Mechanism Of Electron Spin Relaxation Research Articles

Comparison of spin photocurrent in devices based on in-plane or out-of-plane magnetized CoFeB spin detectors

We have measured a helicity-dependent photocurrent at zero external magnetic field in a device based on a semiconductor quantum well embedded in a p-i-n junction. The device is excited under vertical incidence with circularly polarized light. The spin filtering effect is evidenced in the temperature range 77--300 K owing to a CoFeB/MgO spin filter with out-of-plane magnetization in remanence. The helicity-dependent photocurrent is explored as a function of the temperature and bias. These characteristics are compared with those of a spin photocurrent device with in-plane magnetized CoFeB/MgO spin filter, excited under oblique incidence with circularly polarized light. In contrast to the in-plane spin filter device, the circularly polarized light asymmetry of the photocurrent in the out-of-plane device depends weakly on the external bias. The two devices are sensitive to the spin filtering of either the in-plane $({S}_{x})$ or out-of-plane $({S}_{z})$ photogenerated electron spin in the semiconductor quantum well. The helicity-dependent photocurrent results can be explained by the Dyakonov-Perel electron spin-relaxation mechanism. Our study reveals the giant spin relaxation anisotropy in III-V zinc-blende quantum wells in the presence of a vertical electric field.

Electron spin relaxation of C60 monoanion in liquid solution: applicability of Kivelson-Orbach mechanism.

We report the results of our investigation on the electron spin relaxation mechanism of the monoanion of C60 fullerene in liquid solution. The solvent chosen was carbon disulfide, which is rather uncommon in EPR spectroscopy but proved very useful here because of its liquid state over a wide temperature range. The conditions for exclusive formation of the monoanion of C60 in CS2 were first determined using electrochemical measurements. Using these results, only the monoanion of C60 was prepared by chemical reduction using Hg2I2/Hg as the reducing agent. The EPR line width was measured over a wide temperature range of 120-290 K. The line widths show weak dependence on temperature, changing by a factor of only about 2, over this temperature range. We show that the observed temperature dependence does not obey the Kivelson-Orbach mechanism of electron spin relaxation in liquids, applicable for radicals with low-lying, thermally accessible excited electronic states. The observed temperature dependence can be empirically fitted to an Arrhenius type of exponential function, from which an activation energy of 74 ± 3 cm(-1) is obtained. From the qualitative similarities in the characteristics of the spin relaxation rates of C60 monoanion radical and the cyclohexane type of cation radicals reported in the literature, we propose that a pseudorotation-induced electron spin relaxation process could be operating in the C60 monoanion radical in liquid solution. The low activation energy of 74 cm(-1) observed here is consistent with the pseudorotation barrier of C60 monoanion, estimated from reported Jahn-Teller energy levels.

Saturation recovery electron spin–lattice relaxation studies on benzene anion radical and its derivatives: application of Kivelson–Orbach mechanism of electron spin relaxation

The role of low-lying excited states on the spin–lattice relaxation times (T1) of organic radicals has been investigated. To test the applicability of Kivelson's electric field fluctuation model (D. Kivelson, J. Chem. Phys. 45, 1324 (1966)), based on the Orbach mechanism of spin relaxation, the T1s of the anion radicals of benzene, benzene-1-d, toluene, ethyl benzene, isopropyl benzene, t-butyl benzene, p-xylene, 1,2,4-trimethyl benzene and 1,3,5-trimethyl benzene in liquid solutions, with potassium cation as the counter ion, have been measured by the pulse saturation recovery technique. The energy gap between the ground and the first excited electronic states changed with the substitutions to different extent. The spin–lattice relaxation rates showed correlation with this energy gap. Anion radicals of benzene and benzene-1-d showed the shortest T1 among the radicals studied here. A small but measurable energy splitting due to the deuterium substitution in benzene-1-d radical was obtained from the temperature dependence of T1. Spin–lattice relaxation times of benzene anion measured here decreased monotonically in the range of −60 to −125 °C, in contrast to some reported claims of very unusual temperature dependence, based on the continuous wave microwave power saturation studies. Our results also showed that the ion pairing between benzene anion and potassium cation did not significantly influence the spin–lattice relaxation times.

Electron tunneling in lithium-ammonia solutions probed by frequency-dependent electron spin relaxation studies.

Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T(1)) and spin-spin (T(2)) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multiexponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1-10) × 10(-12) s over a temperature range 230-290 K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a time scale of ∼10(-13) s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multifrequency EPR measurements to interrogate the microscopic nature and dynamics of ultrafast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer.

Spin-polarized multiexcitons in quantum dots in the presence of spin-orbit interaction

An efficient electron spin-relaxation mechanism has been observed in InAs quantum dots (QDs) that manifests itself as a sharp drop in the circular polarization of the light emitted by Fe spin-light emitting diodes, which incorporate a single layer of InGaAs QDs, for a narrow range of magnetic fields around 5 T. The underlying mechanism occurs when the QDs are occupied by three-electron-hole pairs forming a tri-exciton (3X) and is a two-step process. The first step involves the spin flip of one of the three electrons mediated by the spin-orbit interaction; in the second step the 3X relaxes to its ground state via phonon emission.

Magnetic Field and Temperature Dependencies Shed Light on the Recombination Kinetics of a Transition Metal Donor/Acceptor System

The radical pair recombination of an intramolecular electron-transfer system containing a transition metal moiety has been addressed by femtosecond spectroscopy. The radical pair is formed by ultrafast electron transfer (90 fs) from a ferrocene residue to a photoexcited Nile blue moiety. Its recombination proceeds on the picosecond time scale in a multiexponential fashion. The kinetic pattern is a manifestation of spin processes competing with electron transfer. Magnetic field effects on these kinetics allow one to disentangle the two contributions. Their temperature dependencies yield the activation parameters of the two processes. The discussion focuses on the mechanism of electron spin relaxation. Strong evidence for the Orbach/Kivelson mechanism will be given.

Direct Observation of the Electron Spin Relaxation Induced by Nuclei in Quantum Dots

We have studied the electron spin relaxation in semiconductor InAs/GaAs quantum dots by time-resolved optical spectroscopy. The average spin polarization of the electrons in an ensemble of p-doped quantum dots decays down to 1/3 of its initial value with a characteristic time T(Delta) approximately 500 ps, which is attributed to the hyperfine interaction with randomly oriented nuclear spins. We show that this efficient electron spin relaxation mechanism can be suppressed by an external magnetic field as small as 100 mT.

Electron spin relaxation due to reorientation of a permanent zero field splitting tensor.

Electron spin relaxation of transition metal ions with spin S> or =1 results primarily from thermal modulation of the zero field splitting (zfs) tensor. This occurs both by distortion of the zfs tensor due to intermolecular collisions and, for complexes with less than cubic symmetry, by reorientational modulation of the permanent zfs tensor. The reorientational mechanism is much less well characterized in previous work than the distortional mechanism although it is an important determinant of nuclear magnetic resonance (NMR) paramagnetic relaxation enhancement phenomena (i.e., the enhancement of NMR relaxation rates produced by paramagnetic ions in solution or NMR-PRE). The classical density matrix theory of spin relaxation does not provide an appropriate description of the reorientational mechanism at low Zeeman field strengths because the zero-order spin wave functions are stochastic functions of time. Using spin dynamics simulation techniques, the time correlation functions of the spin operators have been computed and used to determine decay times for the reorientational relaxation mechanism for S=1. In the zfs limit of laboratory field strengths (H(Zeem)<<H(zfs) (composite function)), when the zfs tensor is cylindrical, the spin decay is exponential, the spin relaxation time, tau(S) (composite function) approximately 0.53tau(R)((1)), where tau(R)((1)) is the reorientational correlation time of a molecule-fixed vector. The value of tau(S) (composite function) is independent of the magnitude of the cylindrical zfs parameter (D), but it depends strongly on low symmetry zfs terms (the E/D ratio). Other spin dynamics (SD) simulations examined spin decay in the intermediate regime of field strengths where H(Zeem) approximately H(zfs) (composite function), and in the vicinity of the Zeeman limit. The results demonstrate that the reorientational electron spin relaxation mechanism is often significant when H(zfs) (composite function)> or =H(Zeem), and that its neglect can lead to serious errors in the interpretation of NMR-PRE data.

Ultrafast spin evolution in high-mobility 2DEGs

We describe optical measurements of electron spin dynamics in a high-mobility n-doped GaAs/AlGaAs quantum well which test the customary assumptions of the D'yakonov, Perel’ and Kachorovskii mechanism of electron spin relaxation. At 1.8 K , spin evolution is oscillatory indicating breakdown of collision-dominated relaxation. At higher temperatures spin evolution is exponential but extracted scattering times deviate strongly from transport momentum relaxation times. This discrepancy can be ascribed to electron–electron scattering previously overlooked as a contributor to spin relaxation.

Electron spin relaxation by nuclei in semiconductor quantum dots

We have studied theoretically the electron spin relaxation in semiconductor quantum dots via interaction with nuclear spins. The relaxation is shown to be determined by three processes: (i) -- the precession of the electron spin in the hyperfine field of the frozen fluctuation of the nuclear spins; (ii) -- the precession of the nuclear spins in the hyperfine field of the electron; and (iii) -- the precession of the nuclear spin in the dipole field of its nuclear neighbors. In external magnetic fields the relaxation of electron spins directed along the magnetic field is suppressed. Electron spins directed transverse to the magnetic field relax completely in a time on the order of the precession period of its spin in the field of the frozen fluctuation of the nuclear spins. Comparison with experiment shows that the hyperfine interaction with nuclei may be the dominant mechanism of electron spin relaxation in quantum dots.

Spin relaxation inGaAs/AlxGa1−xAsquantum wells

Spin dynamics of photoexcited carriers in ${\mathrm{G}\mathrm{a}\mathrm{A}\mathrm{s}/\mathrm{A}\mathrm{l}}_{x}{\mathrm{Ga}}_{1\ensuremath{-}x}\mathrm{As}$ quantum wells have been investigated in a wafer containing twelve different single quantum wells, allowing full investigation of well-width and temperature dependences with minimal accidental variations due to growth conditions. The behavior at low temperatures is dominated by excitonic effects, confirming results described in detail by others. Between 50 and 90 K there is a transition from excitonic to free-carrier-dominated behavior; both the temperature and time scale of the transition are in excellent agreement with a theoretical model for exciton dissociation. Above 90 K we find two-component spin decays consisting of an unresolved component (faster than 2 ps) associated with exciton dissociation and hole spin-relaxation and a longer-lived component that yields the electron spin-relaxation time. In the free-carrier regime, the electron spin-relaxation rate in wide wells follows that for bulk GaAs, which varies approximately as ${T}^{2}.$ For narrow wells the rate is approximately independent of temperature and varies quadratically with confinement energy. This behavior is consistent with dominance of the D'yakonov-Perel mechanism of electron-spin relaxation and the expected behavior of the electron mobility. The data show evidence of the influence of electron scattering by interface roughness.

Effects of heavy p doping on the polarized emission spectra and low-temperature luminescence spectra of GaAs/GaAsP strained-layer structures

The optical orientation of electron spins in heavily doped, strained GaAs/GaAsP layers with a deformation-split valence band is studied experimentally. The observed polarized luminescence spectra and polarized photoemission (electron emission) spectra are shown to be described well by a model which allows for smearing of the edges of the bands by the fluctuation potential due to impurities, degeneracy of the carriers at low temperatures, and indirect electron-phonon optical transitions. The dominant mechanism of electron spin relaxation in strained layers is found to be the Bir-Aronov-Pikus mechanism. The parameters of the fluctuation potential and the parameters governing carrier spin relaxation are determined.

Comparative analysis of pulsed electron spin resonance spectrometers at X-band and S-band

Comparative analysis of pulsed electron spin resonance spectroscopy at X-band and at S-band indicates that despite the lower sensitivity at the lower frequency, electron spin echo spectroscopy at S-band provides valuable information on the electron-nuclear interactions in systems where the electron spin echo modulation is too small to study well at X-band. It is shown that independent experimental data on electron spin echo modulation and decay at both X-band and S-band put additional constraints on the structural parameters obtained by comparison of experimental and simulated nuclear modulation patterns, and can also help to elucidate the electron spin relaxation mechanism.

Physicochemical characterization of the four-iron-four-sulphide ferredoxin from Bacillus stearothermophilus

1. A stable ferredoxin was prepared from Bacillus stearothermophilus and purified by chromatography on DEAE-cellulose and by electrophoresis. 2. The minimum molecular weight determined from the amino acid composition was about 7900 and this was in reasonable agreement with a value of 8500 determined by polyacrylamide-gel electrophoresis. The ferredoxin contained four iron atoms and four labile sulphide groups per molecule. 3. The optical absorption, optical-rotatory-dispersion and circular-dichroism spectra are typical of ferredoxins containing 4Fe-4S clusters. 4. Oxidation-reduction titrations, combined with electron-paramagnetic-resonance (e.p.r.) spectroscopy, showed that the protein has a mid-point potential, at pH8, of -280 +/- 10mV, and that only one electron-accepting paramagnetic species is present. 5. The e.p.r. spectrum of the reduced ferredoxin is more readily saturated with microwave power at low temperatures than those of the eight-iron ferredoxins, indicating that there is another mechanism of electron-spin relaxation in the latter. 6. Mossbauer spectra of both redox states were observed over a range of temperatures and in magnetic fields. At high temperatures (77 degrees K and above) both redox states appear as quadrupole-split doublets; in the reduced state two resolved doublets are seen, suggesting appreciable localization of the additional reducing electron. 7. The average chemical shift indicates formal valences of two Fe3+ and two Fe2+ in the oxidized state and three Fe2+ and one Fe3+ in the reduced state. However, the spectra indicate that there are differing degrees of electron delocalization over the iron atoms. 8. At low temperatures (4.2 degrees K) the oxidized form shows no hyperfine magnetic interaction, even in an applied magnetic field, evidence that the oxidized ferredoxin is in a non-magnetic state as a result of antiferromagnetic coupling between the iron atoms. 9. At 4.2 degrees K the reduced form shows a broad asymmetric pattern resulting from magnetic hyperfine interaction. This contrasts with the reduced ferredoxin of Clostridium pasteurianum, which shows a doublet, suggesting that in the latter there may be interaction between the two 4Fe-4S centres. 10. In large applied magnetic fields, positive and negative hyperfine fields are seen in the Mossbauer spectra of the reduced ferredoxin, evidence for antiferromagnetic coupling between the iron atoms in the 4Fe-4S centre. The high-field spectra of the reduced ferredoxin of B. stearothermophilus are similar to those of the reduced ferredoxin of C. pasteurianum.