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 peculiarities
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 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.
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.
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 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…
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…
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…
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 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 offe…
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…
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…
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 …
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…
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…
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…
The easily tunable emission of halide perovskite nanocrystals throughout the visible spectrum makes them an extremely promising material for light-emitting applications. Whereas high quantum yields and long-term colloidal stability have already been achieved for nanocrystals emitting in the red and green spectral range, the blue region currently lags behind, with low quantum yields, broad emission profiles and insufficient colloidal stability. In this work, we present a facile synthetic approach for obtaining two-dimensional CsPbBr3 nanoplatelets with monolayer-precise control over their thick…
We show theoretically that carriers confined in semiconductor colloidal nanoplatelets (NPLs) sense the presence of neighbor, cofacially stacked NPLs in their energy spectrum. When approaching identical NPLs, the otherwise degenerate energy levels redshift and split, forming (for large stacks) minibands of several meV width. Unlike in epitaxial structures, the molecular behavior does not result from quantum tunneling but from changes in the dielectric confinement. The associated excitonic absorption spectrum shows a rich structure of bright and dark states, whose optical activity and multiplici…
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…
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.
Coherent spin dynamics in colloidal CdSe quantum dots (QDs) typically show two spin components with different Larmor frequencies, whose origin is an open question. We exploit the photocharging approach to identify their origin and find that surface states play a key role in the appearance of the spin signals. By controlling the photocharging with electron or hole acceptors, we show that the specific spin component can be enhanced by the choice of acceptor type. In core/shell CdSe/ZnS QDs, the spin signals are significantly weaker. Our results exclude the neutral exciton as the spin origin and …
Recently, the fabrication of CdSe nanoplatelets became an important research topic. Nanoplatelets are often described as having a similar electronic structure as 2D dimensional quantum wells and are promoted as colloidal quantum wells with monolayer precision width. In this paper, we show, that nanoplatelets are not ideal quantum wells, but cover depending on the size: the strong confinement regime, an intermediate regime and a Coulomb dominated regime. Thus, nanoplatelets are an ideal platform to study the physics in these regimes. Therefore, the exciton states of the nanoplatelets are numeri…
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…
Doping a semiconductor quantum dot with just a single impurity atom can completely transform its physical properties. Here, we report and analyze the magnetic circular dichroism (MCD) spectra of colloidal CdSe quantum dot samples containing on average fewer than one Mn2+ per quantum dot. Even at this sub-single-dopant level, the low-temperature low-field data are dominated by impurity-induced Zeeman splittings caused by dopant-carrier sp-d exchange. Unlike in more heavily doped quantum dots, however, the MCD intensity at the first CdSe exciton shows a field-induced sign flip as the field stren…
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…
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…
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…
Strongly quantum-confined 2D colloidal PbS nanoplatelets (NPLs) are highly interesting materials for near-infrared optoelectronic applications. Here, we use ultrafast transient optical absorption spectroscopy to study the characteristics and dynamics of photoexcited excitons in ultrathin PbS NPLs with a cubic (rock-salt) structure. The NPLs are synthesized at near room temperature from lead oleate and thiourea precursors and show an optical absorption onset at 680 nm (1.8 eV) as well as photoluminescence at 720 nm (1.7 eV). By treating PbS NPLs with CdCl2 in a post-synthetic step, their photol…
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 study the effect of Coulomb correlation on the emission properties of the ground state exciton in zincblende CdSe/ZnS core-shell and in wurtzite ZnO quantum dots. We validate our theory model by comparing results of computed exciton energies of CdSe/ZnS quantum dots to photoluminescence and scanning near-field optical microscopy measurements. We use that to estimate the diameter of the quantum dots using a simple model based on infinitely deep quantum well and compare the results with the statistics of the atomic force microscopy scans of CdSe/ZnS dots, obtaining excellent agreement. Therea…
Doping of bulk semiconductors has revealed widespread success in optoelectronic applications. In the past few decades, substantial effort has been engaged for doping at the nanoscale. Recently, doped zero-dimensional quantum dots made of semiconductor nanocrystals have been demonstrated to be promising materials for luminescent solar concentrators (LSCs) as they can be engineered for providing Stokes-shifted tunable emission in the solar spectrum. However, existing doped colloidal quantum dots suffer from moderately low quantum efficiency and intrinsically small absorption cross-section, which…
Coupled colloidal quantum dot molecules composed of two fused CdSe/CdS core/shell sphere monomers were recently presented. Upon fusion, the potential energy landscape is changing into two quantum dots separated by a pre-tuned potential barrier with energetics dictated by the conduction and valence band offsets of the core/shell semiconductors, and width controlled by the shell thickness and the fusion reaction conditions. In close proximity of the two nanocrystals, orbital hybridization occurs, forming bonding and anti-bonding states in analogy to the hydrogen molecule. In this study, we exami…
Coupling to phonon modes is a primary mechanism of excitonic dephasing and energy loss in semiconductors. However, low-energy phonons in colloidal quantum dots and their coupling to excitons are poorly understood, since their experimental signatures are weak and usually obscured by unavoidable inhomogeneous broadening of colloidal dot ensembles. We use multi-dimensional coherent spectroscopy at cryogenic temperatures to extract the homogeneous nonlinear optical response of excitons in a CdSe/CdZnS core/shell colloidal quantum dot ensemble. Comparison to simulation provides evidence that the ob…
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…
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…
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…
For high-speed optoelectronic applications relying on fast relaxation or energy transfer mechanisms, understanding of carrier relaxation and recombination dynamics is critical. Here, we compare the differences in photoexcited carrier dynamics in 2D and quasi-3D colloidal methylammonium lead iodide perovskite nanoplatelets via differential transmission spectroscopy. We find that the cooling of excited electron-hole pairs by phonon emission progresses much faster and is intensity-independent in the 2D-case. This is due to the low dielectric surrounding of the thin perovskite layers, for which th…
The picosecond dynamics of excitons in colloidal CdSe nanorods are directly measured via their 1s to 2p-like internal transitions by ultra-broadband terahertz spectroscopy. Broadened absorption peaks from both the longitudinal and transverse states are observed at 8.5 and 11 THz, respectively. The onset of exciton-LO phonon coupling appears as a bleach in the optical conductivity spectra at the LO phonon energy for times > 1 ps after excitation. Simulations show a suppressed exciton temperature due to thermally excited hole states being rapidly captured onto ligands or unpassivated surface sta…
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…
