Dangling-bond spin relaxation and magnetic 1/f noise from the amorphous-semiconductor/oxide interface: Theory

We propose a model for magnetic noise based on spin-flips (not electron-trapping) of paramagnetic dangling-bonds at the amorphous-semiconductor/oxide interface. A wide distribution of spin-flip times is derived from the single-phonon cross-relaxation mechanism for a dangling-bond interacting with the tunneling two-level systems of the amorphous interface. The temperature and frequency dependence is sensitive to three energy scales: The dangling-bond spin Zeeman energy delta, as well as the minimum (E_min) and maximum (E_max) values for the energy splittings of the tunneling two-level systems. We compare and fit our model parameters to a recent experiment probing spin coherence of antimony donors implanted in nuclear-spin-free silicon [T. Schenkel {\it et al.}, Appl. Phys. Lett. 88, 112101 (2006)], and conclude that a dangling-bond area density of the order of 10^{14}cm^{-2} is consistent with the data. This enables the prediction of single spin qubit coherence times as a function of the distance from the interface and the dangling-bond area density in a real device structure. We apply our theory to calculations of magnetic flux noise affecting SQUID devices due to their Si/SiO_2 substrate. Our explicit estimates of flux noise in SQUIDs lead to a noise spectral density of the order of 10^{-12}Phi_{0}^{2} {Hz}^{-1} at f=1Hz. This value might explain the origin of flux noise in some SQUID devices. Finally, we consider the suppression of these effects using surface passivation with hydrogen, and the residual nuclear-spin noise resulting from a perfect silicon-hydride surface.Comment: Final published versio

Electron Spin-Relaxation Times of Phosphorus Donors in Silicon

Pulsed electron paramagnetic resonance measurements of donor electron spins in natural phosphorus-doped silicon (Si:P) and isotopically-purified 28Si:P show a strongly temperature-dependent longitudinal relaxation time, T1, due to an Orbach process with DeltaE = 126 K. The 2-pulse echo decay is exponential in 28Si:P, with the transverse relaxation (decoherence) time, T2, controlled by the Orbach process above ~12 K and by instantaneous diffusion at lower temperatures. Spin echo experiments with varying pulse turning angles show that the intrinsic T2 of an isolated spin in 28Si:P is ~60 ms at 7 K.Comment: Submitted to PRL on 02.28.200

Electron spin dynamics in quantum dots and related nanostructures due to hyperfine interaction with nuclei

We review and summarize recent theoretical and experimental work on electron spin dynamics in quantum dots and related nanostructures due to hyperfine interaction with surrounding nuclear spins. This topic is of particular interest with respect to several proposals for quantum information processing in solid state systems. Specifically, we investigate the hyperfine interaction of an electron spin confined in a quantum dot in an s-type conduction band with the nuclear spins in the dot. This interaction is proportional to the square modulus of the electron wave function at the location of each nucleus leading to an inhomogeneous coupling, i.e. nuclei in different locations are coupled with different strength. In the case of an initially fully polarized nuclear spin system an exact analytical solution for the spin dynamics can be found. For not completely polarized nuclei, approximation-free results can only be obtained numerically in sufficiently small systems. We compare these exact results with findings from several approximation strategies.Comment: 26 pages, 9 figures. Topical Review to appear in J. Phys.: Condens. Matte

Probing Flexibility in Porphyrin-Based Molecular Wires Using Double Electron Electron Resonance

A series of butadiyne-linked zinc porphyrin oligomers, with one, two, three, and four porphyrin units and lengths of up to 75 angstrom, have been spin-labeled at both ends with stable nitroxide TEMPO radicals. The pulsed EPR technique of double electron electron resonance (DEER) was used to probe the distribution of intramolecular end-to-end distances, under a range of conditions. DEER measurements were carried out at 50 K in two types of dilute solution glasses: deutero-toluene (with 10% deutero-pyridine) and deutero-o-terphenyl (with 5% 4-benzyl pyridine). The complexes of the porphyrin oligomers with monodentate ligands (pyridine or 4-benzyl pyridine) principally adopt linear conformations. Nonlinear conformations are less populated in the lower glass-transition temperature solvent. When the oligomers bind star-shaped multidentate ligands, they are forced to bend into nonlinear geometries, and the experimental end-to-end distances for these complexes match those from molecular mechanics calculations. Our results show that porphyrin-based molecular wires are shape-persistent, and yet that their shapes can deformed by binding to multivalent ligands. Self-assembled ladder-shaped 2:2 complexes were also investigated to illustrate the scope of DEER measurements for providing structural information on synthetic noncovalent nanostructures

Determination of the g-Tensors and Their Orientations for cis,trans-(L-N₂S₂)Mo^VOX (X = Cl, SCH₂Ph) by Single-Crystal EPR Spectroscopy and Molecular Orbital Calculations

A single-crystal study of cis,trans-(L-N2S2)MoVOCl (1) doped into cis,trans-(N2S2)MoVIO2 (3) has enabled the g-tensor of 1 and its orientation with respect to the molecular structure to be determined. The EPR parameters (g1, 2.004; g2, 1.960; g3, 1.946; A1, 71.7 × 10-4 cm-1; A2, 11.7 × 10-4 cm-1; A3, 32.0 × 10-4 cm-1) of cis,trans-(L-N2S2)MoVOCl [L-N2S2H2 = N,N‘-dimethyl-N,N‘-bis(mercaptophenyl)ethylenediamine] mimic those of the low-pH form of sulfite oxidase and the “very rapid” species of xanthine oxidase. The principal axis that corresponds to g1 is rotated ∼10° from the Mo⋮O vector, while the principal axis that corresponds to g3 is located in the equatorial plane and ∼38° from the Mo−Cl vector. Independent theoretical calculations of the g-tensor of 1 were performed using two types of techniques:  (1) the spectroscopically parametrized intermediate neglect of differential overlap technique (INDO/S) combined with single-excitation configuration interaction (CIS); (2) a scalar relativistic DFT (BP86 and B3LYP functionals) treatment using the zeroth order regular approximation to relativistic effects (ZORA) in combination with recently developed accurate multicenter mean field spin−orbit operators (RI-SOMF) and the estimation of solvent effects using dielectric continuum theory at the conductor-like screening model (COSMO) level. The excellent agreement between experiment and theory, as well as the high consistency between the INDO/S and BP86/ZORA results, provides a sound basis for analysis of the calculated orientation of the g-tensor for cis,trans-(L-N2S2)MoVO(SCH2Ph) (2), for which single-crystal EPR data are not available but which contains three equatorial sulfur donor atoms, as occurs in sulfite oxidase and xanthine oxidase. The implications of these results for the EPR spectra of the Mo(V) centers of enzymes are discussed

Pulsed EPR studies of a bacterial sulfite-oxidizing enzyme with pH-invariant hyperfine interactions from exchangeable protons

Variable-frequency pulsed electron paramagnetic resonance studies of the molybdenum(V) center of sulfite dehydrogenase (SDH) clearly show couplings from nearby exchangeable protons that are assigned to a (MoOHn)-O-v group. The hyperfine parameters for these exchangeable protons of SDH are the same at both low and high pH and similar to those for the high-pH forms of sulfite oxidases (SOs) from eukaryotes. The SDH proton parameters are distinctly different from the low-pH forms of chicken and human so