Polarized emission of CdSe nanocrystals in magnetic field: the role of phonon-assisted recombination of the dark exciton
Gang Qiang, Aleksandr A. Golovatenko, Elena V. Shornikova, Dmitri R. Yakovlev, Anna V. Rodina, Evgeny A. Zhukov, Ina V. Kalitukha, Victor F. Sapega, Vadim K. Ka… 展开作者
Gang Qiang, Aleksandr A. Golovatenko, Elena V. Shornikova, Dmitri R. Yakovlev, Anna V. Rodina, Evgeny A. Zhukov, Ina V. Kalitukha, Victor F. Sapega, Vadim K. Kaibyshev, Mikhail A. Prosnikov, Peter C. M. Christianen, Aleksei A. Onushchenko, Manfred Bayer
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 the 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 circular polarized PL maxima from the ensemble of nanocrystals is a result of competition between the zero phonon (ZPL) and one optical phonon (1PL) assisted 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.
A new mechanism of electron paramagnetic resonance in spherical zinc-blende semiconductor nanocrystals, based on the extended orbital motion of electrons in the entire nanocrystal, is presented. Quantum confinement plays a crucial role in making the resonance signal observable. The mechanism remains operative in nanocrystals with uniaxially distorted shape. A theoretical model based on the proposed mechanism is in good quantitative agreement with unusual ODMR spectra observed in nearly spherical CdSe nanocrystals.
We present theoretical and experimental investigations of the magnetism of paramagnetic semiconductor CdSe:Mn nanocrystals and propose an efficient approach to the exposure and analysis of the underlying anti-ferromagnetic interactions between magnetic ions therein. A key advance made here is the build-up of an analysis method with the exploitation of group theory technique that allows us to distinguish the anti-ferromagnetic interactions between aggregative Mn2+ ions from the overall pronounced paramagnetism of magnetic ion doped semiconductor nanocrystals. By using the method, we clearly rev…
We investigate the photon statistics of the light emitted by single self-assembled hybrid gold-CdSe/CdS/CdZnS colloidal nanocrystal supraparticles through the detailed analysis of the intensity autocorrelation function $g^{(2)}(τ)$. We first reveal that, despite the large number of nanocrystals involved in the supraparticle emission, antibunching can be observed. We then present a model based on non-coherent Förster energy transfer and Auger recombination that well captures photon antibunching. Finally, we demonstrate that some supraparticles exhibit a bunching effect at short time scales corr…
Large surface to volume ratios of semiconductor nanocrystals cause susceptibility to charge trapping, which can modify luminescence yields and induce single-particle blinking. Optical spectroscopies cannot differentiate between bulk and surface traps in contrast to spin-resonance techniques, which in principle avail chemical information on such trap sites. Magnetic resonance detection via spin-controlled photoluminescence enables the direct observation of interactions between emissive excitons and trapped charges. This approach allows the discrimination of two functionally different trap state…
High quality factor dielectric cavities designed to a nanoscale accuracy are mostly used to increase the spontaneous emission rate of a single emitter. Here we show that the coupling, at room temperature, between thick shell CdSe/CdS nanocrystals and random metallic films offers a very promising alternative approach. Optical modes confined at the nanoscale induce strong Purcell factors reaching values as high as 60. Moreover the quantum emission properties can be tailored: strong antibunching or radiative biexcitonic cascades can be obtained with high photon collection efficiency and extremely…
We report on the synthesis of hybrid light emitting particles with a diameter ranging between 100 and 500 nm, consisting in a compact semiconductor CdSe/CdS/CdZnS nanocrystal aggregate encapsulated by a controlled nanometric size silica and gold layers. We first characterize the Purcell decay rate enhancement corresponding to the addition of the gold nanoshell as a function of the particle size and find a good agreement with the predictions of numerical simulations. Then, we show that the contribution corresponding to Förster resonance energy transfer is inhibited.
We perform photoluminescence excitation measurements on individual CdSe/ZnS nanocrystal quantum dots (NCQDs) at room temperature to study optical transition energies and broadening. The observed features in the spectra are identified and compared to calculated transition energies using an effective mass model. The observed broadening is attributed to phonon broadening, spectral diffusion and size and shape inhomogeneity. The former two contribute the broadening transitions in individual QDs while the latter contributes to the QD-to-QD variation. We find that phonon broadening is often not the …
We present results for electronic transport measurements on large three-dimensional arrays of CdSe nanocrystals. In response to a step in the applied voltage, we observe a power-law decay of the current over five orders of magnitude in time. Furthermore, we observe no steady-state dark current for fields up to 10^6 V/cm and times as long as 2x10^4 seconds. Although the power-law form of the decay is quite general, there are quantitative variations with temperature, applied field, sample history, and the material parameters of the array. Despite evidence that the charge injected into the film d…
Transport properties of artificial solids composed of colloidal CdSe nanocrystals (NCs) are studied from 6 K to 250 K, before and after annealing. Annealing results in greatly enhanced dark and photocurrent in NC solids, while transmission electron microscopy (TEM) micrographs show that the inter-dot separation decreases. The increased current can be attributed to the enhancement of inter-dot tunneling caused by the decreased separation between NCs and by chemical changes in their organic cap. In addition, the absorption spectra of annealed solids are slightly red-shifted and broadened. These …
The blinking dynamics of colloidal core-shell CdSe/CdS dot-in-rods is studied in detail at the single particle level. Analyzing the autocorrelation function of the fluorescence intensity, we demonstrate that these nanoemitters are characterized by a short value of the mean duration of bright periods (ten to a few hundreds of microseconds). The comparison of the results obtained for samples with different geometries shows that not only the shell thickness is crucial but also the shape of the dot- in-rods. Increasing the shell aspect ratio results in shorter bright periods suggesting that surfac…
A novel method to image charge is used to measure the diffusion coefficient of electrons in films of CdSe nanocrystals at room temperature. This method makes possible the study of charge transport in films exhibiting high resistances or very small diffusion coefficients.
Cadmium selenide nanocrystal quantum dots (NC-QDs) are site-selectively synthesized by sequential ion beam implantation of selenium and cadmium ions in a SiO2 matrix through sub-micron apertures followed by a rapid thermal annealing step. The size, areal density and optical emission energy of the NC-QDs are controlled by the ion fluence during implantation and the diameter of implantation aperture. For low fluences and small apertures the emission of these optically active emitters is blue-shifted compared to that of the bulk material by $>100\,{\rm meV}$ due to quantum confinement. The emissi…
Although poorly understood, cation-exchange reactions are increasingly used to dope or transform colloidal semiconductor nanocrystals (quantum dots). We used density-functional theory and kinetic Monte Carlo simulations to develop a microscopic theory that explains structural, optical, and electronic changes observed experimentally in Ag-cation-exchanged CdSe nanocrystals. We find that Coulomb interactions, both between ionized impurities and with the polarized nanocrystal surface, play a key role in cation exchange. Our theory also resolves several experimental puzzles related to photolumines…
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 …
We study the low-temperature magneto-photoluminescence (PL) from individual CdSe nanocrystals. Nanocrystals having a small "bright" exciton fine structure splitting ($<$0.5 meV) exhibit a conventional left- and right-circularly polarized Zeeman PL doublet in applied magnetic fields. In contrast, nanocrystals with large fine structure splitting ($>$1 meV) show an anomalous magneto-PL polarization, wherein the lower-energy peak becomes circularly polarized with increasing field, while the higher-energy peak remains linearly polarized. This unusual behavior arises from strong mixing between the a…
We present a theoretical description of excitons and positively and negatively charged trions in "giant" CdSe/CdS core-shell nanocrystals (NCs). The developed theory provides the parameters describing the fine structure of excitons in CdSe/CdS core/thick shell NCs as a function of the CdSe/CdS conduction band offset and the CdSe core radius. We have also developed a general theory describing the fine structure of positively charged trions created in semiconductor NCs with a degenerate valence band. The calculations take into account the complex structure of the CdSe valence band and inter-part…
Engineering semiconductors to enhance carrier multiplication (CM) could lead to increased photovoltaic cell performance and a significant widening of the materials range suitable for future solar technologies. Semiconductor nanocrystals (NCs) have been proposed as a favourable structure for CM enhancement, and recent measurements by transient absorption have shown evidence for highly efficient CM in lead chalcogenide and CdSe NCs. We report here an assessment of CM yields in CdSe and CdTe NCs by a quantitative analysis of biexciton and exciton signatures in transient photoluminescence decays. …
To understand and optimize optical spin initialization in room temperature CdSe nanocrystal quantum dots (NCQDs) we studied the dependence of the time-resolved Faraday rotation signal on pump energy $E_p$ in a series of NCQD samples with different sizes. In larger NCQDs, we observe two peaks in the spin signal vs. $E_p$, whereas in smaller NQCDs, only a single peak is observed before the signal falls to a low, broad plateau at higher energies. We calculate the spin-dependent oscillator strengths of optical transitions using a simple effective mass model to understand these results. The observe…
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 mag…
Magnetic doping of semiconductor nanostructures is actively pursued for applications in magnetic memory and spin-based electronics. Central to these efforts is a drive to control the interaction strength between carriers (electrons and holes) and the embedded magnetic atoms. In this respect, colloidal nanocrystal heterostructures provide great flexibility via growth-controlled `engineering' of electron and hole wavefunctions within individual nanocrystals. Here we demonstrate a widely tunable magnetic sp-d exchange interaction between electron-hole excitations (excitons) and paramagnetic manga…
The optical spectra of CdSe nanocrystals up to 55 A in diameter are analyzed in a wide range of energies from the fine structure of the low-energy excitations to the so-called high-energy transitions. We apply a symmetry-based method in two steps. First we take the tight-binding (TB) parameters from the bulk sp^{3}s^{*} TB model, extended to include the spin-orbit interaction. The full single-particle spectra are obtained from an exact diagonalization by using a group-theoretical treatment. The electron-hole interaction is next introduced: Both the Coulomb (direct) and exchange terms are consi…
The kinetics and thermodynamics of structural transformations under pressure depend strongly on particle size due to the influence of surface free energy. By suitable design of surface structure, composition, and passivation it is possible, in principle, to prepare nanocrystals in structures inaccessible to bulk materials. However, few realizations of such extreme size-dependent behavior exist. Here we show with molecular dynamics computer simulation that in a model of CdSe/ZnS core/shell nanocrystals the core high pressure structure can be made metastable under ambient conditions by tuning th…
Theory of electronic and optical properties of exciton and bi-exciton complexes confined in CdSe spherical nanocrystals is presented. The electron and hole states are computed using atomistic $sp^3d^5s^*$ tight binding Hamiltonian including an effective crystal field splitting, spin-orbit interactions, and model surface passivation. The optically excited states are expanded in electron-hole configurations and the many-body spectrum is computed in the configuration-interaction approach. Results demonstrate that the low-energy electron spectrum is organized in shells ($s$, $p$, ...), whilst the …
By performing spectroscopic single-particle measurements at cryogenic temperatures over the course of hours we study %By performing spectroscopic longtime single-particle measurements at cryogenic temperatures we study both the spectral diffusion as well as the diffusion of the decay rates of the fluorescence emission of core/shell CdSe/CdS dot/rod nanoparticles. A special analysis of the measurements allow for a correlation of data for single neutral excitons only, undisturbed by the possible emission of other excitonic complexes. We find a nearly linear dependency of the fluorescence decay r…
We propose a method to overcome Auger recombination in nanocrystal quantum dot lasers using cavity-enhanced spontaneous emission. We derive a numerical model for a laser composed of nanocrystal quantum dots coupled to optical nanocavities with small mode-volume. Using this model, we demonstrate that spontaneous emission enhancement of the biexciton transition lowers the lasing threshold by reducing the effect of Auger recombination. We analyze a photonic crystal nanobeam cavity laser as a realistic device structure that implements the proposed approach.
We study how shape affects multiexciton generation (MEG) rates in a semiconducting nanocrystal by considering CdSe nanorods with varying diameters and aspect ratios. The calculations employ an atomistic semiempirical pseudopotential model combined with an efficacious stochastic approach applied to systems containing up to 20,000 atoms. The effect of nanorod diameter and aspect ratio on multiexciton generation rates is analyzed in terms of the scaling of the density of trion states and the scaling of the Coulomb couplings. Both show distinct scaling from spherical nanocrystals leading to a surp…
We present a theory of highly excited interacting carriers confined in a semiconductor nanostructure, incorporating Auger coupling between excited states with different number of excitations. The Coulomb matrix elements connecting exciton, bi-exciton and tri-exciton complexes are derived and an intuitive picture of breaking neutral multi-exction complexes into positively and negatively charged multi-exciton complexes is given. The general approach is illustrated by analyzing the coupling of biexciton and exciton in CdSe spherical nanocrystals. The electron and hole states are computed using at…
We measured the intrinsic ground-state exciton dephasing and population dynamics in colloidal quasi two-dimensional (2D) CdSe nanoplatelets at low temperature (5-50K) using transient resonant four-wave mixing in heterodyne detection. Our results indicate that below 20K the exciton dephasing is lifetime limited, with the exciton population lifetime being as fast as 1ps. This is consistent with an exciton lifetime given by a fast radiative decay due to the large in-plane coherence area of the exciton center-of-mass motion in these quasi 2D systems compared to spherical nanocrystals.
In this letter, we propose a new model to determine the recombination oscillator strength of trions and biexcitons for bound and unbound cases in the effective mass approximation. The validity of our model has been confirmed by the radiative lifetime of the trion and biexciton in a spherical quantum dot. The results show that the model works sufficient accuracy in comparison with results of more complex methods such as quantum monte carlo techniques and atomistic calculations.
Exciton binding energy and electron-hole recombination probability are presented as the two important metrics for investigating effect of dot size on electron-hole interaction in CdSe quantum dots. Direct computation of electron-hole recombination probability is challenging because it requires an accurate mathematical description of electron-hole wavefunction in the neighborhood of the electron-hole coalescence point. In this work, we address this challenge by solving the electron-hole Schrodinger equation using the electron-hole explicitly correlated Hartree-Fock (eh-XCHF) method. The calcula…
Having already achieved near-unity quantum yields, with promising properties for light-emitting diode, lasing, and charge separation applications, colloidal core/shell quantum dots have great technological potential. The shell thickness and band alignment of the shell and core materials are known to influence the efficiency of these devices. In many such applications, a key to improving the efficiency requires a deep understanding of multiexcitonic states. Herein, we elucidate the shell thickness and band alignment dependencies of the biexciton Auger recombination lifetime for quasi-type-II Cd…
Time-resolved Faraday rotation is used to study both transverse and longitudinal spin relaxation in chemically-synthesized CdSe nanocrystals (NCs) 22-80 Angstroms in diameter. The precession of optically-injected spins in a transverse magnetic field occurs at distinct frequencies whose assignment to electron and exciton spins is developed through systematic studies of the size-dependence and theoretical calculations. It is shown that the transverse spin lifetime is limited by inhomogeneous dephasing to a degree that cannot be accounted for by the NC size distribution alone. Longitudinal spin r…
Previous single-particle spectroscopic studies of colloidal quantum dots have indicated a significant spread in biexciton lifetimes across an ensemble of nominally identical nanocrystals. It has been speculated that in addition to dot-to-dot variation in physical dimensions, this spread is contributed to by variations in the structure of the quantum dot interface, which controls the shape of the confinement potential. Here we directly evaluate the effect of the composition of the core-shell interface on single- and multi-exciton dynamics via side-by-side measurements of individual core-shell C…
The rates of elementary photophysical processes in nanocrystals, such as carrier cooling, multiexciton generation, Auger recombination etc., are determined by monitoring the transient occupation of the lowest exciton band. The underlying assumption is that hot carriers relax rapidly to their lowest quantum level. Using femtosecond transient absorption spectroscopy in CdSe/CdS nanodots we challenge this assumption. Results show, that in nanodots containing a preexisting cold exciton "spectator", \emph{only half of the photoexcited electrons}relax directly to the band-edge and the complementary …
CdSe quantum dots (QDs) with different organic linker molecules are attached to ZnO nanowires (NWs) to study the luminescence dynamics and the electron tunneling from the QDs to the nanowires in time-resolved photoluminescence (PL) and photoconductivity measurements. The PL transients of the QD luminescence indicate two different recombination channels: the direct recombination inside the QD core and the recombination via QD surface defect states. After linking the QDs to the ZnO NW surface, photo-induced electron tunneling from an excited state of the QD into the conduction band of the nanowi…
The surface of nominally diamagnetic colloidal CdSe nanoplatelets can demonstrate paramagnetism 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 gr…
The observed intermittent light emission from colloidal semiconductor nanocrystals has long been associated with Auger recombination assisted quenching. We test this view by observing transient emission dynamics of CdSe/CdS/ZnS semiconductor nanocrystals using time-resolved photon counting. The size and intensity dependence of the observed decay dynamics are inconsistent with the those expected from Auger processes. Moreover, the data suggests that in the `off' state the quantum dot cycles in a three-step process: photoexcitation, rapid trapping and subsequent slow nonradiative decay.
Multi-phonon Raman scattering in semiconductor nanocrystals is treated taking into account both adiabatic and non-adiabatic phonon-assisted optical transitions. Because phonons of various symmetries are involved in scattering processes, there is a considerable enhancement of intensities of multi-phonon peaks in nanocrystal Raman spectra. Cases of strong and weak band mixing are considered in detail. In the first case, fundamental scattering takes place via internal electron-hole states and is participated by s- and d-phonons, while in the second case, when the intensity of the one-phonon Raman…
Seeded CdSe/CdS nanorods exhibit intense polarized emission along the rod main axis. The degree of linear polarization cannot be explained by dielectric effects alone, an additional electronic contribution is present whose nature has not been settled up to date. Using multi-band k.p theory, we analyse the potential influence of several factors affecting excitonic emission and show that shear strain is the main electronic mechanism promoting linear polarization. It favors energetically light hole excitons over heavy hole ones, via deformation potential, and makes their radiative recombination f…
The photon statistics of CdSe/CdS dot-in-rods nanocrystals is studied with a method involving post-selection of the photon detection events based on the photoluminescence count rate. We show that flickering between two states needs to be taken into account to interpret the single-photon emission properties. With post-selection we are able to identify two emitting states: the exciton and the charged exciton (trion), characterized by different lifetimes and different second order correlation functions. Measurements of the second order autocorrelation function at zero delay with post- selection s…
We present a comparative study of two self-assembled quantum dot (QD) systems based on II-VI compounds: CdTe/ZnTe and CdSe/ZnSe. Using magneto-optical techniques we investigated a large population of individual QDs. The systematic photoluminescence studies of emission lines related to the recombination of neutral exciton X, biexciton XX, and singly charged excitons (X$^+$, X$^-$) allowed us to determine average parameters describing CdTe QDs (CdSe QDs): X-XX transition energy difference 12 meV (24 meV); fine-structure splitting $δ_{1}=$0.14 meV ($δ_{1}=$0.47 meV); $g$-factor $g=$2.12 ($g=$1.71…
ZnTe/CdSe/(Zn,Mg)Te core/double-shell nanowires are grown by molecular beam epitaxy by employing the vapor-liquid-solid growth mechanism assisted with gold catalysts. A photoluminescence study of these structures reveals the presence of an optical emission in the near infrared. We assign this emission to the spatially indirect exciton recombination at the ZnTe/CdSe type II interface. This conclusion is confirmed by the observation of a significant blue-shift of the emission energy with an increasing excitation fluence induced by the electron-hole separation at the interface. Cathodoluminescenc…
We have explored the influence of different matrices on the emission line shape of individual homogeneously coated CdSe/CdS/ZnS nanocrystals. The results obtained corroborate previous observations of a correlation between blinking events and spectral diffusion but in addition we have found that the extent of spectral diffusion is almost independent of the dielectric environment of the NC. Additionally, we report the observation of a correlation between the line width and emission energy which is not expected to occur in the spherical - symmetric NCs employed in this work. The implications of t…
We present a magneto-optical study of individual self-assembled CdSe/ZnSe quantum dots doped with single Mn$^{2+}$ ions. Properties of the studied dots are analyzed analogously to more explored system of Mn-doped CdTe/ZnTe dots. Characteristic sixfold splitting of the neutral exciton emission line as well as its evolution in the magnetic field are described using a spin Hamiltonian model. Dynamics of both exciton recombination and Mn$^{2+}$ spin relaxation are extracted from a series of time-resolved experiments. Presence of a single dopant is shown not to affect the average excitonic lifetime…
The dephasing time of the lowest bright exciton in CdSe/ZnS wurtzite quantum dots is measured from 5 K to 170 K and compared with density dynamics within the exciton fine structure using a sensitive three-beam four-wave-mixing technique unaffected by spectral diffusion. Pure dephasing via acoustic phonons dominates the initial dynamics, followed by an exponential zero-phonon line dephasing of 109 ps at 5 K, much faster than the ~10 ns exciton radiative lifetime. The zero-phonon line dephasing is explained by phonon-assisted spin-flip from the lowest bright state to dark exciton states. This is…
Some basic radiative and non-radiative processes taking place in semiconductor nanocrystals are discussed, and rates of these processes are calculated. In particular, in the present review we explore both intra-crystallite processes, such as the photon emission, Auger recombination, phonon-assisted exciton relaxation, capture on surface defects, multi-exciton generation, and inter-crystallite processes realized through the exciton migration in ensembles of nanocrystals. Exciton transitions, creation, and annihilation accompanied by the photon and (or) phonon emission or absorption are consider…
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 incr…
The optoelectronic properties of metal chalcogenide colloidal nanoplatelets are often interpreted in terms of excitonic states. However, recent spectroscopic experiments evidence the presence of trion states, enabled by the slow Auger recombination in these structures. We analyze how the presence of an additional charge in trions modifies the emission energy and oscillator strength as compared to neutral excitons. These properties are very sensitive to dielectric confinement and electronic correlations, which we describe accurately using image-charge and variational Quantum Monte Carlo methods…
In recent years many experiments have demonstrated the possibility to achieve efficient photoluminescence from Si/SiO2 nanocrystals. While it is widely known that only a minor portions of the nanocrystals in the samples contribute to the observed photoluminescence, the high complexity of the Si/SiO2 interface and the dramatic sensitivity to the fabrication conditions make the identification of the most active structures at the experimental level not a trivial task. Focusing on this aspect we have addressed the problem theoretically, by calculating the radiative recombination rates for differen…
We present a systematic experimental study along with theoretical modeling of the energy transfer in an ensemble of closely-packed CdTe colloidal nanocrystals identified as the Förster resonant energy transfer (FRET). We prove that at low temperature of 4.2 K, mainly the ground dark exciton states in the initially excited small-size (donor) nanocrystals participate in the dipole-dipole FRET leading to additional excitation of the large-size (acceptor) nanocrystals. The FRET becomes possible due to the weak admixture of the bright exciton states to the dark states. The admixture takes place eve…
We theoretically study the effect of the dielectric environment on the exciton ground state of CdSe and CdTe/CdSe/CdTe nanorods. We show that insulating environments enhance the exciton recombination rate and blueshift the emission peak by tens of meV. These effects are particularly pronounced for type-II nanorods. In these structures, the dielectric confinement may even modify the spatial distribution of electron and hole charges. A critical electric field is required to separate electrons from holes, whose value increases with the insulating strength of the surroundings.
