $1s$ exciton energy. Surprisingly, the THG signal, which is allowed in this geometry, is considerably reduced by the electric field. We develop a theory which provides good agreement with the experimental data. In particular, it shows that the optical nonlinearities for the $1s$ exciton resonance are modified in an electric field by the Stark effect, which mixes the $1s$ and $2p$ exciton states of opposite parity. This mixing acts in opposite way on the SHG and THG processes, as it leads to the appearance of forbidden SHG in (001)-oriented GaAs and decreases the crystallographic THG.

The exciton spin dynamics and polarization properties of the related emission are investigated in colloidal CdSe/CdS dot-in-rod (DiR) and spherical core/shell nanocrystal (NC) ensembles by magneto-optical photoluminescence (PL) spectroscopy in magnetic fields up to 15 T. It is shown that the degree of circular polarization (DCP) of the exciton emission induced by the magnetic field is affected by the NC geometry as well as the exciton fine structure and can provide information on nanorod orientation. A theory to describe the circular and linear polarization properties of the NC emission in magnetic field is developed. It takes into account phonon mediated coupling between the exciton fine structure states as well as the dielectric enhancement effect resulting from the anisotropic shell of DiR NCs. This theoretical approach is used to model the experimental results and allows us to explain most of the measured features. The spin dynamics of the dark excitons is investigated in magnetic fields by time-resolved photoluminescence. The results highlight the importance of confined acoustic phonons in the spin relaxation of dark excitons. The bare core surface as well as the core/shell interface give rise to an efficient spin relaxation channel, while the surface of core/shell NCs seems to play only a minor role., Comment: 18 pages, 15 figures

We calculate the rate of nonradiative Auger recombination in negatively charged CdSe nanocrystals (NCs). The rate is nonmonotonic, strongly oscillating with NC size, and sensitive to the NC surface. The oscillations result in nonexponential decay of carriers in NC ensembles. Using a standard single-exponential approximation of the decay dynamics, we determine the apparent size dependence of the Auger rate in an ensemble and derive CdSe surface parameters consistent with the experimental dependence on size.

An identification of shallow bound exciton centers in ZnO is presented based on magneto-optical measurements and diffusion experiments. The thermalization behavior of the Zeeman split components confirms that the I 4 , I 6 , I 8 and I 9 exciton lines stem from donor bound exciton complexes. The results are supported by theoretical analysis of shallow bound exciton complexes revealing the Γ 7 symmetry of the upper valence band. The presence of two-electron satellites related to the respective transitions is further evidence for the donor bound complexes and enabled the determination of donor binding energies. Hydrogen, aluminum, gallium and indium were identified to origin the I 4 , I 6 , I 8 and I 9 lines by doping, diffusion and annealing experiments combined with photoluminescence and secondary ion mass spectrometry.

The optical properties of excitonic recombinations in bulk, n-type ZnO are investigated by photoluminescence (PL) and spatially resolved cathodoluminescence (CL) measurements. At liquid helium temperature in undoped crystals the neutral donor bound excitons dominate in the PL spectrum. Two electron satellite transitions (TES) of the donor bound excitons allow to determine the donor binding energies ranging from 46 to 73 meV. These results are in line with the temperature dependent Hall effect measurements. In the as-grown crystals a shallow donor with an activation energy of 30 meV controls the conductivity. Annealing annihilates this shallow donor which has a bound exciton recombination at 3.3628 eV. Correlated by magnetic resonance experiments we attribute this particular donor to hydrogen. The Al, Ga and In donor bound exciton recombinations are identified based on doping and diffusion experiments and using secondary ion mass spectroscopy. We give a special focus on the recombination around 3.333 eV, i.e. about 50 meV below the free exciton transition. From temperature dependent measurements one obtains a small thermal activation energy for the quenching of the luminescence of 10 ± 2 meV despite the large localization energy of 50 meV. Spatially resolved CL measurements show that the 3.333 eV lines are particularly strong at crystal irregularities and occur only at certain spots hence are not homogeneously distributed within the crystal contrary to the bound exciton recombinations. We attribute them to excitons bound to structural defects (Y-line defect) very common in II–VI semiconductors. For the bound exciton lines which seem to be correlated with Li and Na doping we offer a different interpretation. Li and Na do not introduce any shallow acceptor level in ZnO which otherwise should show up in donor–acceptor pair recombinations. Nitrogen creates a shallow acceptor level in ZnO. Donor–acceptor pair recombination with the 165 meV deep N-acceptor is found in nitrogen doped and implanted ZnO samples, respectively. In the best undoped samples excited rotational states of the donor bound excitons can be seen in low temperature PL measurements. At higher temperatures we also see the appearance of the excitons bound to the B-valence band, which are approximately 4.7 meV higher in energy. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

AbstractThe biexciton binding energy in spherical CdSe/ZnSe quantum dots is calculated variationally in the framework of kp-perturbation theory. Smooth and abrupt confining potentials with the same localization area of carriers are compared for two limiting cases of light hole to heavy hole mass ratio β = m_ lh /m_ hh : β = 1 and β = 0. Accounting for correlations between carriers results in their polarized configuration and significantly increases the biexciton binding energy in comparison with the first order perturbation theory. For β = 0 in smooth confining potentials there are three nearby biexciton states separated by small energy gap between 1 S _3/2 and 1 P _3/2 hole states.

We report on time-resolved photoluminescence studies of Forster resonance energy transfer (FRET) in structures with two arrays of epitaxial Cd(Zn)Se quantum dots (QDs) of different sizes separated ...

We study quantum confinement and surface effects on the linear Zeeman splitting of the electron quantum size energy levels in spherical semiconductor nanocrystals and spherical layered semiconductor heterostructures. We find that heterostructure interfaces and nanocrystal surfaces directly affect the values of the electron Lande factors. We calculate the size dependence of the electron effective g-values in bare CdSe and ZnO nanocrystals using different choices of boundary conditions (BC) for the envelope functions at the surface using 8×8 and 14×14 Kane models, respectively.

The recombination and spin dynamics of excitons in colloidal CdTe nanocrystals (NCs) are studied by time-resolved photoluminescence in high magnetic fields up to 15 T and at cryogenic temperatures. The recombination decay shows a nonexponential temporal behavior, with the longest component corresponding to the dark excitons having 260 ns decay time at zero magnetic field and 4.2 K temperature. This long component shortens to 150 ns at 15 T due to the magnetic-field-induced mixing of the bright and dark exciton states. The spin dynamics, assessed through the evolution of the magnetic-field-induced circular polarization degree of the photoluminescence, has a fast component shorter than 1 ns related to the bright excitons and a slow component of 5-10 ns associated with the dark excitons. The latter shortens with increasing magnetic field, which is characteristic for a phonon-assisted spin relaxation mechanism. The relatively low saturation level of the associated magnetic-field-induced circular polarization degree of -30 % is explained by a model that suggests the CdTe NCs to constitute an ensemble of prolate and oblate NCs, both having a structural quantization axis. The exciton g-factor of 2.4-2.9 evaluated from fitting the experimental data in the frame of the suggested approach is in good agreement with the expected value for the dark excitons in CdTe NCs., 3 figures, 8 pages