M.J. Graf

Spin Dynamics in the Negatively Charged Terbium (III) Bis-phthalocyaninato Complex

The experimental and theoretical study of the electron spin dynamics in the anionic form of a single-ion molecule magnet (SIMM), the bis-phthalocyaninato terbium (III) molecule [Pc(2)Tb](-)[TBA](+), has been addressed by means of solid state (1)H NMR spectroscopy. The magnetic properties of the caged Tb(3+) metal center were investigated in a series of diamagnetically diluted preparations, where the excess of tetrabutylamonium bromide ([TBA]Br)(n) salt was used as diamagnetic matrix complement. We found that a high temperature activated spin dynamics characterizes the systems, which involved phonon-assisted transitions among the crystal field levels in qualitative agreements with literature results. However, the activation barriers in these processes range from 641 cm(-1) for the diamagnetically diluted samples to 584 cm(-1) for those undiluted; thus, they exhibit barriers 2-3 times larger than witnessed in earlier (230 cm(-1)) reports (e.g., Ishikawa, N.; Sugita, M.; Ishikawa, T.; Koshihara, S.; Kaizu, Y. J. Am. Chem. Soc. 2003, 125, 8694-8695). At cryogenic temperatures, fluctuations are driven by tunneling processes between the m = +6 and -6 low-energy levels. We found that the barrier Delta and the tunneling rates change from sample to sample and especially the diamagnetically diluted [Pc(2)Tb](-) molecules appear affected by the samples magneto/thermal history. These observations emphasize that matrix arrangements around [Pc(2)Tb](-) can appreciably alter the splitting of the crystal field levels, its symmetry, and hence, the spin dynamics. Therefore, understanding how small differences in molecular surroundings (as for instance occurring by depositing on surfaces) can trigger substantial modifications in the SIMM property is of utmost importance for the effective operation of such molecules for single-molecule data storage, for example.

Confinement effects and surface-induced charge carriers in Bi quantum wires

We present measurements of Shubnikov–de Haas oscillations in arrays of bismuth nanowires. For 80 nm wires, the hole concentration is less than 30% that of bulk Bi, a finding that is consistent with current models of quantum confinement effects. However, 30-nm-diam nanowires which are predicted to be semiconductors show a nearly isotropic short period of 0.025 T−1, consistent with a heavy carrier concentration five times that of bulk Bi. These results are discussed in terms of surface-induced charge carriers in a spherical Fermi surface pocket that are uniformly distributed in the 30 nm nanowire volume and that inhibit the semimetal-to-semiconductor transition.

Processing and Characterization of High-conductance Bismuth Wire Array Composites

We fabricated Bi nanowire array composites with wire diameters from 30 to 200 nm by high-pressure injection (HPI) of Bi melt into porous anodic alumina templates. The composites were dense, with Bi volume fraction in excess of 50%. The parallel Bi nanowires, whose length appeared to be limited only by the thickness of the host template (up to 55 μm), terminated at both sides of the composite in the Bi bulk. The individual Bi nanowire crystal structure was rhombohedral, with the same lattice parameters as that of bulk Bi; the wires in the array were predominantly oriented with the trigonal axis along the wire length. Low contact resistance was achieved by bonding the composite to copper electrodes.

Surface state band mobility and thermopower in semiconducting bismuth nanowires

Many thermoelectrics like Bi exhibit Rashba spin-orbit surface bands for which topological insulator behavior consisting of ultrahigh mobilities and enhanced thermopower has been predicted. Bi nanowires realize surface-only electronic transport since they become bulk insulators when they undergo the bulk semimetal-semiconductor transition as a result of quantum confinement for diameters close to 50 nm. We studied 20-, 30-, 50- and 200-nm trigonal Bi wires. Shubnikov-de Haas magnetoresistance oscillations caused by surface electrons and bulklike holes enable the determination of their densities and mobilities. Surface electrons have high mobilities exceeding 2(m^2)/(Vsec) and contribute strongly to the thermopower, dominating for temperatures T< 100 K. The surface thermopower is - 1.2 T microvolt/(K^2), a value that is consistent with theory, raising the prospect of developing nanoscale thermoelectrics based on surface bands.

Quantum interference of surface states in bismuth nanowires probed by the Aharonov-Bohm oscillatory behavior of the magnetoresistance

We report the observation of a dependence of the low temperature resistance of individual single-crystal bismuth nanowires on the Aharonov-Bohm phase of the magnetic flux threading the wire. 55 and 75-nm wires were investigated in magnetic fields of up to 14 T. For 55 nm nanowires, longitudinal magnetoresistance periods of 0.8 and 1.6 T that were observed at magnetic fields over 4 T are assigned to h/2e to h/e magnetic flux modulation. The same modes of oscillation were observed in 75-nm wires. The observed effects are consistent with models of the Bi surface where surface states give rise to a significant population of charge carriers of high effective mass that form a highly conducting tube around the nanowire. In the 55-nm nanowires, the Fermi energy of the surface band is estimated to be 15 meV. An interpretation of the magnetoresistance oscillations in terms of a subband structure in the surface states band due to quantum interference in the tube is presented.

Magnetic order in the pyrochlore iridates A(2)Ir(2)O(7) (A = Y, Yb)

We present results from muon spin relaxation/rotation, magnetization, neutron scattering, and transport measurements on polycrystalline samples of the pyrochlore iridates Y2Ir2O7 (Y-227) and Yb2Ir2O7 (Yb-227). Well-defined spontaneous oscillations of the muon asymmetry are observed together with hysteretic behavior in magnetization below 130 K in Yb-227, indicative of commensurate long-range magnetic order. Similar oscillations are observed in Y-227 below 150 K; however, the onset of hysteretic magnetization at T = 190 K indicates a transition to an intermediate state lacking long-range order as observed in Nd-227. Our results also show that insulating members of the iridate family have nearly identical magnetic ground states, and that the presence of magnetic A-site species does not play any significant role in altering the ground-state properties.

Weak magnetism phenomena in heavy-fermion superconductors: selected µSR studies

The behaviour of the so-called weak-moment antiferromagnetic states, observed in the heavy-fermion superconductors UPt3 and URu2Si2, is discussed in view of recent ?SR results obtained as functions of control parameters such as chemical substitution and external pressure. In UPt3, the Pd substitution for Pt reveals the dynamical character of the weak-moment order. On the other hand, ?SR measurements performed on samples in which Th substitutes U suggest that crystallographic disorder on the magnetic sites deeply affects the fluctuation timescale. In URu2Si2, a phase separation between the so-called hidden order state, present at ambient pressure, and an antiferromagnetic state, occurring under pressure, is observed. In view of the pressure?temperature phase diagram obtained by ?SR, it is deduced that the respective order parameters have different symmetries.

Observation of three-dimensional behavior in surface states of bismuth nanowires and the evidence for bulk-Bi surface quasiparticles

We studied trigonal Bi nanowires

Magnetic quantum critical point and superconductivity in UPt3 doped with Pd.

(30\text{ }\text{nm}l\text{diameter}l200\text{ }\text{nm})

Short-range correlations in the magnetic ground state of na4ir3 O8

via low-temperature magnetotransport for fields up to 14 T in order to investigate the role of their surfaces. A two-dimensional behavior was expected; we found instead a three-dimensional behavior, with a rich spectrum of Landau levels in a nearly spherical Fermi surface. We show that recent observations of sharp peaks in the bulk-Bi Nernst thermopower near the 9 T quantum limit attributed to charge fractionalization, can be more plausibly interpreted in terms of surface states. Bismuth has a true quantum limit at around 70 T.