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 optical $E$ modes that arise from the folding of TA phonon of bulk CdSe.
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 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…
Phonon spectra of CdSe nanoplatelets (2-6 ML) with the zinc-blende structure were calculated from first principles within the density-functional theory. It turned out that the Lamb modes in nanoplatelets are in fact optical rather than acoustic vibrations. Phonon spectra of the nanoplatelets show the appearance of a large number of low-frequency modes inherited from TA phonons in bulk CdSe. Calculations of the Raman spectra indicate a need to revise the interpretation of available experimental data. The largest contribution to the Raman spectra is provided by the quasi-Lamb modes with the $A_1…
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…
Atomically flat semiconductor nanostructures have sharp photoluminescence emission, short radiative lifetimes and a well-defined planar structure. However, these nanostructures lack the optical and electronic fine-tuning that justify extensive research in colloidal quantum dots. Here, we propose a heterostructure based on CdS nanoplatelets with laterally grown CdSe. Samples of two different thickness and varying ring width are synthesized by a one-pot method during which CdSe ring width is controlled by Se precursor amount. The CdSe dimensionality is continuously tuned from a 0D array of CdSe …
Accurate energy-size dependence of excitonic transitions in semiconductor nanocrystals in the strong confinement regime using classical theoretical approaches such as effective mass approximation, tight binding, or empirical pseudo-potential is difficult. We propose a simple empirical expression with three fitting parameters that accurately relates the size dependence of most known excitonic transitions in CdSe and in InAs nanocrystals. We show that this empirical expression can be deduced from a phase jump approach if the charge carriers are considered to travel on the atomic lattice of the n…
The vibrational spectroscopy of semiconductor nanostructures can provide important information on their structure. In this work, experimental Raman and infrared spectra are compared with vibrational spectra of CdSe/CdS core/shell nanoplatelets calculated from first principles using the density functional theory. The calculations confirm the two-mode behavior of phonon spectra of nanostructures. An analysis of the experimental spectra reveals the absence of modes with a high amplitude of vibrations of surface atoms, which indicates their strong damping. Taking into account the difference in the…
Zinc-blende CdSe semiconducting nanoplatelets (NPL) show outstanding quantum confinement properties thanks to their small, atomically-controlled, thickness. For example, they display extremely sharp absorption peaks that make them very interesting objects for optoelectronic applications. However, the presence of a ground-state electric dipole for these nanoparticles has not yet been investigated. We therefore used transient electric birefringence (TEB) to probe the electric dipole of 5-monolayer thick zinc-blende CdSe NPL with a parallelepipedic shape. We studied a dilute dispersion of isolate…
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…
CdSe nanoplatelets show perfectly quantized thicknesses of few monolayers. They present a situation of extreme, yet well defined quantum confinement. Due to large dielectric contrast between the semiconductor and its ligand environment, interaction between carriers and their dielectric images strongly renormalize bare single particle states. We discuss the electronic properties of this original system in an advanced tight-binding model, and show that Coulomb interactions, including self-energy corrections and enhanced electron-hole interaction, lead to exciton binding energies up to several hu…
The near-field Coulomb interaction between a nano-emitter and a graphene monolayer results in strong Förster-type resonant energy transfer and subsequent fluorescence quenching. Here, we investigate the distance dependence of the energy transfer rate from individual, i) zero-dimensional CdSe/CdS nanocrystals and ii) two-dimensional CdSe/CdS/ZnS nanoplatelets to a graphene monolayer. For increasing distances $d$, the energy transfer rate from individual nanocrystals to graphene decays as $1/d^4$. In contrast, the distance dependence of the energy transfer rate from a two-dimensional nanoplatele…
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…
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…
The electronic structure of CdSe/CdS core/shell seeded nanorods of experimentally relevant size is studied using a combination of molecular dynamics and semiempirical pseudopotential techniques, with the aim to address the transition from type-I to a quasi-type-II band alignment. The hole is found to be localized in the core region regardless of its size. The overlap of the electron density with the core region depends markedly on the size of the CdSe core: For small cores, we observe little overlap, consistent with type-II behavior. For large cores, significant core-overlap of a number of exc…
Due to the spatial confinement, two-dimensional metal chalcogenides display an extraordinary optical re-sponse and carrier transport ability. Solution-based synthesis techniques such as colloidal hot injection and ion exchange provide a cost-effective way to fabricate such low-dimensional semiconducting nanocrystals. Over the years, developments in colloidal chemistry made it possible to synthesize various kinds of ultrathin colloidal nanoplatelets, including wurtzite- and zinc blende-type CdSe, rocksalt PbS, black phosphorus-like SnX (X=S or Se), hexagonal copper sulfides, selenides and even …
