RESUMEN
Incorporating magnetic ions into semiconductor nanocrystals has emerged as a prominent research field for manipulating spin-related properties. The magnetic ions within the host semiconductor experience spin-exchange interactions with photogenerated carriers and are often involved in the recombination routes, stimulating special magneto-optical effects. The current account presents a comparative study, emphasizing the impact of engineering nanostructures and selecting magnetic ions in shaping carrier-magnetic ion interactions. Various host materials, including the II-VI group, halide perovskites, and I-III-VI2 in diverse structural configurations such as core/shell quantum dots, seeded nanorods, and nanoplatelets, incorporated with magnetic ions such as Mn2+, Ni2+, and Cu1+/2+ are highlighted. These materials have recently been investigated by us using state-of-the-art steady-state and transient optically detected magnetic resonance (ODMR) spectroscopy to explore individual spin-dynamics between the photogenerated carriers and magnetic ions and their dependence on morphology, location, crystal composition, and type of the magnetic ion. The information extracted from the analyses of the ODMR spectra in those studies exposes fundamental physical parameters, such as g-factors, exchange coupling constants, and hyperfine interactions, together providing insights into the nature of the carrier (electron, hole, dopant), its local surroundings (isotropic/anisotropic), and spin dynamics. The findings illuminate the importance of ODMR spectroscopy in advancing our understanding of the role of magnetic ions in semiconductor nanocrystals and offer valuable knowledge for designing magnetic materials intended for various spin-related technologies.
RESUMEN
In recent years, it was found that current passing through chiral molecules exhibits spin preference, an effect known as Chiral Induced Spin Selectivity (CISS). The effect also enables the reduction of scattering and therefore enhances delocalization. As a result, the delocalization of an exciton generated in the dots is not symmetric and relates to the electronic and hole excited spins. In this work utilizing fast spectroscopy on hybrid multilayered QDs with a chiral polypeptide linker system, we probed the interdot chiral coupling on a short time scale. Surprisingly, we found strong coherent coupling and delocalization despite having long 4-nm chiral linkers. We ascribe the results to asymmetric delocalization that is controlled by the electron spin. The effect is not measured when using shorter nonchiral linkers. As the system mimics light-harvesting antennas, the results may shed light on a mechanism of fast and efficient energy transfer in these systems.
RESUMEN
Numerous studies have reported that transient absorption spectra in core CdSe nanocrystals do not register state filling in 1Sh, an absence which has profound consequences in light-emitting applications. It has been assigned alternatively to rapid hole trapping, or to distribution over a dense degenerate valence band manifold which includes dark states. Here we attempt to observe early contributions of nascent holes to the bleaching of the band edge exciton transition by conducting 1Se1Sh pump-1Se1Sh probe spectroscopy with <10 fs laser pulses on organic ligand passivated CdSe crystals. The results show no rapidly hole-state filling effects in transient absorption measurements even at the earliest delay, despite the use of pulses which are capable of resolving all dissipation mechanisms reflected in the homogeneous 1Se1Sh bandwidth. This proves that neither hole trapping nor rapid redistribution of the nascent hole over energetically available valence band states can explain the absence of hole contributions to band edge bleaching, calling for a mechanistic review of this phenomenon.
RESUMEN
Controlling the spin degrees of freedom of photogenerated species in semiconductor nanostructures via magnetic doping is an emerging scientific field that may play an important role in the development of new spin-based technologies. The current work explores spin properties in colloidal CdSe/CdS:Mn seeded-nanorod structures doped with a dilute concentration of Mn2+ ions across the rods. The spin properties were determined using continuous-wave optically detected magnetic resonance (ODMR) spectroscopy recorded under variable microwave chopping frequencies. These experiments enabled the deconvolution of a few different radiative recombination processes: band-to-band, trap-to-band, and trap-to-trap emission. The results uncovered the major role of carrier trapping on the spin properties of elongated structures. The magnetic parameters, determined through spin-Hamiltonian simulation of the steady-state ODMR spectra, reflect anisotropy associated with carrier trapping at the seed/rod interface. These observations unveiled changes in the carriers' g-factors and spin-exchange coupling constants as well as extension of radiative and spin-lattice relaxation times due to magnetic coupling between interface carriers and neighboring Mn2+ ions. Overall, this work highlights that the spin degrees of freedom in seeded nanorods are governed by interfacial trapping and can be further manipulated by magnetic doping. These results provide insights into anisotropic nanostructure spin properties relevant to future spin-based technologies.
RESUMEN
The incorporation of magnetic impurities into semiconductor nanocrystals with size confinement promotes enhanced spin exchange interaction between photogenerated carriers and the guest spins. This interaction stimulates new magneto-optical properties with significant advantages for emerging spin-based technologies. Here we observe and elaborate on carrier-guest interactions in magnetically doped colloidal nanoplatelets with the chemical formula CdSe/Cd1-xMnxS, explored by optically detected magnetic resonance and magneto-photoluminescence spectroscopy. The host matrix, with a quasi-type II electronic configuration, introduces a dominant interaction between a photogenerated electron and a magnetic dopant. Furthermore, the data convincingly presents the interaction between an electron and nuclear spins of the doped ions located at neighboring surroundings, with consequent influence on the carrier's spin relaxation time. The nuclear spin contribution by the magnetic dopants in colloidal nanoplatelets is considered here for the first time.
RESUMEN
The conjecture that, as in bulk semiconductors, hot multiexcitons in nanocrystals cool rapidly to the lowest available energy levels is tested here by recording the effects of a single cold "spectator" exciton on the relaxation dynamics of a subsequently deposited hot counterpart. Results in CdSe/CdS nanodots show that a preexisting cold "spectator exciton" allows only half of the photoexcited electrons to relax directly to the band-edge. The rest are blocked in an excited quantum state due to conflicts in spin orientation. The latter fully relax in this sample only after â¼25 ps as the blocked electrons spins flip, prolonging the temporal window of opportunity for harvesting the retained energy more than 100 fold! Common to all quantum-confined nanocrystals, this process will delay cooling and impact the spectroscopic signatures of hot multiexcitons in all envisioned generation scenarios. How the spin-flipping rate scales with particle size and temperature remains to be determined.
RESUMEN
Semiconductor colloidal quantum dots (CQDs) have attracted vast scientific and technological interest throughout the past three decades, due to the unique tuneability of their optoelectronic properties by variation of size and composition. However, the nanoscale size brings about a large surface-to-bulk volume ratio, where exterior surfaces have a pronounced influence on the chemical stability and on the physical properties of the semiconductor. Therefore, numerous approaches have been developed to gain efficient surface passivation, including a coverage by organic or inorganic molecular surfactants as well as the formation of core/shell heterostructures (a semiconductor core epitaxially covered by another semiconductor shell). This review focuses on special designs of core/shell heterostructures from the IV-VI and II-VI semiconductor compounds, and on synthetic approaches and characterization of the optical properties. Experimental observations revealed the formation of core/shell structures with type-I or quasi-type-II band alignment between the core and shell constituents. Theoretical calculations of the electronic band structures, which were also confirmed by experimental work, exposed surplus electronic tuning (beyond the radial diameter) with adaptation of the composition and control of the interface properties. The studies also considered strain effects that are created between two different semiconductors. It was disclosed experimentally and theoretically that the strain can be released via the formation of alloys at the core-shell interface. Overall, the core/shell and core/alloyed-shell heterostructures showed enhancement in luminescence quantum efficiency with respect to that of pure cores, extended lifetime, uniformity in size and in many cases good chemical sustainability under ambient conditions.
