Anatolii Polovitsyn

Efficient charge transfer in solution-processed PbS quantum dot–reduced graphene oxide hybrid materials

Quantum dot–graphene hybrid materials have attracted significant interest due to the unique synergy of the optical properties of colloidal quantum dots (QDs) and the transport properties of graphene. This stimulated the development of low-cost and up-scalable solution-processed strategies for hybrid materials with potential applications in light harvesting and optoelectronic devices. Herein, we report a versatile covalent linking-based approach for the functionalization of reduced graphene oxide (rGO), to prepare a variety of QD–rGO hybrid dispersions with QDs of different sizes and compositions (PbS, PbS–CdS and CdSe QDs), and shapes (CdSe–CdS dot-in-rods). We achieved a well-controlled QD coverage of the rGO sheets by functionalizing the rGO surface with mercapto-silane linkers. A further spectroscopic investigation of near-infrared PbS QD–rGO materials demonstrates efficient electronic coupling between both materials. The QD photoluminescence emission quenching and exciton lifetime shortening of up to 95%, together with subtle graphene Raman G-band shifts upon QD linking, support electron transfer as the dominant relaxation pathway from the QD to the rGO. The use of core–shell PbS–CdS QDs allows tuning of the transfer efficiency from 94% for a 0.2 nm thin CdS shell, down to 30% for a 1.1 nm thick shell.

Shape control of zincblende CdSe nanoplatelets

The lateral dimensions of CdSe nanoplatelets have a strong and unique influence on their opto-electronic properties, with sizes that can be tuned from the weak to the strong exciton confinement regime. There are state-of-the-art reports on several nanoplatelet syntheses; however, at present only the thickness is well-controlled. We demonstrate here that we can achieve a control over the aspect ratio and overall nanoplate area by carefully adjusting the reagents that induce the in-plane growth. A variation of the fraction of hydrated Cd(OAc)2 in a Cd(OAc)2/Cd(OAc)2·2H2O mixture tailors the nanoplatelet aspect ratio. This occurs independently of the reaction time, which can be used to fine-tune the overall length and width. An interpretation is given by the in situ formation of a small amount of hydroxide anions that alter the surface energy of specific planes.

Piezoelectric Control of the Exciton Wave Function in Colloidal CdSe/CdS Nanocrystals

Using multiband k·p calculations, we show that strain-engineered piezoelectricity is a powerful tool to modulate the electron-hole spatial separation in a wide class of wurtzite CdSe/CdS nanocrystals. The inherent anisotropy of the hexagonal crystal structure leads to anisotropic strain and, consequently, to a pronounced piezoelectric field along the c axis, which can be amplified or quenched through a proper design of the core-shell structure. The use of large cores and thick shells promotes a gradual departure from quantum confined nanocrystals to a regime dominated by piezoelectric confinement. This allows excitons to evolve from the usual type-I and quasi-type-II behavior to a type-II behavior in dot-in-dots, dot-in-rods, rod-in-rods, and dot-in-plates. Piezoelectric fields explain experimental observations for giant-shell nanocrystals, whose time-resolved photoluminescence reveals long exciton lifetimes for large cores, contrary to the expectations of standard quantum confinement models. They also explain the large differences in exciton lifetimes reported for different classes of CdSe/CdS nanocrystals.

Ultrafast emission from colloidal nanocrystals under pulsed X-ray excitation

Fast timing has emerged as a critical requirement for radiation detection in medical and high energy physics, motivating the search for scintillator materials with high light yield and fast time response. However, light emission rates from conventional scintillation mechanisms fundamentally limit the achievable time resolution, which is presently at least one order of magnitude slower than required for next-generation detectors. One solution to this challenge is to generate an intense prompt signal in response to ionizing radiation. In this paper, we present colloidal semiconductor nanocrystals (NCs) as promising prompt photon sources. We investigate two classes of NCs: two-dimensional CdSe nanoplatelets (NPLs) and spherical CdSe/CdS core/giant shell quantum dots (GS QDs). We demonstrate that the emission rates of these NCs under pulsed X-ray excitation are much faster than traditional mechanisms in bulk scintillators, i.e. 5d-4f transitions. CdSe NPLs have a sub-100 ps effective decay time of 77 ps and CdSe/CdS GS QDs exhibit a sub-ns value of 849 ps. Further, the respective CdSe NPL and CdSe/CdS GS QD X-ray excited photoluminescence have the emission characteristics of excitons (X) and multiexcitons (MX), with the MXs providing additional prospects for fast timing with substantially shorter lifetimes.