High-Frequency EPR and ENDOR Spectroscopy on Semiconductor Quantum Dots

It is shown that high-frequency electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy are excellent tools for the investigation of the electronic properties of semiconductor quantum dots (QDs). The great attractions of these techniques are that, in contrast to optical methods, they allow the identification of the dopants and provide information about the spatial distribution of the electronic wave function. This latter aspect is particularly attractive because it allows for a quantitative measurement of the effect of confinement on the shape and properties of the wave function. In this contribution EPR and ENDOR results are presented on doped ZnO QDs. Shallow donors (SDs), related to interstitial Li and Na and substitutional Al atoms, have been identified in this material by pulsed high-frequency EPR and ENDOR spectroscopy. The shallow character of the wave function of the donors is evidenced by the multitude of ENDOR transitions of the 67Zn nuclear spins and by the hyperfine interaction of the 7Li, 23Na and 27Al nuclear spins that are much smaller than for atomic lithium, sodium and aluminium. The EPR signal of an exchange-coupled pair consisting of a shallow donor and a deep Na-related acceptor has been identified in ZnO nanocrystals with radii smaller than 1.5 nm. From ENDOR experiments it is concluded that the deep Na-related acceptor is located at the interface of the ZnO core and the Zn(OH)2 capping layer, while the shallow donor is in the ZnO core. The spatial distribution of the electronic wave function of a shallow donor in ZnO semiconductor QDs has been determined in the regime of quantum confinement by using the nuclear spins as probes. Hyperfine interactions as monitored by ENDOR spectroscopy quantitatively reveal the transition from semiconductor to molecular properties upon reduction of the size of the nanoparticles. In addition, the effect of confinement on the g-factor of SDs in ZnO as well as in CdS QDs is observed. Finally, it is shown that an almost complete dynamic nuclear polarization (DNP) of the 67Zn nuclear spins in the core of ZnO QDs and of the 1H nuclear spins in the Zn(OH)2 capping layer can be obtained. This DNP is achieved by saturating the EPR transition of SDs present in the QDs with resonant high-frequency microwaves at low temperatures. This nuclear polarization manifests itself as a hole and an antihole in the EPR absorption line of the SD in the QDs and a shift of the hole (antihole). The enhancement of the nuclear polarization opens the possibility to study semiconductor nanostructures with nuclear magnetic resonance techniques. © 2010 The Author(s)

High-frequency EPR, ESE, and ENDOR spectroscopy of Co- and Mn-doped ZnO quantum dots

Co- and Mn-doped ZnO quantum dots (QDs) with ZnO/Zn(OH)2 core-shell structure were studied using high-frequency electron paramagnetic resonance (EPR), electron spin echo, and electron-nuclear double resonance (ENDOR) at low temperature. The shape of the EPR spectrum of cobalt ions was observed to change as a result of Co2+ coupling with optically created shallow donors (SDs). This, along with a shift of SDs line, is a direct demonstration of interaction between the magnetic ion and donor electron in confined system of ZnO QD. ENDOR resonance of the 1H hydrogen nuclei detected by the EPR signal of Co2+ and Mn2+ evidence the hyperfine coupling between these ions, located in the ZnO core, and the protons outside the quantum dot core in the shell. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Electron paramagnetic resonance based spectroscopic techniques

© 2014 Springer-Verlag Berlin Heidelberg. All rights reserved. This chapter addresses the use of electron paramagnetic resonance based spectroscopic techniques to study nanostructures. Particular attention is given to high frequency electron spin echo, electron-nuclear double resonance and optically detected magnetic resonance spectroscopy

Проблематика переходу до інформаційного суспільства

Аналізуються фундаментальні передумови, що є первинними в процесі творення інформаційного суспільства. Обґрунтовується теза, що електронна готовність та електронне залучення є основоположними факторами переходу суспільства від індустріального до інформаційного устрою. Подано основні характеристики цих понять та наголошено на їх значенні

Dynamical nuclear polarization and confinement effects in ZnO quantum dots

The spatial distribution of the electronic wave function of a shallow donor (SD) in a ZnO semiconductor quantum dots (QD's) has been determined in the regime of quantum confinement by using the nuclear spins as probes. Hyperfine (HF) interactions as monitored by electron nuclear double resonance spectroscopy quantitatively reveal the transition from semiconductor to molecular properties upon reduction of the size of the nanoparticles. Influence of confinement effect on g-factor value of SD's in ZnO and CdS QD's was displayed. The almost complete dynamic nuclear polarization (DNP) of nuclear spins has been demonstrated can be achieved in ZnO QD's by saturating the EPR transition of the SD present in the QD's with using high-frequency at low temperatures. Polarization of 67Zn nuclear spins in ZnO core and of 1H nuclear spins in the Zn(OH) 2 capping layer have been obtained which manifests itself via the creation of a hole and an antihole in the EPR absorption line of the SD in QD's and a shift of the hole (antihole). The enhancement of the nuclear polarization opens the possibility to study semiconductor nanostructures with NMR techniques. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Direct Observation of Electron-to-Hole Energy Transfer in CdSe Quantum Dots

Euan Hendry, Mattijs Koeberg, F. Wang, H. Zhang, C. de Mello Donegá, D. Vanmaekelbergh, and Mischa Bonn, Physical Review Letters, Vol. 96, article 057408 (2006). "Copyright © 2006 by the American Physical Society."We independently determine the subpicosecond cooling rates for holes and electrons in CdSe quantum dots. Time-resolved luminescence and terahertz spectroscopy reveal that the rate of hole cooling, following photoexcitation of the quantum dots, depends critically on the electron excess energy. This constitutes the first direct, quantitative measurement of electron-to-hole energy transfer, the hypothesis behind the Auger cooling mechanism proposed in quantum dots, which is found to occur on a 1±0.15 ps time scale

Origins of Photoluminescence Decay Kinetics in CdTe Colloidal Quantum Dots

Recent experimental studies have identified at least two nonradiative components in the fluorescence decay of solutions of CdTe colloidal quantum dots (CQDs). The lifetimes reported by different groups, however, differed by orders of magnitude, raising the question of whether different types of traps were at play in the different samples and experimental conditions and even whether different types of charge carriers were involved in the different trapping processes. Considering that the use of these nanomaterials in biology, optoelectronics, photonics, and photovoltaics is becoming widespread, such a gap in our understanding of carrier dynamics in these systems needs addressing. This is what we do here. Using the state-of-the-art atomistic semiempirical pseudopotential method, we calculate trapping times and nonradiative population decay curves for different CQD sizes considering up to 268 surface traps. We show that the seemingly discrepant experimental results are consistent with the trapping of the hole at unsaturated Te bonds on the dot surface in the presence of different dielectric environments. In particular, the observed increase in the trapping times following air exposure is attributed to the formation of an oxide shell on the dot surface, which increases the dielectric constant of the dot environment. Two types of traps are identified, depending on whether the unsaturated bond is single (type I) or part of a pair of dangling bonds on the same Te atom (type II). The energy landscape relative to transitions to these traps is found to be markedly different in the two cases. As a consequence, the trapping times associated with the different types of traps exhibit a strikingly contrasting sensitivity to variations in the dot environment. Based on these characteristics, we predict the presence of a sub-nanosecond component in all photoluminescence decay curves of CdTe CQDs in the size range considered here if both trap types are present. The absence of such a component is attributed to the suppression of type I traps

Nano-engineered electron–hole exchange interaction controls exciton dynamics in core–shell semiconductor nanocrystals

A strong electron–hole exchange interaction (EI) in semiconductor nanocrystals (NCs) gives rise to a large (up to tens of meV) splitting between optically active ('bright') and optically passive ('dark') excitons. This dark–bright splitting has a significant effect on the optical properties of band-edge excitons and leads to a pronounced temperature and magnetic field dependence of radiative decay. Here we demonstrate a nanoengineering-based approach that provides control over EI while maintaining nearly constant emission energy. We show that the dark–bright splitting can be widely tuned by controlling the electron–hole spatial overlap in core–shell CdSe/CdS NCs with a variable shell width. In thick-shell samples, the EI energy reduces to <250 μeV, which yields a material that emits with a nearly constant rate over temperatures from 1.5 to 300 K and magnetic fields up to 7 T. The EI-manipulation strategies demonstrated here are general and can be applied to other nanostructures with variable electron–hole overlap

Type-II Colloidal Quantum Wells: CdSe/CdTe Core/Crown Heteronanoplatelets

Solution-processed quantum wells, also known as colloidal nanoplatelets (NPLs), are emerging as promising materials for colloidal optoelectronics. In this work, we report the synthesis and characterization of CdSe/CdTe core/crown NPLs exhibiting a Type-II electronic structure and Type-II specific optical properties. Here, based on a core-seeded approach, the CdSe/CdTe core/crown NPLs were synthesized with well-controlled CdTe crown coatings. Uniform and epitaxial growth of CdTe crown region was verified by using structural characterization techniques including transmission electron microscopy (TEM) with quantitative EDX analysis and X-ray diffraction (XRD). Also the optical properties were systematically studied in these Type-II NPLs that reveal strongly red-shifted photoluminescence (up to similar to 150 nm) along with 2 orders of magnitude longer fluorescence lifetimes (up to 190 ns) compared to the Type-I NPLs owing to spatially indirect excitons at the Type-II interface between the CdSe core and the CdTe crown regions. Photoluminescence excitation spectroscopy confirms that this strongly red-shifted emission actually arises from the CdSe/CdTe NPLs. In addition, temperature-dependent time-resolved fluorescence spectroscopy was performed to reveal the temperature-dependent fluorescence decay kinetics of the Type-II NPLs exhibiting interesting behavior. Also, water-soluble Type-II NPLs were achieved via ligand exchange of the CdSe/CdTe core/crown NPLs by using 3-mercaptopropionic acid (MPA), which allows for enhanced charge extraction efficiency owing to their shorter chain length and enables high quality film formation by layer-by-layer (LBL) assembly. With all of these appealing properties, the CdSe/CdTe core/crown heterostructures having Type-II electronic structure presented here are highly promising for light-harvesting applications