High Electron Spin Polarization Research Articles

Effect of dilute nitride GaNAs quantum well thickness on spin amplification dynamics of tunnel-coupled InAs quantum dots

Electron spin dynamics of dilute nitride GaNAs quantum well (QW)-InAs quantum dots (QDs) tunnel-coupled structures having different QW thicknesses were studied via circularly polarized time-resolved photoluminescence. The rate equation fitting considering a capture of QD electron spins by the GaNAs localized states via tunnel transfer revealed that the spin amplification dynamics of the QDs depended on the QW thickness. For the QW thickness of 5 nm, although the temporal amplification of QD electron spin polarization was slow owing to the weak wavefunction coupling between the QW and QD, the long duration of high electron spin polarization was observed because of the suppressed capture of QD majority spins relative to the efficient removal of QD minority spins. When the QW thickness increased from 5 to 20 nm, the strong spin filtering in GaNAs and strong wavefunction coupling led to the fast amplification of QD electron spin polarization with high initial spin polarization. However, the spin polarization rapidly decays after the amplification owing to the removal of both QD majority and minority spins, originating from many effective localized states. These results indicate that the time-dependent QD electron spin polarization and the resultant spin amplification can be widely tuned by changing the thickness of the tunnel-coupled GaNAs QW.

Macroscopic sample shape effect on pulse electron double resonance (PELDOR) signal

Pulse electron double resonance (PELDOR), also called double electron–electron resonance (DEER), is a technique capable of measuring the strength of electron spin dipolar interactions, revealing spin–spin distance distributions in ordered and disordered solid materials. Previous work has shown that PELDOR signals acquire an out-of-phase component under conditions of high electron spin polarization, such as at low temperatures and high fields. In this paper, we show theoretically and experimentally that the size and sign of this effect depends on the macroscopic shape of the sample and its orientation in the external magnetic field. This effect is caused by dipolar interactions between distant spins and provides new insights into the fundamental physics of PELDOR.

EPR and Related Magnetic Resonance Imaging Techniques in Cancer Research.

Imaging tumor microenvironments such as hypoxia, oxygenation, redox status, and/or glycolytic metabolism in tissues/cells is useful for diagnostic and prognostic purposes. New imaging modalities are under development for imaging various aspects of tumor microenvironments. Electron Paramagnetic Resonance Imaging (EPRI) though similar to NMR/MRI is unique in its ability to provide quantitative images of pO2 in vivo. The short electron spin relaxation times have been posing formidable challenge to the technology development for clinical application. With the availability of the narrow line width trityl compounds, pulsed EPR imaging techniques were developed for pO2 imaging. EPRI visualizes the exogenously administered spin probes/contrast agents and hence lacks the complementary morphological information. Dynamic nuclear polarization (DNP), a phenomenon that transfers the high electron spin polarization to the surrounding nuclear spins (1H and 13C) opened new capabilities in molecular imaging. DNP of 13C nuclei is utilized in metabolic imaging of 13C-labeled compounds by imaging specific enzyme kinetics. In this article, imaging strategies mapping physiologic and metabolic aspects in vivo are reviewed within the framework of their application in cancer research, highlighting the potential and challenges of each of them.

Temperature dependence of inter-dot electron-spin transfer among laterally coupled excited states in high-density InGaAs quantum dots

The temperature dependence of interdot spin-transfer dynamics at laterally coupled excited states (ESs) in high-density InGaAs quantum dots (QDs) was studied using spin- and time-resolved photoluminescence spectroscopy. At low temperatures below 100 K, temporary suppression of electron-spin polarization decay due to selective relaxation of minority spins from emissive ESs to lower-energy states in neighboring QDs was observed. In the temperature range from 20 K to 140 K, thermal activation of electron spins from lower-energy QD states to higher-energy states via interdot transfer prevents the aforementioned selective relaxation of minority spins, leading to a faster decay of electron-spin polarization during light emission. At high temperatures above 140 K, reinjection of depolarized electron spins from barriers after thermal escape from QD ESs accelerates the further decay of the electron-spin polarization, wherein the electron spins can be activated via ladderlike interdot transfer. These findings indicate that the suppression of reinjection of electron spins from barriers in a high-density QD system is crucial for maintaining high electron-spin polarization during light emission at high temperatures.

Room-temperature polarized spin-photon interface based on a semiconductor nanodisk-in-nanopillar structure driven by few defects

Owing to their superior optical properties, semiconductor nanopillars/nanowires in one-dimensional (1D) geometry are building blocks for nano-photonics. They also hold potential for efficient polarized spin-light conversion in future spin nano-photonics. Unfortunately, spin generation in 1D systems so far remains inefficient at room temperature. Here we propose an approach that can significantly enhance the radiative efficiency of the electrons with the desired spin while suppressing that with the unwanted spin, which simultaneously ensures strong spin and light polarization. We demonstrate high optical polarization of 20%, inferring high electron spin polarization up to 60% at room temperature in a 1D system based on a GaNAs nanodisk-in-GaAs nanopillar structure, facilitated by spin-dependent recombination via merely 2–3 defects in each nanodisk. Our approach points to a promising direction for realization of an interface for efficient spin-photon quantum information transfer at room temperature—a key element for future spin-photonic applications.

Influence of interfaces on the phonon density of states of nanoscale metallic multilayers: Phonon confinement and localization

Isotope-selective $^{57}\mathrm{Fe}$ nuclear resonant inelastic x-ray scattering (NRIXS) measurements and atomic-layer resolved density functional theory (DFT) calculations were used to investigate the effect of interfaces on the vibrational (phonon) density of states (VDOS) of (001)-oriented nanoscale Fe/Ag and Fe/Cr multilayers. The multilayers in the experiment contained isotopically enriched $^{57}\mathrm{Fe}$ monolayers as probe layers located either at the Fe/Ag or Fe/Cr interfaces or in the center of the Fe films. This allows probing of the vibrational dynamics of Fe sites either at the buried interfaces or in the center of the Fe films. For Fe/Ag multilayers, distinct differences were observed experimentally between the Fe-partial VDOS at the interface and in the center. At the Fe/Ag interface, the high-energy longitudinal-acoustic (LA) phonon peak of Fe near $\ensuremath{\sim}35$ meV is suppressed and slightly shifted to lower energy, and the low-energy part of the VDOS below $\ensuremath{\sim}20$ meV is drastically enhanced, as compared to the Fe-specific VDOS in the center Fe layers or in bulk Fe. Similar phenomena are found to a less degree in the Fe/Cr multilayers. The measured Fe-partial VDOS was used to determine the Fe site-selective vibrational thermodynamic properties of the multilayers. Our theoretical findings for the layer-dependent VDOS of the multilayers are in qualitative agreement with the experimental results obtained by NRIXS. For Fe/Ag multilayers, which are characterized by a large atomic mass ratio, the experimental and theoretical results demonstrate phonon confinement in the Fe layers and phonon localization at the Fe/Ag interfaces due to the energy mismatch between Ag and Fe LA phonons. These phenomena are reduced or suppressed in the Fe/Cr multilayers with their about equal atomic masses. Moreover, direction-projected Fe VDOS along the (nearly in-plane) incident x-ray beam was computed in order to address the intrinsic vibrational anisotropy of the Fe/Ag multilayer. We have also performed spin-resolved electronic band structure (DFT) calculations, predicting an enhanced magnetic moment $({\ensuremath{\mu}}_{\mathrm{Fe}}=2.8\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}})$ of the interfacial Fe atoms and a high electron spin polarization (79%) at the Fermi energy for the Fe/Ag interface, as compared to the case of Fe center layers. This is a result of charge transfer from Fe to Ag at the interface. On the contrary, Cr tends to donate electrons to Fe, thus reducing the interfacial Fe moment $({\ensuremath{\mu}}_{\mathrm{Fe}}=1.9\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}})$. This implies strong chemical bonding at the Fe/Ag and Fe/Cr interfaces, affecting the interfacial VDOS.

Paramagnetic Metal-Ion Dopants as Polarization Agents for Dynamic Nuclear Polarization NMR Spectroscopy in Inorganic Solids.

Dynamic nuclear polarization (DNP), a technique in which the high electron spin polarization is transferred to surrounding nuclei via microwave irradiation, equips solid-state NMR spectroscopy with unprecedented sensitivity. The most commonly used polarization agents for DNP are nitroxide radicals. However, their applicability to inorganic materials is mostly limited to surface detection. Paramagnetic metal ions were recently introduced as alternatives for nitroxides. Doping inorganic solids with paramagnetic ions can be used to tune material properties and introduces endogenous DNP agents that can potentially provide sensitivity in the particles' bulk and surface. Here we demonstrate the approach by doping Li4 Ti5 O12 (LTO), an anode material for lithium ion batteries, with paramagnetic ions. By incorporating Gd(III) and Mn(II) in LTO we gain up to 14 fold increase in signal intensity in static 7 Li DNP-NMR experiments. These results suggest that doping with paramagnetic ions provides an efficient route for sensitivity enhancement in the bulk of micron size particles.

Robust techniques for polarization and detection of nuclear spin ensembles

Highly sensitive nuclear spin detection is crucial in many scientific areas including nuclear magnetic resonance spectroscopy (NMR), imaging (MRI) and quantum computing. The tiny thermal nuclear spin polarization represents a major obstacle towards this goal which may be overcome by Dynamic Nuclear Spin Polarization (DNP) methods. The latter often rely on the transfer of the thermally polarized electron spins to nearby nuclear spins, which is limited by the Boltzmann distribution of the former. Here we demonstrate the polarization and read out of a nuclear spin bath consisting of $^{13}$C nuclear spins in diamond by using a single nitrogen-vacancy (NV) center. Our method utilizes microwave dressed states to transfer the NV's high ($>$~92~\%) non-equilibrium electron spin polarization induced by short laser pulses to the surrounding carbon nuclear spins, where the NV is repeatedly repolarized optically, thus providing an effectively infinite polarization reservoir. A saturation of the polarization in the nuclear "frozen core" is achieved, which is confirmed by the decay of the polarization transfer signal and shows an excellent agreement with theoretical simulations. Hereby we introduce the Polarization Read Out by Polarization Inversion (PROPI) method as a quantitative magnetization measure of the nuclear spin bath. Moreover, we show that using the integrated solid effect both for single and double quantum transitions a nuclear spin polarization can be achieved even when the static magnetic field is not aligned along the NV's crystal axis. This opens a path for the application of our DNP technique to spins in and outside of nanodiamonds, enabling their application as MRI tracers.

Spectral diffusion and dynamic nuclear polarization: Beyond the high temperature approximation

Dynamic Nuclear Polarization (DNP) has proven itself most powerful for the orientation of nuclear spins in polarized targets and for hyperpolarization in magnetic resonance imaging (MRI). Unfortunately, the theoretical description of some of the processes involved in DNP invokes the high temperature approximation, in which Boltzmann factors are expanded up to first order, while the high electron and nuclear spin polarization required for many applications do not justify such an approximation. A previous article extended the description of one of the mechanisms of DNP—thermal mixing—beyond the high temperature approximation (Wenckebach, 2017). But that extension is still limited: it assumes that fast spectral diffusion creates a local equilibrium in the electron spin system.Provotorov’s theory of cross-relaxation enables a consistent further extension to slower spectral diffusion, but also invokes the high temperature approximation. The present article extends the theory of cross-relaxation to low temperature and applies it to spectral diffusion in glasses doped with paramagnetic centres with anisotropic g-tensors. The formalism is used to describe DNP via the mechanism of the cross effect. In the limit of fast spectral diffusion the results converge to those obtained in Wenckebach (2017) for thermal mixing. In the limit of slow spectral diffusion a hole is burnt in the electron spin resonance (ESR) signal, just as predicted by more simple models. The theory is applied to DNP of proton and 13C spins in samples doped with the radical TEMPO.

Record-level quantum efficiency from a high polarization strained GaAs/GaAsP superlattice photocathode with distributed Bragg reflector

Photocathodes that provide high electron-spin polarization (ESP) and high quantum efficiency (QE) can significantly enhance the physics capabilities of electron accelerators. We report record-level QE from a high-polarization strained GaAs/GaAsP superlattice photocathode fabricated with a Distributed Bragg Reflector (DBR). The DBR photocathode technique enhances the absorption of incident laser light thereby enhancing QE, but as literature suggests, it is very challenging to optimize all of the parameters associated with the fabrication of complicated photocathode structures composed of many distinct layers. Past reports of DBR photocathodes describe high polarization but typically QE of only ∼1%, which is comparable to QE of high polarization photocathodes grown without a DBR structure. This work describes a strained GaAs/GaAsP superlattice DBR photocathode exhibiting a high polarization of 84% and significantly enhanced QE of 6.4%.

A New Horizon of DNP technology: Application to In-vivo 13C Magnetic Resonance Spectroscopy and Imaging.

Dynamic nuclear polarization (DNP) is an emerging technique for increasing the sensitivity (>10,000-fold) of magnetic resonance spectroscopy and imaging (MRSI), in particularly for low-γ nuclei. DNP methodology is based on polarizing nuclear spins in an amorphous solid state at low temperature (ca. 1 K) through coupling of the nuclear spins with unpaired electron spins that are added to the sample via an organic free radical. In an amorphous solid state, the high electron spin polarization can be transferred to the nuclear spins by microwave irradiation. While this technique has been utilized in solid-state research for many years, it is only recently that dissolution methods and the required hardware have been developed to produce the high nuclear polarization provided by DNP to produce injectable hyperpolarized solutions suitable for in vivo studies. It has been applied to a number of 13C-labeled cell metabolites in biological systems and their real-time metabolic conversion has been imaged. This review focuses the DNP methodology briefly and the significant molecules investigated to date in preclinical cancer models, in terms of their downstream metabolism in vivo or the biological processes that they can probe. In particular, conversion between hyperpolarized 13C-labeled pyruvate and lactate, catalyzed by lactate dehydrogenase, has been shown to have a number of potential applications such as diagnosis, staging tumor grade and monitoring therapy response. Strategies for making this technique more viable to use in clinical settings has been discussed.

Enhanced orbital mixing in the valence band of strained germanium

We give a theoretical explanation of the very high electron-spin polarization measured in compressively strained Ge layers through spin-polarized photoemission experiments, based on the enhancement of the band orbital mixing between light-hole (LH) and split-off (SO) bands along the growth direction of Ge thin films. We deduce an increased valence-band mixing, with respect to the bulk case, from the measured spin-polarization values, which exceed the bulk limit when optical transitions away from the $\ensuremath{\Gamma}$ point of the tetragonally distorted Brillouin zone are taken into account. Furthermore, we show that the degree of LH-SO band orbital mixing is directly proportional to the degree of compressive strain in the Ge layer.

NMR of Insensitive Nuclei Enhanced by Dynamic Nuclear Polarization.

Despite the powerful spectroscopic information it provides, Nuclear Magnetic Resonance (NMR) spectroscopy suffers from a lack of sensitivity, especially when dealing with nuclei other than protons. Even though NMR can be applied in a straightforward manner when dealing with abundant protons of organic molecules, it is very challenging to address biomolecules in low concentration and/or many other nuclei of the periodic table that do not provide as intense signals as protons. Dynamic Nuclear Polarization (DNP) is an important technique that provides a way to dramatically increase signal intensities in NMR. It consists in transferring the very high electron spin polarization of paramagnetic centers (usually at low temperature) to the surrounding nuclear spins with appropriate microwave irradiation. DNP can lead to an enhancement of the nuclear spin polarization by up to four orders of magnitude. We present in this article some basic concepts of DNP, describe the DNP apparatus at EPFL, and illustrate the interest of the technique for chemical applications by reporting recent measurements of the kinetics of complexation of 89Y by the DOTAM ligand.

Effect of adsorbates on the formation of doubly excited He atoms during impact of He 2+ ions on a Ni(1 1 0) surface

The formation of doubly excited states of He atoms during impact of He 2+ ions with projectile energies of 60–1000 eV under near-grazing angles of incidence of 5°–20° on clean and adsorbate-covered Ni(1 1 0) surfaces is studied by means of Auger electron spectroscopy. Pronounced dependencies of electron spectra from autoionization of atoms in doubly excited 2 s 2, 2 s2 p and 2 p 2 configurations on the coverage of the target surface with adsorbates are observed. These are directly related to work function changes, which are studied for the controlled adsorption of oxygen. Changes of the electron spectra on the target temperature are found for adsorbate-covered surfaces only, which puts into question recent interpretations of similar electron spectra in terms of a high local electron spin polarization of Ni(1 1 0) by an alternative interpretation based on thermal desorption or dissolution into bulk of surface contaminations. The formation of doubly excited states is studied for the oxygen p(2 × l) and p(3 × l) superstructures on Ni(1 1 0) in order to provide well-defined experimental data for theoretical investigations.

Comment on “High efficiency electron spin polarization analyzer based on exchange scattering at Fe/W(001)” [Rev. Sci. Instrum. 79, 083303 (2008)

A recent article [Winkelmann et al., Rev. Sci. Instrum. 79, 083303 (2008)] reports on a compact detector to analyze the electron spin based on exchange scattering at Fe(001) thin film grown on W(001) with chemisorbed oxygen in the p(1x1) structure. The results obtained with the same detector without oxygen coverage show, however, a better performance in terms of both asymmetry and figure of merit. It is also argued that the characterization performed only allows to make qualitative comparisons with other existing detectors based on the same exchange scattering since the polarization of the incident beam has not been measured in situ.

Response to “Comment on ‘High efficiency electron spin polarization analyzer based on exchange scattering at Fe/W(001)’” [Rev. Sci. Instrum. 80, 057103 (2009)

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High efficiency electron spin polarization analyzer based on exchange scattering at Fe∕W(001)

We report on a compact electron spin analyzer based on exchange scattering from a magnetic surface. The heart of the detector is an Fe(001) thin film grown on W(001) with chemisorbed oxygen in the p(1 x 1) structure. The device is mounted at the exit of an energy dispersive analyzer and works at a scattering energy of about 13.5 eV. Its figure of merit is 2 x 10(-3), combined with an excellent stability of more than 2 weeks in UHV.

The theory of nuclear orientation via electron spin locking (NOVEL)

Nuclear orientation via electron spin locking (NOVEL) is a technique to orient nuclear spins embedded in a solid. Like other methods of dynamic nuclear polarization (DNP) it employs a small amount of unpaired electron spins and uses a microwave field to transfer the polarization of these unpaired electron spins to the nuclear spins. Traditional DNP uses CW microwave fields, but NOVEL uses pulsed electron spin resonance (ESR) techniques: a 90 degree pulse–90 degree phase shift–locking pulse sequence is applied and during the locking pulse the polarization transfer is assured by satisfying the Hartmann–Hahn condition. The transfer is coherent and similar to coherence transfer between nuclear spins. However, NOVEL requires an extension of the existing theory to many, inequivalent nuclear spins and to arbitrary, i.e. high electron and nuclear spin polarization. In this paper both extensions are presented. The theory is applied to the system naphthalene doped with pentacene, where the proton spins are polarized using the photo-excited triplet states of the pentacene molecules and found to show excellent agreement with the experimentally observed evolution of the polarization transfer during the locking pulse.

A Davies/Hahn multi-sequence for studies of spin relaxation in pulsed ENDOR

We extend earlier studies of the effects of relaxation on the intensities of pulsed ENDOR signals by introducing a Davies/Hahn (D/H) pulsed ENDOR multi-sequence that corresponds to a series of Davies sequences with the preparation pulse ‘turned off’. In this pulse train, the Hahn [π/2, π] detection pulse pair of sequence n−1 both generates the echo detected for that sequence and acts as the preparation portion of sequence n, in effect replacing the π preparation pulse of the Davies sequence. We show both theoretically, through a master-equation approach, and with both 1H ( I = 1/2) and 14N ( I = 1) ENDOR experiments on the non-heme Fe enzymes, superoxide reductase (SOR) ( S = 1/2) and AntDO ( S = 3/2), that under conditions of high electron–spin polarization (high microwave frequency/low temperature) the D/H multi-sequence allows simplification of ENDOR spectra by suppression of nuclear transitions associated with the m S = +1/2 ( α) manifold. As such suppression depends on the sign of A, it allows determination of this sign. The suppression as a function of the time between individual sequences is found to exhibit behaviors that can be classified into three regimes of the ratio of cross-relaxation to spin–lattice relaxation rates: strong cross-relaxation (X-case); comparable rates (XL); negligible cross relaxation (L). Interestingly, the ENDOR behavior of the S = 1/2 SOR center indicates it is an L case, while the S = 3/2 AntDO is an L case. Overall, the D/H protocol appears to be a robust and general tool for using relaxation effects to manipulate ENDOR spectra.

UTILIZATION OF POLARIZED ELECTRON SPIN OF ORGANIC MOLECULES IN QUANTUM COMPUTING

The possibility of utilizing highly polarized electron spin of the photo-excited triplet state of organic semiconductors (pentacene molecules) embedded in organic crystals and mesoporous materials by zero-field (ZF) and near zero-field (NZF) pulsed electron paramagnetic resonance (EPR) techniques in a quantum computer will be explored. A simple logic gate, such as CNOT, utilizing such highly polarized electron spins communicating with the surrounding paramagnetic nuclei via hyperfine interaction will be discussed. Major advantages of these approaches are: (1) high electron spin polarization, (2) possible single-molecule detection, (3) orchestrated quantum perturbations can be imposed, and (4) pulsed ZF and NZF EPR techniques can be performed without high magnetic field.