We present the phase diagram of free charges (electrons and holes), excitons, and biexcitons in highly excited CdSe nanoplatelets that predicts a crossover to a biexciton-dominated region at easily attainable low temperatures or high photoexcitation densities. Our findings extend previous work describing only free charges and excitons by introducing biexcitons into the equation of state, while keeping the exciton and biexciton binding energies constant in view of the relatively low density of free charges in this material. Our predictions are experimentally testable in the near future and offer the prospect of creating a quantum degenerate, and possibly even superfluid, biexciton gas. Furthermore, we also provide simple expressions giving analytical insight into the regimes of photoexcitation densities and temperatures in which excitons and biexcitons dominate the response of the nanoplatelets.
We investigated the nonlinear optical properties of CdSe/CdS nanoplatelets in the vicinity of heavy hole and light hole exciton resonances. The two color pump-probe technique was applied. The first intense pulse created non-equilibrium exciton population, which was detected as a decrease of probe light absorption. We observed intense scattering of excitons between heavy- and light-hole excitonic states. We also studied experimentally saturation of absorption in nanoplatelets. Theoretical description of these phenomena allowed us to determine parameters of exciton dynamics in nanoplatelets.
Two-dimensional electron-hole gases in colloidal semiconductors have a wide variety of applications. Therefore, a proper physical understanding of these materials is of great importance. In this paper we present a detailed theoretical analysis of the recent experimental results by Tomar et al., that show an unexpected stability of excitons in CdSe nanoplatelets at high photoexcitation densities. Including the screening effects by free charges on the exciton properties, our analysis shows that CdSe nanoplatelets behave very differently from bulk CdSe, and in particular do not show a crossover t…
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…
We report excited state emission from p-states at excitation fluences well below ground state saturation in CdSe nanoplatelets. Size dependent exciton ground state-excited state energies and dynamics are determined by three independent methods, time-resolved photoluminescence (PL), time-integrated PL and Hartree renormalized k$\cdot$p calculations -- all in very good agreement. The ground state-excited state energy spacing strongly increases with the lateral platelet quantization. Our results suggest that the PL decay of CdSe platelets is governed by an LO-phonon bottleneck, related to the rep…
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.
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 p…
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 in-plane coefficient of thermal expansion (CTE) for CdSe nanoplatelets with the zinc-blende structure containing from two to five monolayers is calculated from first principles within the quasiharmonic approximation. A comparison of the obtained results with those for bulk CdSe with both the zinc-blende and wurtzite structures finds a significant increase in the magnitude of negative CTE and the temperature range of its observation in nanoplatelets. The main contribution to the negative thermal expansion in CdSe nanoplatelets is given by the out-of-plane flexural ZA mode and in-plane optic…
We report on the experimental and theoretical studies of optical alignment and optical orientation effects in an ensemble of core/shell CdSe/CdS colloidal nanoplatelets. The dependences of three Stokes parameters on the magnetic field applied in the Faraday geometry are measured under continuous wave resonant excitation of the exciton photoluminescence. Theoretical model is developed to take into account both bright and dark exciton states in the case of strong electron and hole exchange interaction and random in-plane orientation of the nanoplatelets in ensemble. The data analysis allows us t…
Excitons in diluted magnetic semiconductors represent excellent probes for studying the magnetic properties of these materials. Various magneto-optical effects, which depend sensitively on the exchange interaction of the excitons with the localized spins of the magnetic ions can be used for probing. Here, we study core/shell CdSe/(Cd,Mn)S colloidal nanoplatelets hosting diluted magnetic semiconductor layers. The inclusion of the magnetic Mn$^{2+}$ ions is evidenced by three magneto-optical techniques using high magnetic fields up to 15 T: polarized photoluminescence, optically detected magneti…
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 …
Charge carrier dynamics essentially determine the performance of various optoelectronic applications of colloidal semiconductor nanocrystals. Among them, two-dimensional nanoplatelets provide new adjustment freedom for their unique core/crown heterostructure. Herein, we demonstrate that by fine-tuning the core size and the lateral quantum confinement, the charge carrier transfer rate from the crown to the core can be varied by one order of magnitude in CdSe/CdSeS core/alloy-crown nanoplatelets. In addition, the transfer can be affected by a carrier blocking mechanism, i.e., the filled carriers…
Colloidal semiconductor nanoplatelets combine weak lateral confinement with strong Coulomb interactions, enhanced by dielectric confinement. When the platelets are charged with carriers of the same sign, this results in severe Coulomb repulsions which shape the electronic structure. To illustrate this point, the shell filling of type-I (CdSe/CdS) and type-II (CdSe/CdTe) core/crown nanoplatelets with up to 4 electrons or holes is investigated theoretically. We find that Coulomb repulsions enable addition energies exceeding room temperature thermal energy and promote the occupation of high-spin …
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…
Using semi-analytical models we calculate the energy, effective Bohr radius and radiative lifetime of neutral excitons confined in CdSe colloidal nanoplatelets (NPLs). The excitonic properties are largely governed by the electron-hole in-plane correlation, which in NPLs is enhanced by the quasi-two-dimensional motion and the dielectric mismatch with the organic environment. In NPLs with lateral size $L \gtrsim 20$ nm the exciton behavior is essentially that in a quantum well, with superradiance leading to exciton lifetimes of 1 ps or less, only limited by the NPL area. However, for $L < 20$ nm…
We experimentally investigated for the first time the lowest four band structure of Cd Se nanoplatelets at the r point of Brillouin zone [heavy-hole (hh), light-hole (lh) and two spin-orbital bands] and its modification due to the changing of the CdS shell thickness. The results of an experimental and theoretical study of exciton dynamics in colloidal CdSe/CdS nanoplateles are presented in the case of stationary laser excitation. The excitation was performed by means of the powerful nanosecond laser and the pump and probe technique was utilized. The differential transmission spectra peculiarit…
We show that the finite lateral sizes of ultrathin CdSe nanoplatelets strongly affect both their photoluminescence and optical absorption spectra. This is in contrast to the situation in quantum wells, in which the large lateral sizes may be assumed to be infinite. The lateral sizes of the nanoplatelets are varied over a range of a few to tens of nanometers. For these sizes excitons experience in-plane quantum confinement, and their center-of-mass motion becomes quantized. Our direct experimental observation of the discretization of the exciton center-of-mass states can be well understood on t…
Colloidal 2D semiconductor nanoplatelets are highly efficient light emitters, which exhibit large absorption and emission cross sections, and constitute promising laser gain media. However, if dispersed in solutions, such nanoplatelets lack a suitable optical platform for scalable and application-oriented integration into optical setups such as lasers. Here, we demonstrate the first successful integration of solution-processed 2D CdSe/CdS Core/Crown nanoplatelets in m-scale liquid core optical fibers. We compare the nanoplatelets' spectroscopic properties before and after filling them into the…
We demonstrate high quantum yield broad photoluminescence emission of ultrathin sub-nanometer CdSe nanoplatelets (two-monolayer). They also exhibit polarization-characterized lateral size dependent anomalous heavy hole and light/split-off hole absorption intensities.
A theory of the trion and biexciton in a nanowire (NW) in the framework of the effective-mass model using the Born-Oppenheimer approximation is presented. We consider the formation of trions and biexcitons under the action of both the lateral confinement and the localization potential. The analytical expressions for the binding energy and eigenfunctions of the trion and biexciton are obtained and expressed by means of matrix elements of the effective one-dimensional cusp-type Coulomb potentials whose parameters are determined self-consistently by employing the same eigenfunctions of the confin…
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…
Recent experiments suggest that the photoluminescence line width of CdSe and CdSe/CdS nanoplatelets (NPLs) may be broadened by the presence of shakeup (SU) lines from negatively charged trions. We carry out a theoretical analysis, based on effective mass and configuration interaction (CI) simulations, to identify the physical conditions that enable such processes. We confirm that trions in colloidal NPLs are susceptible of presenting SU lines up to one order of magnitude stronger than in epitaxial quantum wells, stimulated by dielectric confinement. For these processes to take place trions mus…
Colloidal semiconductor nanoplatelets exhibit quantum size effects due to their thickness of only few monolayers, together with strong optical band-edge transitions facilitated by large lateral extensions. In this article we demonstrate room temperature strong coupling of the light and heavy hole exciton transitions of CdSe nanoplatelets with the photonic modes of an open planar microcavity. Vacuum Rabi splittings of $66 \pm 1$ meV and $58 \pm 1$ meV are observed for the heavy and light hole excitons respectively, together with a polariton-mediated hybridisation of both transitions. By measuri…
Colloidal semiconductor nanoplatelets (NPLs) with electronic structure as quantum wells have recently emerged as exciting materials for optoelectronic applications. Here we investigate how morphology affects important photoluminescence (PL) properties of single CdSe and core/shell CdSe/CdZnS nanoplatelets. By analyzing PL intensity-lifetime correlation and second-order photon correlation results, we demonstrate that, irrespective of morphology, Auger recombination cannot be responsible for PL blinking of single NPLs. We propose that hot carrier trapping plays a significant role in blinking and…
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. …
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 loca…
Giant shell CdSe/CdS quantum dots are bright and flexible emitters, with near-unity quantum yield and suppressed blinking, but their single photon purity is reduced by efficient multiexcitonic emission. We report the observation, at the single dot level, of a large blueshift of the photoluminescence biexciton spectrum ($24\pm5$ nm over a sample of 32 dots) for pure-phase wurtzite quantum dots. By spectral filtering, we demonstrate a 2.3 times reduction of the biexciton quantum yield relative to the exciton emission, while preserving as much as 60% of the exciton single photon emission, thus im…
Colloidal semiconductor nanoplatelets, in which carriers are strongly confined only along one dimension, present fundamentally different excitonic properties than quantum dots, which support strong confinement in all three dimensions. In particular, multiple excitons strongly confined in just one dimension are free to re-arrange in the lateral plane, reducing the probability for multi-body collisions. Thus, while simultaneous multiple photon emission is typically quenched in quantum dots, in nanoplatelets its probability can be tuned according to size and shape. Here, we focus on analyzing mul…
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 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…
Colloidal Cadmium Selenide (CdSe) nanoplatelets (NPLs) are a recently developed class of efficient luminescent nanomaterial suitable for optoelectronic device applications. A change in temperature greatly affects their electronic bandstructure and luminescence properties. It is important to understand how-and-why the characteristics of NPLs are influenced, particularly at elevated temperature, where both reversible and irreversible quenching processes come into picture. Here we present a study on the effect of elevated temperature on the characteristics of colloidal CdSe NPLs. We used an effec…
Semiconductor nanoparticles of cadmium chalcogenides are known to exhibit pronounced thickness-dependent $E_0$ series of exciton transitions at the $Γ$ point of the Brillouin zone (BZ). In this work, we report an experimental evidence for high-energy series of exciton transitions, which originates from BZ points different from the $Γ$ point, in the family of cadmium chalcogenide quasi-2D nanoplatelets (NPLs). Intensive UV absorption bands demonstrating a pronounced size effect are observed for CdTe, CdSe, and CdS NPLs in addition to the $E_0$ exciton bands in the visible region. These new band…
Cd(Se,Te) Quantum Dots (QD) in ZnSe barrier typically exhibit a very high spectral density, which precludes investigation of single dot photoluminescence. We design, grow and study individual Cd(Se,Te)/ZnSe QDs of low spectral density of emission lines achieved by implementation of a Mn-assisted epitaxial growth. We find an unusually large variation of exciton-biexciton energy difference (3 meV $\leq$ $Δ\mathrm{E_{X-XX}}$ $\leq$ 26 meV) and of exciton radiative recombination rate in the statistics of QDs. We observe a strong correlation between the exciton-biexciton energy difference, exciton …
Luminescent colloidal CdSe nanorings are a new type of semiconductor structure that have attracted interest due to the potential for unique physics arising from their non-trivial toroidal shape. However, the exciton properties and dynamics of these materials with complex topology are not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and single particle measurements to study these materials. We find that on transformation of CdSe nanoplatelets to nanorings, by perforating the center of platelets, the emissio…
