Coherent Electron Spin Dynamics Research Articles

Coherent Carrier Spin Dynamics in FAPbBr3 Perovskite Crystals.

Coherent spin dynamics of electrons and holes are studied in hybrid organic-inorganic lead halide perovskite FAPbBr3 bulk single crystals using the time-resolved Kerr ellipticity technique at cryogenic temperatures. The Larmor spin precession of the carrier spins in a magnetic field is monitored to measure the Landé g-factors of electrons (+2.44) and holes (+0.41). These g-factors are highly isotropic. The measured spin dephasing times amount to a few nanoseconds, and the longitudinal hole spin relaxation time is 470 ns. The important role of the strong hyperfine interaction between carrier spins and nuclear spins is demonstrated via dynamic nuclear polarization. At low temperatures, electron and hole spin relaxation predominantly occurs via the hyperfine interaction, whose importance significantly decreases at temperatures above 12 K. We overview the spin dynamics in various lead halide perovskite crystals and polycrystalline films and conclude on their common features provided by charge carrier localization at cryogenic temperatures.

Temperature dependence of the electron and hole Landé g-factors in CsPbI3 nanocrystals embedded in a glass matrix.

The coherent spin dynamics of electrons and holes in CsPbI3 perovskite nanocrystals in a glass matrix are studied by the time-resolved Faraday ellipticity technique in magnetic fields up to 430 mT across a temperature range from 6 K to 120 K. The Landé g-factors and spin dephasing times are evaluated from the observed Larmor precession of electron and hole spins. The nanocrystal size in the three studied samples varies from about 8 to 16 nm, resulting in exciton transition varying from 1.69 to 1.78 eV at a temperature of 6 K, allowing us to study the corresponding energy dependence of the g-factors. The electron g-factor decreases with increasing confinement energy in the NCs as a result of NC size reduction, and also with increasing temperature. The hole g-factor shows the opposite trend. Model analysis shows that the variation of g-factors with NC size arises from the transition energy dependence of the g-factors, which becomes strongly renormalized by temperature.

Coherent Spin Dynamics of Electrons in CdSe Colloidal Nanoplatelets

Coherent spin dynamics of electrons in CdSe colloidal nanoplatelets are investigated by time-resolved pump–probe Faraday rotation at room and cryogenic temperatures. We measure electron spin precession in a magnetic field and determine g-factors of 1.83 and 1.72 at low temperatures for nanoplatelets with a thickness of 3 and 4 monolayers, respectively. The dephasing time of spin precession T2* amounts to a few nanoseconds and has a weak dependence on temperature, while the longitudinal spin relaxation time T1 exceeds 10 ns even at room temperature. Observations of single and double electron spin–flips confirm that the nanoplatelets are negatively charged. The spin–flip Raman scattering technique reveals g-factor anisotropy by up to 10% in nanoplatelets with thicknesses of 3, 4, and 5 monolayers. In the ensemble with a random orientation of nanoplatelets, our theoretical analysis shows that the measured Larmor precession frequency corresponds to the in-plane electron g-factor. We conclude that the experimentally observed electron spin dephasing and its acceleration in the magnetic field are not provided by the electron g-factor anisotropy and can be related to the localization of the resident electrons and fluctuations of the localization potential.

Electron Spin Coherence in CdSe Nanocrystals in a Glass Matrix.

The coherent spin dynamics of electrons in CdSe nanocrystals embedded in a glass matrix with diameters from 3.3 up to 6.1 nm are investigated by time-resolved Faraday ellipticity at room and cryogenic temperatures. Only one Larmor precession frequency is detected, which corresponds to the larger of the two precession frequencies and thus g-factor values found in the typical signal from solution-grown colloidal CdSe nanocrystals. We identify this frequency accordingly as associated with the spin precession of resident electrons localized in the nanocrystals in the vicinity of the surface. We provide a detailed theoretical analysis of the exciton level spin structure in the magnetic field and model the spin dynamics in CdSe nanocrystals of different symmetries. This allows us to exclude the exciton as the origin of the experimentally observed oscillating signal. At a cryogenic temperature of 6 K, an additional nonoscillating component emerges in the spin dynamics. We consider several possible origins of this signal and conclude that it is related to the hole spin polarization.

Coherent Spin Dynamics of Localized Electrons in Monolayer MoS2.

Compared with itinerant electrons in monolayer transition-metal dichalcogenides, localized electrons exhibit coherent spin precession in transverse magnetic fields B and usually have longer spin relaxation times. Here, we uncover the intrinsic spin dephasing processes of localized electrons whose mechanism remains unclear. Electron spin coherence dynamics are studied by time-resolved Faraday rotation spectroscopy in monolayer MoS2, where four subensembles of localized electrons are found with different g factor values and inhomogeneous broadening. The spin dephasing rates of all four subensembles include a linearly B-dependent part due to g-factor inhomogeneity and a B-independent part dominated by electron-nuclear hyperfine interaction and/or anisotropic exchange interaction. The hyperfine-induced spin dephasing time is ∼30-40 ns, and the anisotropic exchange-induced spin dephasing time is on the order of subnanoseconds. The findings give insight into the coherent spin dynamics of localized electrons in monolayers and the interaction between the electron spin and its environment.

Lead-Dominated Hyperfine Interaction Impacting the Carrier Spin Dynamics in Halide Perovskites.

The outstanding optical quality of lead halide perovskites inspires studies of their potential for the optical control of carrier spins as pursued in other materials. Entering largely uncharted territory, time-resolved pump-probe Kerr rotation is used to explore the coherent spin dynamics of electrons and holes in bulk formamidinium caesium lead iodine bromide (FA0.9 Cs0.1 PbI2.8 Br0.2 ) and to determine key parameters characterizing interactions of their spins, such as the g-factors and relaxation times. The demonstrated long spin dynamics and narrow g-factor distribution prove the perovskites as promising competitors for conventional semiconductors in spintronics. The dynamic nuclear polarization via spin-oriented holes is realized and the identification of the lead (207 Pb) isotope in optically detected nuclear magnetic resonance proves that the hole-nuclei interaction is dominated by the lead ions. A detailed theoretical analysis accounting for the specifics of the lead halide perovskite materials allows the evaluation of the underlying hyperfine interaction constants, both for electrons and holes. Recombination and spin dynamics evidence that at low temperatures, photogenerated electrons and holes are localized at different regions of the perovskite crystal, resulting in their long lifetimes up to 44μs. The findings form the base for the tailored development of spin-optoelectronic applications for the large family of lead halide perovskites and theirnanostructures.

Suppression of nuclear spin fluctuations in an InGaAs quantum dot ensemble by GHz-pulsed optical excitation

The coherent electron spin dynamics of an ensemble of singly charged (In,Ga)As/GaAs quantum dots in a transverse magnetic field is driven by periodic optical excitation at 1 GHz repetition frequency. Despite the strong inhomogeneity of the electron g factor, the spectral spread of optical transitions, and the broad distribution of nuclear spin fluctuations, we are able to push the whole ensemble of excited spins into a single Larmor precession mode that is commensurate with the laser repetition frequency. Furthermore, we demonstrate that an optical detuning of the pump pulses from the probed optical transitions induces a directed dynamic nuclear polarization and leads to a discretization of the total magnetic field acting on the electron ensemble. Finally, we show that the highly periodic optical excitation can be used as universal tool for strongly reducing the nuclear spin fluctuations and preparation of a robust nuclear environment for subsequent manipulation of the electron spins, also at varying operation frequencies.

Short range proximity effect induced by exchange interaction in tunnel-coupled CdTe and (Cd,Mn)Te quantum wells

The coherent spin dynamics of electrons in tunnel-coupled CdTe and (Cd,Mn)Te quantum wells (QWs) is studied by time-resolved pump-probe Kerr rotation. The coupled QWs have different thicknesses; the narrow one is doped by ${\mathrm{Mn}}^{2+}$ magnetic ions. A short range proximity effect between them is observed: the Zeeman splitting of electrons in the wide QW is given in addition to the intrinsic electron $g$ factor by the exchange interaction with the ${\mathrm{Mn}}^{2+}$ ions mediated by electron tunneling into the narrow QW. The exchange interaction strength scales with the ${\mathrm{Cd}}_{0.88}{\mathrm{Mg}}_{0.12}\mathrm{Te}$ barrier thickness separating the QWs. The Kerr rotation signal measured on the wide QW shows two close frequencies of electron spin Larmor precession in a transverse magnetic field. These components have very different spin dephasing times, 50 ps and 1 ns. The two frequencies originate from electrons in the wide QW being either part of an exciton or being resident. The proximity effect of the exciton electron is smaller due to the binding by Coulomb interaction, which decreases the tunneling to the narrow well. The experimental data are in good agreement with model calculations.

Spin dephasing of electrons and holes in isotopically purified ZnSe/(Zn,Mg)Se quantum wells

The coherent spin dynamics of resident electrons and holes in an isotopically purified ZnSe/(Zn,Mg)Se single quantum well is investigated in different regimes, requiring corresponding adaption of the applied time-resolved pump-probe Kerr rotation technique. The purification of the Zn and Se atom species in the crystal to the isotopes with zero nuclear spin is expected to lead to an extension of the spin dephasing times of resident carriers, due to the suppression of their interaction with the nuclear spins. Indeed, we find no indication of carrier-nuclear interaction in this sample and link the observed carrier spin relaxation to the spin-orbit interaction. Theoretical considerations support the experimental results.

Radiofrequency driving of coherent electron spin dynamics inn-GaAs detected by Faraday rotation

We suggest a new pump-probe method for studying semiconductor spin dynamics based on pumping of carrier spins by a pulse of oscillating radiofrequency (rf) magnetic field and probing by measuring the Faraday rotation of a short laser pulse. We demonstrate this technique on $n$-GaAs and observe the onset and decay of coherent spin precession during and after the course of rf pulse excitation. We show that the rf field resonantly addresses the electron spins with Larmor frequencies close to that of the rf field. This opens the opportunity to determine the homogeneous spin coherence time $T_2$, that is inaccessible directly in standard all-optical pump-probe experiments.

Radical pair intersystem crossing: Quantum dynamics or incoherent kinetics?

Magnetic field effects on radical pair reactions arise due to the interplay of coherent electron spin dynamics and spin relaxation effects, a rigorous treatment of which requires the solution of the Liouville-von Neumann equation. However, it is often found that simple incoherent kinetic models of the radical pair singlet-triplet intersystem crossing provide an acceptable description of experimental measurements. In this paper, we outline the theoretical basis for this incoherent kinetic description, elucidating its connection to exact quantum mechanics. We show, in particular, how the finite lifetime of the radical pair spin states, as well as any additional spin-state dephasing, leads to incoherent intersystem crossing. We arrive at simple expressions for the radical pair spin state interconversion rates to which the functional form proposed recently by Steiner et al. [J. Phys. Chem. C 122, 11701 (2018)] can be regarded as an approximation. We also test the kinetic master equation against exact quantum dynamical simulations for a model radical pair and for a series of PTZ•+-Phn-PDI•- molecular wires.

Nuclear spin dynamics influenced and detected by electron spin polarization in CdTe/(Cd,Mg)Te quantum wells

Nuclear spin coherence and relaxation dynamics of all constituent isotopes of an n-doped CdTe/(Cd,Mg)Te quantum well structure are studied employing optically detected nuclear magnetic resonance. Using time-resolved pump-probe Faraday ellipticity, we generate and detect the coherent spin dynamics of the resident electrons. The photogenerated electron spin polarization is transferred into the nuclear spin system, which becomes polarized and acts back on the electron spins as the Overhauser field. Under the influence of resonant radio frequency pulses, we trace the coherent spin dynamics of the nuclear isotopes $^{111}$Cd, $^{113}$Cd, and $^{125}$Te. We measure nuclear Rabi oscillations, the inhomogeneous dephasing time $T_2^*$, the spin coherence time $T_2$, and the longitudinal relaxation time $T_1$. Furthermore, we investigate the influence of the laser excitation and the corresponding electron spin polarization on the nuclear spin relaxation time and find a weak extension of this time induced by interaction with the electron spins.

Discretization of the total magnetic field by the nuclear spin bath in fluorine-doped ZnSe

The coherent spin dynamics of fluorine donor-bound electrons in ZnSe induced by pulsed optical excitation is studied in a perpendicular applied magnetic field. The Larmor precession frequency serves as a measure for the total magnetic field exerted onto the electron spins and, surprisingly, does not increase linearly with the applied field, but shows a step-like behavior with pronounced plateaus, given by multiples of the laser repetition rate. This discretization occurs by a feedback mechanism in which the electron spins polarize the nuclear spins, which in turn generate a local Overhauser field adjusting the total magnetic field accordingly. Varying the optical excitation power, we can control the plateaus, in agreement with our theoretical model. From this model, we trace the observed discretization to the optically induced Stark field, which causes the dynamic nuclear polarization.

Photocharging Dynamics in Colloidal CdS Quantum Dots Visualized by Electron Spin Coherence

We use a time-resolved technique with three laser pulses (pump, orientation and probe) to study the photocharging dynamics with picosecond resolution on a long timescale ranging from ps to ms in CdS colloidal quantum dots. The detection is based on measuring the coherent spin dynamics of electrons, allowing us to distinguish the type of carrier in the dot core (electron or hole). We find that although initially negative photocharging happens because of fast hole trapping on surface states, eventually it evolves to positive photocharging due to electron trapping and hole detrapping. The positive photocharging lasts up to hundreds of microseconds at room temperature.

Photocharging dynamics in colloidal CdS quantum dots visualized by electron spin coherence

AbstractWe use a time-resolved technique with three laser pulses (pump, orientation and probe) to study the photocharging dynamics with picosecond resolution on a long timescale ranging from ps to ms in CdS colloidal quantum dots. The detection is based on measuring the coherent spin dynamics of electrons, allowing us to distinguish the type of carrier in the dot core (electron or hole). We find that although initially negative photocharging happens because of fast hole trapping on surface states, eventually it evolves to positive photocharging due to electron trapping and hole detrapping. The positive photocharging lasts up to hundreds of microseconds at room temperature.

Dynamic Evolution from Negative to Positive Photocharging in Colloidal CdS Quantum Dots.

The optical properties of colloidal semiconductor nanocrystals are largely influenced by the trapping of charge carriers on the nanocrystal surface. Different concentrations of electron and hole traps and different rates of their capture to the traps provide dynamical charging of otherwise neutral nanocrystals. We study the photocharging formation and evolution dynamics in CdS colloidal quantum dots with native oleic acid surface ligands. A time-resolved technique with three laser pulses (pump, orientation, and probe) is developed to monitor the photocharging dynamics with picosecond resolution on wide time scales ranging from picoseconds to milliseconds. The detection is based on measuring the coherent spin dynamics of electrons, allowing us to distinguish the type of carrier in the QD core (electron or hole). We find that although initially negative photocharging happens because of fast hole trapping, it eventually evolves to positive photocharging due to electron trapping and hole detrapping. The positive photocharging lasts up to hundreds of microseconds at room temperature. These findings give insight into the photocharging process and provide valuable information for understanding the mechanisms responsible for the emission blinking in colloidal nanostructures.

The Quantum Biology of Reactive Oxygen Species Partitioning Impacts Cellular Bioenergetics.

Quantum biology is the study of quantum effects on biochemical mechanisms and biological function. We show that the biological production of reactive oxygen species (ROS) in live cells can be influenced by coherent electron spin dynamics, providing a new example of quantum biology in cellular regulation. ROS partitioning appears to be mediated during the activation of molecular oxygen (O2) by reduced flavoenzymes, forming spin-correlated radical pairs (RPs). We find that oscillating magnetic fields at Zeeman resonance alter relative yields of cellular superoxide (O2•−) and hydrogen peroxide (H2O2) ROS products, indicating coherent singlet-triplet mixing at the point of ROS formation. Furthermore, the orientation-dependence of magnetic stimulation, which leads to specific changes in ROS levels, increases either mitochondrial respiration and glycolysis rates. Our results reveal quantum effects in live cell cultures that bridge atomic and cellular levels by connecting ROS partitioning to cellular bioenergetics.

Characterization of spin-orbit fields in InGaAs quantum wells

Coherent electron spin dynamics in 10-nm-wide InGaAs/InAlAs quantum wells is studied from 10 K to room temperature using time-resolved Kerr rotation. The spin lifetime exceeds 1 ns at 10 K and decreases with temperature. By varying the spatial overlap between pump and probe pulses, a diffusive velocity is imprinted on the measured electron spins and a spin precession in the spin-orbit field is measured. A Rashba symmetry of the spin-orbit interaction is determined. By comparing the spatial precession frequency gradient with the spin decay rate, an upper limit for the Rashba coefficients α of 2 × 10−12 eVm is estimated.

Determination ofs-dexchange coupling in GaMnN by time-resolved Kerr rotation spectroscopy

Coherent electron-spin dynamics in ${\text{Ga}}_{1\ensuremath{-}x}{\text{Mn}}_{x}\text{N}$ has been investigated by time-resolved Kerr rotation spectroscopy. The effective electron $g$ factor shows a linear increase with the Mn concentration due to the s-d exchange coupling between the conduction electrons and the $d$-shell electrons of ${\mathrm{Mn}}^{3+}$ impurities. The magnitude and sign of the s-d exchange constant are determined precisely to be ${N}_{0}\ensuremath{\alpha}=+0.23\ifmmode\pm\else\textpm\fi{}0.02\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$, indicative of a ferromagnetic s-d exchange coupling in GaMnN. The determined ${N}_{0}\ensuremath{\alpha}$ is consistent with the typical value found in most diluted magnetic semiconductors and reveals that GaMnN is indeed not an exception.

Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions.

We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene triad containing considerably more nuclear spins which has recently been used to establish a "proof of principle" for the operation of a chemical compass [K. Maeda, K. B. Henbest, F. Cintolesi, I. Kuprov, C. T. Rodgers, P. A. Liddell, D. Gust, C. R. Timmel, and P. J. Hore, Nature (London) 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C(·+)PF(·-) radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical.