Slow oxidation of magnetite nanoparticles elucidates the limits of the Verwey transition.

Magnetite (Fe3O4) is of fundamental importance for the Verwey transition near TV = 125 K, below which a complex lattice distortion and electron orders occur. The Verwey transition is suppressed by chemical doping effects giving rise to well-documented first and second-order regimes, but the origin of the order change is unclear. Here, we show that slow oxidation of monodisperse Fe3O4 nanoparticles leads to an intriguing variation of the Verwey transition: an initial drop of TV to a minimum at 70 K after 75 days and a followed recovery to 95 K after 160 days. A physical model based on both doping and doping-gradient effects accounts quantitatively for this evolution between inhomogeneous to homogeneous doping regimes. This work demonstrates that slow oxidation of nanoparticles can give exquisite control and separation of homogeneous and inhomogeneous doping effects on the Verwey transition and offers opportunities for similar insights into complex electronic and magnetic phase transitions in other materials.

Nanometer-Scale Water Dynamics in Nafion Polymer Electrolyte Membranes: Influence of Molecular Hydrophobicity and Water Content Revisited.

The ionic conductivity of polymer electrolyte membranes (PEMs) is an essential parameter for their device applications. In water-swollen PEMs, protons and other ions are transferred through hydrophilic channels of a few nanometers in diameter at most. Thus, optimizing the chemical and physical properties of the channels can enhance the conductivity of PEMs. However, the factors controlling the conductivity have not been completely clarified. Here, we report that measurements taken near the channel walls by a special nuclear magnetic resonance technique with ≤1 nm spatial resolution showed the largest water diffusivity when ∼80% of hydrophilic sulfonic acid groups were blocked, but the proton conductivity was low. The water diffusivity was much less affected by differences in water content. Our results provide a concept for changing the properties of PEMs and a challenge to implement the improved diffusivity in a way that enhances net ion conductivity.

Interactions in the bond-frustrated helimagnet ZnCr2Se4 investigated by NMR.

The zero field 53Cr nuclear magnetic resonance was measured at low temperatures to investigate the interactions in the bond-frustrated S = 3/2 Heisenberg helimagnet ZnCr2Se4. A quadratic decrease of the sublattice magnetization was determined from the temperature dependence of the isotropic hyperfine field. We calculated the magnetization using linear spin wave theory for the incommensurate spiral spin order and compared this outcome with experimental results to estimate the coupling constants. The hyperfine fields at Cr and Se ions provide evidences that the spin polarization of Cr ions is transferred to neighboring Se ions due to the covalent bonding between them, resulting in reduced magnetic moment in the Cr ion. This observation indicates that the Jahn-Teller effect, which leads to distortion inducing spin-lattice coupling, is not completely missing in ZnCr2Se4.

Electron spin relaxations of phosphorus donors in bulk silicon under large electric field.

Modulation of donor electron wavefunction via electric fields is vital to quantum computing architectures based on donor spins in silicon. For practical and scalable applications, the donor-based qubits must retain sufficiently long coherence times in any realistic experimental conditions. Here, we present pulsed electron spin resonance studies on the longitudinal (T1) and transverse (T2) relaxation times of phosphorus donors in bulk silicon with various electric field strengths up to near avalanche breakdown in high magnetic fields of about 1.2 T and low temperatures of about 8 K. We find that the T1 relaxation time is significantly reduced under large electric fields due to electric current, and T2 is affected as the T1 process can dominate decoherence. Furthermore, we show that the magnetoresistance effect in silicon can be exploited as a means to combat the reduction in the coherence times. While qubit coherence times must be much longer than quantum gate times, electrically accelerated T1 can be found useful when qubit state initialization relies on thermal equilibration.

Giant thermal hysteresis in Verwey transition of single domain Fe3O4 nanoparticles.

Most interesting phenomena of condensed matter physics originate from interactions among different degrees of freedom, making it a very intriguing yet challenging question how certain ground states emerge from only a limited number of atoms in assembly. This is especially the case for strongly correlated electron systems with overwhelming complexity. The Verwey transition of Fe3O4 is a classic example of this category, of which the origin is still elusive 80 years after the first report. Here we report, for the first time, that the Verwey transition of Fe3O4 nanoparticles exhibits size-dependent thermal hysteresis in magnetization, 57Fe NMR, and XRD measurements. The hysteresis width passes a maximum of 11 K when the size is 120 nm while dropping to only 1 K for the bulk sample. This behavior is very similar to that of magnetic coercivity and the critical sizes of the hysteresis and the magnetic single domain are identical. We interpret it as a manifestation of charge ordering and spin ordering correlation in a single domain. This work paves a new way of undertaking researches in the vibrant field of strongly correlated electron physics combined with nanoscience.

Microscopic States and the Verwey Transition of Magnetite Nanocrystals Investigated by Nuclear Magnetic Resonance.

57Fe nuclear magnetic resonance (NMR) of magnetite nanocrystals ranging in size from 7 nm to 7 µm is measured. The line width of the NMR spectra changes drastically around 120 K, showing microscopic evidence of the Verwey transition. In the region above the transition temperature, the line width of the spectrum increases and the spin-spin relaxation time decreases as the nanocrystal size decreases. The line-width broadening indicates the significant deformation of magnetic structure and reduction of charge order compared to bulk crystals, even when the structural distortion is unobservable. The reduction of the spin-spin relaxation time is attributed to the suppressed polaron hopping conductivity in ferromagnetic metals, which is a consequence of the enhanced electron-phonon coupling in the quantum-confinement regime. Our results show that the magnetic distortion occurs in the entire nanocrystal and does not comply with the simple model of the core-shell binary structure with a sharp boundary.

Fe and Co NMR studies of magnetoelectric Co2 Y-type hexaferrite BSCFAO.

The Fe3+ and Co2+ NMR spectra for Ba0.3Sr1.7Co2(Fe0.96Al0.04)12O22 (BSCFAO) and Ba0.3Sr1.7Co2Fe12O22 (BSCFO) were obtained in a zero magnetic field at a low temperature. We observed change in the enhancement effect of the NMR signals depending on the setting field, which was varied when applied along the b-axis and then turned off before the measurement was taken. The experimental results indicate that the magnetic structure changes from an alternating longitudinal cone to a transverse cone when the setting field is 250 mT. They also show that the spins of Co2+ ions together with those of Fe3+ ions constitute a part of the overall magnetic structure and that the substitution of Al3+ for Fe3+ weakens the magnetic anisotropy within the easy plane. From a comparison of the enhancement factors of the Fe3+ NMR obtained with the RF pulse applied along the a-axis and the c-axis, we found that the magnetic easy plane anisotropy is approximately 16 times greater than the anisotropy within the easy plane. No changes of the NMR spectra were observed under an electric field of 1.2 MV m-1.

Orbital reorientation in MnV2O4 observed by V NMR.

The simultaneous occurrence of the structural and magnetic phase transitions observed in MnV2O4 is one clear example of strong interplay among the spin, orbital and lattice degrees of freedom. The structure of MnV2O4 is switched by the magnetic field and the linear magnetostriction is very high. The orbital order mediates the interaction between the spin and the lattice generating these phenomena. In this work, we present experimental evidence of an orbital order in MnV2O4 and its reorientation under a rotating magnetic field as obtained by nuclear magnetic resonance(NMR). The shift in the resonance frequency of the V NMR spectrum is symmetrical with respect to 45° as an external magnetic field of 7 T rotates from the c-axis to the b-axis, indicating that the initial easy axis flips to the orthogonal direction most parallel to the field direction. The spectrum of V3+ ions splits into four peaks with a maximum shift of 40 MHz. Our analysis revealed that this is the combined effect of the anisotropic hyperfine field due to an ordered orbital and the dipolar hyperfine field. Reorientation of the orbital order in response to an external magnetic field accompanies the macroscopically observed magnetostriction in MnV2O4.

Sensitive detection of NMR for thin films.

NMR can provide valuable information about thin films, but its relatively low sensitivity allows data acquisition only from bulk samples. The sensitivity problem is circumvented by detection schemes with higher sensitivity and/or enhanced polarization. In most of these ingenious techniques, electrons play a central role through hyperfine interactions with the nuclei of interest or the conversion of the spin orientation to an electric charge. The state of the art in NMR is the control of a single nuclear spin state, the complete form of which is one of the ultimate goals of nanotechnology.

NMR spin-lattice relaxation time T(1) of thin films obtained by magnetic resonance force microscopy.

We obtained the NMR spectrum and the spin-lattice relaxation time (T1) for thin film samples by magnetic resonance force microscopy (MRFM). The samples were CaF2 thin films which were 50 nm and 150 nm thick. T1 was measured at 18 K using a cyclic adiabatic inversion method at a fixed frequency. A comparison of the bulk and two thin films showed that T1 becomes shorter as the film thickness decreases. To make the comparison as accurate as possible, all three samples were loaded onto different beams of a multi-cantilever array and measured in the same experimental environment.

Electrical control of large magnetization reversal in a helimagnet.

Reversal of magnetization M by an electrical field E has been a long-sought phenomenon in materials science because of its potential for applications such as memory devices. However, the phenomenon has rarely been achieved and remains a considerable challenge. Here we report the large M reversal by E in a multiferroic Ba0.5Sr1.5Zn2(Fe0.92Al0.08)12O22 crystal without any external magnetic field. Upon sweeping E through the range of ±2 MV m(-1), M varied quasi-linearly in the range of ±2 µB per f.u., resulting in the M reversal. Strong electrical modulation of M at zero magnetic field were observable up to ~\n150 K. Nuclear magnetic resonance measurements provided microscopic evidence that the electric field and the magnetic field play equivalent roles in modulating the volume of magnetic domains. Our results suggest that the soft ferrimagnetism and the associated transverse conical state are key ingredients to achieve the large magnetization reversal at fairly high temperatures.

Effects of Al substitution and thermal annealing on magnetoelectric Ba0.5Sr1.5Zn2Fe12O22 investigated by the enhancement factor of 57Fe nuclear magnetic resonance.

The magnetoelectric properties of hexaferrite Ba0.5Sr1.5Zn2Fe12O22 are significantly improved by Al substitution and thermal annealing. Measuring the enhancement factor of 57Fe NMR, we found direct microscopic evidence that the magnetic moments of the L and S blocks are rotated by a magnetic field in such a way as to increase the net magnetic moment of a magnetic unit, even after the field is removed. Al substitution makes magnetoelectric property arise easily by suppressing the easy-plane anisotropy. The effect of thermal annealing is to stabilize the multiferroic state by reducing the number of pinning sites and the electron spin fluctuation. The transverse conic structure gradually changes to the alternating longitudinal conic structure where spins fluctuate more severely.

NMR spectroscopy for thin films by magnetic resonance force microscopy.

Nuclear magnetic resonance (NMR) is a fundamental research tool that is widely used in many fields. Despite its powerful applications, unfortunately the low sensitivity of conventional NMR makes it difficult to study thin film or nano-sized samples. In this work, we report the first NMR spectrum obtained from general thin films by using magnetic resonance force microscopy (MRFM). To minimize the amount of imaging information inevitably mixed into the signal when a gradient field is used, we adopted a large magnet with a flat end with a diameter of 336 µm that generates a homogeneous field on the sample plane and a field gradient in a direction perpendicular to the plane. Cyclic adiabatic inversion was used in conjunction with periodic phase inversion of the frequency shift to maximize the SNR. In this way, we obtained the (19)F NMR spectrum for a 34 nm-thick CaF2 thin film.

Spin dynamics of isolated donor electrons in phosphorus-doped silicon from high-frequency electron spin resonance.

We present the spin dynamics of isolated donor electrons in phosphorus-doped silicon at low temperature and in a high magnetic field. We performed a steady-state electron spin resonance (ESR) on the sample with a dopant concentration of 6.5 × 10(16) cm(- 3) in a high field of 2.87 T (80 GHz) and at temperatures from 48 down to 1.8 K. As the temperature decreases below 16 K, the resonance spectral line changes from the usual derivative form characteristic of absorptions. Very long spin-lattice relaxation time T(1) at low temperature gives rise to rapid passage effects and results in a dramatic change in the line shape and intensity as a function of temperature. We show that the numerical analysis based on the passage effects well explains the observed spectral changes with temperature. The spin-lattice relaxation time T(1) is derived by numerical fit to the experimental data. We discuss the dynamic nuclear polarization of (31)P nuclear spins which shows up as asymmetric intensities of the hyperfine-split ESR resonance lines.

MR microscopy of micron scale structures.

Magnetic resonance (MR) microscopy of up to 1-5-microm resolutions have been reported previously. The tested phantom structures, however, had widths one order of magnitude bigger than the reported resolutions, e.g., spherical beads or capillary tubes of tens-of-micron diameters or wall thicknesses have been imaged. In this study, we fabricated structures having a few micron widths on a silicon wafer and imaged them using our 1-microm-resolution MR microscopy at 14.1 T. Micron scale width structures were, for the first time, resolved by MR microscopy.

Coexistence of two different Cr ions by self-doping in half-metallic CrO2 nanorods.

We investigated the physical properties of Cr ions in half-metallic CrO(2) using 53Cr nuclear magnetic resonance (NMR). The 53Cr NMR spectra showed two peaks with a similar intensity instead of the single peak anticipated from a uniform single valence Cr(+4). Both Cr peaks exhibited a strong anisotropy in the hyperfine field and similar values in the enhancement factor and T2 relaxation time. These results suggest the coexistence of two different Cr ions (provisionally, Cr(+4 +/- 1/3)) by a self-doping effect, which is a likely origin of the metallic ferromagnetism in CrO(2).

Experimental demonstration of a programmable quantum computer by NMR.

A programmable quantum computer is experimentally demonstrated by nuclear magnetic resonance using one qubit for the program and two qubits for data. A non-separable two-qubit operation is performed in a programmable way to show the successful demonstration. Projective measurements required in the programmable quantum computer are simulated by averaging the results of experiments just like when producing an effective pure state.