Electron Spin Relaxation Rate Research Articles

Electron Spin Relaxation Rates of Radicals in Irradiated Boron Oxides

Electron Spin Relaxation Rates of Radicals in Irradiated Boron Oxides

Fast electron and slow hole spin relaxation in CsPbI3 nanocrystals

Spin-dependent properties of lead halide perovskites (LHPs) have recently gained significant attention paving their way toward spin-optoelectronic applications. However, separate measurements of the electron and hole spin relaxation rates are so far missing in LHPs. The knowledge of the electron and hole spin relaxation timescales is necessary to understand the spin-dependent properties of LHPs. Here, we report on the spin polarization dynamics in CsPbI3 nanocrystals (NCs). We employ polarization dependent ultrafast differential transmission spectroscopy (DTS) at room temperature to study the spin polarization dynamics in this system. In the case of pure CsPbI3 NCs, it is not possible to measure separately electron and hole spin relaxation rates from the polarization dependent DTS. Here, we introduce the soluble fullerene derivative PC60BM as an electron acceptor along with CsPbI3 to create an imbalance between the photoexcited electrons and holes in the NCs and, thus, affecting their spin-dependent carrier distribution. CsPbI3:PC60BM blend sample shows a distinct difference in the spin dependent kinetics of the DTS spectra as compared to the NCs-only sample. With the help of a kinetic model for the spin-dependent charge carrier distributions, we separately determine the electron and hole spin relaxation times in CsPbI3 NCs. We find that the room temperature hole spin lifetime (τh ∼ 5 ps) is ∼13 times longer than the electron spin lifetime (τe ∼ 0.4 ps). We ascribe the fast electron spin relaxation to the presence of strong spin–orbit coupling in the conduction band, which is ineffective for holes in the s-type valence band.

Analysis on the effect of electron spin polarization on a hybrid optically pumped K-Rb-21Ne co-magnetometer.

In this paper, the effect of longitudinal electron spin polarization under the combined action of alkali metal density ratio and pump laser power density on the hybrid optically pumped co-magnetometer operated in the spin-exchange relaxation-free (SERF) regime is studied. The AC response model of rotation velocity and magnetic noise of the SERF co-magnetometer system is proposed, and the factors of frequency and system bandwidth are considered. Based on the proposed response model, the error equation of the system is obtained, and the relationship between alkali metal density ratio and pump laser power density and the system noise response is theoretically analyzed and experimentally tested. The results show that when the product of pumping rate and alkali metal density ratio is greater than the electron spin relaxation rate, there is a longitudinal electron spin polarization point that minimizes the system error. In addition, the range of minimum error calculated results obtained by changing the pumping rate for the cells with different alkali metal density ratios is within 5% of the average value, that is, their minimum error potential is roughly the same within a certain range. Under the experimental conditions in this paper, due to the limitation of the electron spin relaxation rate and the operating capacity of the pump laser, the optimal alkali metal density ratio range is about 1/100-1/300.

Temperature-dependent electron spin relaxation at the metal-to-insulator transition in n -type GaAs

We present a detailed study of the temperature-dependent electron spin relaxation rate in $n$-type bulk GaAs in the regime of the metal-to-insulator transition at vanishing magnetic fields. The high-accuracy measurements reveal the longest spin relaxation time for a doping concentration slightly below the metal-to-insulator transition at a finite temperature of $\ensuremath{\sim}7\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. This global minimum of the electron spin relaxation rate results from a delicate interplay of hyperfine interaction, variable range hopping, and the Dyakonov-Perel mechanism. At higher doping densities, the Dyakonov-Perel mechanism becomes dominant at all temperatures changing with temperature gradually from the degenerate to the nondegenerate regime. A theoretical model including temperature-dependent transport data yields not only quantitative agreement with the experimental data but reveals additionally the gradual change from percolation-based large angle momentum scattering to ionized impurity small angle scattering. A simple interpolation of all available data allows to extract a maximal-possible spin relaxation time in $n$-doped, bulk GaAs for negligible external magnetic fields of $\ensuremath{\approx}1\phantom{\rule{0.16em}{0ex}}\mathrm{\ensuremath{\mu}}\mathrm{s}$.

Electron Spin Relaxation in Carbon Materials.

This article focuses on EPR relaxation measurements in various carbon samples, e.g., natural carbons—anthracite, coal, higher anthraxolites, graphite; synthetically obtained carbons—glassy carbons, fullerenes, graphene, graphene oxide, reduced graphene oxide, graphite monocrystals, HOPG, nanoribbons, diamonds. The short introduction presents the basics of resonant electron spin relaxation techniques, briefly describing the obtained parameters. This review presents gathered results showing the processes leading to electron spin relaxation and typical ranges of electron spin relaxation rates for many different carbon types.

Fast extraction of the electron spin-relaxation rate in the SERF magnetometer from a transient response.

The magnitude of the electron spin-relaxation rate Rrel of the atomic ensemble directly affects the sensitivity of the spin-exchange relaxation-free (SERF) atomic magnetometer (AM). The rapid and in-situ characterization of Rrel is of great importance. In this work, a fast extraction method of Rrel is proposed with a measurement period shorten to 0.5 s, merely detecting the transient response of SERF AM to a transverse DC excitation magnetic field after switching off the pump beam. In contrast to the conventional methods based on the measurement of the magnetic resonance linewidth, this method circumvents the involvement of optical pumping rate, and enables monitoring Rrel under arbitrary polarization, which is expected to improve the authenticity of Rrel measurement in a more convenient way.

In-Situ Measurement of the Density Ratio of the K-Rb-21Ne Comagnetometer Based on Electron Spin Relaxation Rate

Accurate measurement of alkali metal density ratio in hybrid vapor cells is essential for high sensitivity of comagnetometers. We introduce and investigate a new method of measuring the density ratio based on electron spin-relaxation rate. The Bloch equations including the parameter of density ratio are studied, and the density measurement results show that measurement uncertainty is less than 12%. The advantage of this method is measuring the in-situ density ratio, which is more precise and useful for optimizing sensitivity of comagnetometers by adjusting the density ratio in real time.

Quantum polyspectra for modeling and evaluating quantum transport measurements: A unifying approach to the strong and weak measurement regime

Quantum polyspectra of up to fourth order are introduced for modeling and evaluating quantum transport measurements offering a powerful alternative to methods of the traditional full counting statistics. Experimental time traces of the occupation dynamics of a single quantum dot are evaluated via simultaneously fitting their second-, third-, and fourth-order spectra. The scheme recovers the same electron tunneling and spin relaxation rates as previously obtained from an analysis of the same data in terms of factorial cumulants of the full counting statistics and waiting-time distributions. Moreover, the evaluation of time traces via quantum polyspectra is demonstrated to be feasible also in the weak measurement regime even when quantum jumps can no longer be identified from time traces and methods related to the full counting statistics cease to be applicable. A numerical study of a double dot system shows strongly changing features in the quantum polyspectra for the transition from the weak measurement regime to the Zeno regime where coherent tunneling dynamics is suppressed. Quantum polyspectra thus constitute a general unifying approach to the strong and weak regime of quantum measurements with possible applications in diverse fields as nanoelectronics, circuit quantum electrodynamics, spin noise spectroscopy, or quantum optics.

Giant Anisotropy of Spin Relaxation and Spin-Valley Mixing in a Silicon Quantum Dot.

In silicon quantum dots (QDs), at a certain magnetic field commonly referred to as the "hot spot," the electron spin relaxation rate (T_{1}^{-1}) can be drastically enhanced due to strong spin-valley mixing. Here, we experimentally find that with a valley splitting of 78.2±1.6 μeV, this hot spot in spin relaxation can be suppressed by more than 2 orders of magnitude when the in-plane magnetic field is oriented at an optimal angle, about 9° from the [100] sample plane. This directional anisotropy exhibits a sinusoidal modulation with a 180° periodicity. We explain the magnitude and phase of this modulation using a model that accounts for both spin-valley mixing and intravalley spin-orbit mixing. The generality of this phenomenon is also confirmed by tuning the electric field and the valley splitting up to 268.5±0.7 μeV.

Spatiotemporal Spin Noise Spectroscopy.

We report on the potential of a new spin noise spectroscopy approach by demonstrating all-optical probing of spatiotemporal spin fluctuations. This is achieved by homodyne mixing of a spatially phase-modulated local oscillator with spin-flip scattered light, from which the frequency and wave vector dependence of the spin noise power is unveiled. As a first application of the method we measure the spatiotemporal spin noise in weakly n-doped CdTe layers, from which the electron spin diffusion constant and spin relaxation rates are determined. The absence of spatial spin correlations is also shown for this particular system.

Electron spin relaxation of single phosphorus donors in metal-oxide-semiconductor nanoscale devices

We analyze the electron spin relaxation rate $1/T_1$ of individual ion-implanted $^{31}$P donors, in a large set of metal-oxide-semiconductor (MOS) silicon nanoscale devices, with the aim of identifying spin relaxation mechanisms peculiar to the environment of the spins. The measurements are conducted at low temperatures ($T\approx 100$~mK), as a function of external magnetic field $B_0$ and donor electrochemical potential $\mu_{\rm D}$. We observe a magnetic field dependence of the form $1/T_1\propto B_0^5$ for $B_0\gtrsim 3\,$ T, corresponding to the phonon-induced relaxation typical of donors in the bulk. However, the relaxation rate varies by up to two orders of magnitude between different devices. We attribute these differences to variations in lattice strain at the location of the donor. For $B_0\lesssim 3\,$T, the relaxation rate changes to $1/T_1\propto B_0$ for two devices. This is consistent with relaxation induced by evanescent-wave Johnson noise created by the metal structures fabricated above the donors. At such low fields, where $T_1>1\,$s, we also observe and quantify the spurious increase of $1/T_1$ when the electrochemical potential of the spin excited state $|\uparrow\rangle$ comes in proximity to empty states in the charge reservoir, leading to spin-dependent tunneling that resets the spin to $|\downarrow\rangle$. These results give precious insights into the microscopic phenomena that affect spin relaxation in MOS nanoscale devices, and provide strategies for engineering spin qubits with improved spin lifetimes.

Electron paramagnetic resonance of a 10B-containing heterocyclic radical

Electron paramagnetic resonance measurements for a 10B-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), were made at X-band in 9:1 toluene:dichloromethane from 10 to 293 K and in toluene from 180 to 293 K. In well-deoxygenated 0.1 mM toluene solution at room temperature hyperfine couplings to 10B, four pairs of protons and five pairs of fluorines contribute to a continuous wave spectrum with many resolved lines. Hyperfine couplings were adjusted to provide the best fit for spectra of the radical enriched in 10B and the analogous radical synthesized with 10,11B in natural abundance, resulting in small refinements of the hyperfine coupling constants previously reported for the natural abundance sample. Electron spin relaxation rates at temperatures between 15 and 293 K were similar for samples containing 10B and natural isotope abundance. Analysis of electron spin echo envelope modulation and hyperfine correlation spectroscopy data at 80 K found Axx = −7.5 ± 0.3, Ayy = −8.5 ± 0.3, and Azz = −10.8 ± 0.3 MHz for 11B, which indicates small spin density on the boron. The spin echo and hyperfine spectroscopy data for the 10B –containing radical are consistent with the factor of 2.99 smaller hyperfine values for 10B than for 11B.

Increased sensitivity of spin noise spectroscopy using homodyne detection in n -doped GaAs

We implement the homodyne detection scheme for an increase of the polarimetric sensitivity in spin noise spectroscopy. Controlling the laser intensity of the local oscillator, which is guided around the sample and does not perturb the measured spin system, we are able to improve the signal-to-noise ratio. The opportunity of additional amplification of the measured signal strength allows us to reduce the probe laser intensity incident onto the sample and therefore to approach the non-perturbative regime. The efficiency of this scheme with signal enhancement by more than a factor of 3 at low probe powers is demonstrated on bulk $n$-doped GaAs where the reduced electron-spin relaxation rate is shown experimentally. Additionally, the control of the optical phase provides us with the possibility to switch between the measurement of Faraday rotation and ellipticity without changes in the optical setup.

Radical addition to ruthenocene at low temperatures: characterization of ruthenocenyl radicals byμSR spectroscopy

The radicals formed by muonium (Mu) addition to ruthenocene at low temperature (4–200 K) have been characterized by transverse field muon spin rotation (TF-μSR) and avoided level crossing muon spin resonance (ALC-μSR) spectroscopy. The structures of the muoniated radicals have been identified by comparing the experimentally measured muon hyperfine coupling constants with values obtained from DFT calculations (UB3LYP/DGDZVP). Mu addition was observed at the ruthenium and at the cyclopentadiene (Cp) rings, both from the exterior and interior directions. Closer agreement between the DFT calculations and the experimental values are obtained if it is assumed the structures of the Mu adducts of the Cp rings are distorted due to interactions with neighbouring molecules. Changes in the ALC-μSR spectra with temperature indicated that the electron spin relaxation rate of the Cp adducts increases with temperature; however, the specific spin relaxation mechanism is unknown.

Carrier spin relaxation in diluted magnetic quantum wells: Effect of Mn spin correlations

We demonstrate theoretically that the presence of holes, either resident or photocreated, in diluted magnetic quantum wells accelerates the spin relaxation of electrons via a mechanismwhich has been previously overlooked. This effect is due to the spin correlations, which establish between magnetic ions coupled via hole-mediated Ruderman-Kittel-Kasuya-Yoshida interactions in the paramagnetic phase. As a consequence, the electron spin relaxation becomes temperature and hole density dependent, in contrast to existing theories. Our theory qualitatively reproduces the increase of the electron spin relaxation rate with pump power observed in n-doped CdMnTe magnetic quantum wells [Ben Cheikh et al., Phys. Rev. B 88, 201306 (2013)]. It also predicts a decrease of the spin relaxation rate with temperature, as observed, although not in the same temperature range.

ν=2/3 fractional quantum Hall state in an AlAs quantum well probed by electron spin resonance

The electron spin resonance (ESR) of two-dimensional electrons confined in a high-quality, 16-nm AlAs quantum well was investigated near the filling factor $\ensuremath{\nu}=2/3$ of the fractional quantum Hall effect (FQHE). The spin resonance was robust in the vicinity of the fractional filling $\ensuremath{\nu}=2/3$, indicating that the $\ensuremath{\nu}=2/3$ state is at least partially spin polarized. The formation of the $2/3$ FQHE state did not result in any modifications of the ESR linewidth and, hence, of the electron spin relaxation rate. Yet the nuclear spin-lattice relaxation rate extracted from the time decay of the ESR Overhauser shift demonstrated a strong nonmonotonic dependence on the electron filling factor with a minimum near $\ensuremath{\nu}=2/3$. This observation suggests the enhancement of the energy gap in the spin excitation spectrum of two-dimensional electrons at the $\ensuremath{\nu}=2/3$ state.

Rapid-scan EPR imaging

In rapid-scan EPR the magnetic field or frequency is repeatedly scanned through the spectrum at rates that are much faster than in conventional continuous wave EPR. The signal is directly-detected with a mixer at the source frequency. Rapid-scan EPR is particularly advantageous when the scan rate through resonance is fast relative to electron spin relaxation rates. In such scans, there may be oscillations on the trailing edge of the spectrum. These oscillations can be removed by mathematical deconvolution to recover the slow-scan absorption spectrum. In cases of inhomogeneous broadening, the oscillations may interfere destructively to the extent that they are not visible. The deconvolution can be used even when it is not required, so spectra can be obtained in which some portions of the spectrum are in the rapid-scan regime and some are not. The technology developed for rapid-scan EPR can be applied generally so long as spectra are obtained in the linear response region. The detection of the full spectrum in each scan, the ability to use higher microwave power without saturation, and the noise filtering inherent in coherent averaging results in substantial improvement in signal-to-noise relative to conventional continuous wave spectroscopy, which is particularly advantageous for low-frequency EPR imaging. This overview describes the principles of rapid-scan EPR and the hardware used to generate the spectra. Examples are provided of its application to imaging of nitroxide radicals, diradicals, and spin-trapped radicals at a Larmor frequency of ca. 250MHz.

Synthesis and Electron Spin Relaxation of Tetracarboxylate Pyrroline Nitroxides

We report the design, synthesis, and electron spin relaxation properties of hydrophilic tetracarboxylate ester pyrroline nitroxides 1 and 2, which serve as models in the search for new spin labels for DEER distance measurement at room temperature. The nitroxides are designed to have the methyl groups further away from the N–O spin site to decrease the inequivalent couplings of the unpaired electron to the methyl protons that shorten Tm at T > 70 K in currently used labels. The key step in the synthesis of 1 and 2 is the reaction of the dianion of pyrrole-1,2,5-tricarboxylic acid tert-butyl ester dimethyl ester with electrophiles such as methyl chloroformate and methyl bromoacetate. Structures of 1 and 2 are confirmed by X-ray crystallography. Studies of electron spin relaxation rates in rigid trehalose/sucrose matrices reveal approximately temperature independent values of 1/Tm for 1 and 2 up to about 160 K and modest temperature dependence up to 295 K, demonstrating that increasing the distance between the nitroxide moiety and methyl groups is effective in lengthening Tm at T > 70 K.

Triarylmethyl Radical: EPR Signal to Noise at Frequencies between 250 MHz and 1.5 GHz and Dependence of Relaxation on Radical and Salt Concentration and on Frequency.

In vivo oximetry by pulsed electron paramagnetic resonance is based on measurements of changes in electron spin relaxation rates of probe molecules, such as the triarylmethyl radicals. A series of experiments was performed at frequencies between 250 MHz and 1.5 GHz to assist in the selection of an optimum frequency for oximetry. Electron spin relaxation rates for the triarylmethyl radical OX063 as a function of radical concentration, salt concentration, and resonance frequency were measured by electron spin echo 2-pulse decay and 3-pulse inversion recovery in the frequency range of 250 MHz-1.5 GHz. At constant OX063 concentration, 1/T1 decreases with increasing frequency because the tumbling dependent processes that dominate relaxation at 250 MHz are less effective at higher frequency. 1/T2 also decreases with increasing frequency because 1/T1 is a significant contribution to 1/T2 for trityl radicals in fluid solution. 1/T2-1/T1, the incomplete motional averaging contribution to 1/T2, increases with increasing frequency. At constant frequency, relaxation rates increase with increasing radical concentration due to contributions from collisions that are more effective for 1/T2 than 1/T1. The collisional contribution to relaxation increases as the concentration of counter-ions in solution increases, which is attributed to interactions of cations with the negatively charged radicals that decrease repulsion between trityl radicals. The Signal-to-Noise ratio (S/N) of field-swept echo-detected spectra of OX063 were measured in the frequency range of 400 MHz-1 GHz. S/N values, normalized by √Q, increase as frequency increases. Adding salt to the radical solution decreased S/N because salt lowers the resonator Q. Changing the temperature from 19 to 37 °C caused little change in S/N at 700 MHz. Both slower relaxation rates and higher S/N at higher frequencies are advantageous for oximetry. The potential disadvantage of higher frequencies is the decreased depth of penetration into tissue.

The tetrahydrobiopterin radical interacting with high- and low-spin heme in neuronal nitric oxide synthase – A new indicator of the extent of NOS coupling

Reaction intermediates trapped during the single-turnover reaction of the neuronal ferrous nitric oxide synthase oxygenase domain (Fe(II)nNOSOX) show four EPR spectra of free radicals. Fully-coupled nNOSOX with cofactor (tetrahydrobiopterin, BH4) and substrate (l-arginine) forms the typical BH4 cation radical with an EPR spectrum ~4.0mT wide and hyperfine tensors similar to reports for a biopterin cation radical in inducible NOSOX (iNOSOX). With excess thiol, nNOSox lacking BH4 and l-arg is known to produce superoxide. In contrast, we find that nNOSOX with BH4 but no l-arg forms two radicals with rather different, fast (~250μs at 5K) and slower (~500μs at 20K), electron spin relaxation rates and a combined ~7.0mT wide EPR spectrum. Rapid freeze-quench CW- and pulsed-EPR measurements are used to identify these radicals and their origin. These two species are the same radical with identical nuclear hyperfine couplings, but with spin-spin couplings to high-spin (4.0mT component) or low-spin (7.0mT component) Fe(III) heme. Uncoupled reactions of nNOS leave the enzyme in states that can be chemically reduced to sustain unregulated production of NO and reactive oxygen species in ischemia-reperfusion injury. The broad EPR signal is a convenient indicator of uncoupled nNOS reactions producing low-spin Fe(III) heme.