Single crystal surfaces probed by polarized nuclei

Nuclear magnetic resonance has developed into a very powerful technique to study the structure and dynamics of atomic and molecular systems, both in liquid and solid phase. However the investigation of single crystal surfaces with “conventional” NMR methods is essentially impossible due to the small sample size of less than 10¹⁵ sites on a cm². To overcome this for the important class of alkali adsorbates on metals and semiconductors, two methods are presented. Common to both is the preparation of a highly nuclear spin polarized atomic beam of ⁶Li in the one case and ⁸Li in the other. The latter isotope is radioactive and undergoes a \beta‐decay with a halflife of 0.84 s. Li adsorbed on the close packed Ru(001) surface is investigated. The T{in1} relaxation rate is the main observable and is used to deduce the local electronic density of states (LDOS(E_F,r=0)) and the Li diffusion barriers at low and high adsorbate coverage. The second experiment uses ⁶Li as an adsorbate, also studied on Ru(001). The nuclear polarization is measured by beam foil spectroscopy. A novel particle detected (photon counting) Fourier‐Transform NMR technique is demonstrated, by observing the time dependent flux of circularly polarized light emitted behind the foil after a 90^\circ‐pulse has been employed at the surface. Development and prospects of the latter technique are presented. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nuclear depolarization of alkali beams during ionization on surfaces

The depolarization of atomic alkali beams (⁶Li,⁷Li,²³Na) during ionization on oxygen covered hot metal surfaces (Ir, Mo, Re, W) has been investigated. The polarization of the ionized beams was detected by a beam foil experiment. The temperature dependence of the observed depolarization is interpreted as due to a relaxation process caused by the interaction of the nuclear moments with fluctuating fields on the surface.     

Nuclear quadrupole resonance study of heavy fermion superconductors

By using nuclear quadrupole resonance (NQR), nuclear spin-lattice relaxation rate 1 /T₁ of the heavy fermion superconductors (URu₂Si₂, UPd₂Al₃, CeRu₂) has been measured. The NQR measurement requires no external field, and is especially suitable for ¹⁰⁵Pd and ¹⁰¹Ru, which have very small nuclear gyromagnetic ratios and large electric quadrupole moments. In URu₂Si₂ and UPd₂Al₃, the absence of the Hebel–Slichter coherence peak just below the superconducting transition temperature T_C and the power law temperature dependence (T³) in the superconducting state has shown appearance of anisotropic non-s-wave superconductivity. On the contrary, an exponential temperature dependence of 1/T₁ was observed in CeRu₂, indicating the superconductivity to be conventional s-wave. This revised version was published online in August 2006 with corrections to the Cover Date.     

La NMR and As NQR study of the As-based filled skutterudite LaOs4As12

We report experimental results of nuclear magnetic resonance (NMR) at the La site and nuclear quadrupole resonance (NQR) at the As site in the normal state of the superconducting compound LaOs₄As₁₂. Measurements have been performed on powder sample obtained from high quality single crystals. The temperature dependences of the nuclear spin-lattice relaxation rates, 1/T₁, of ⁷⁵As and ¹³⁹La nuclei were measured. No scaling between them was found indicating a local character of relaxation processes. The relaxation of ⁷⁵As nuclei can consistently be understood in terms of antiferromagnetic spin fluctuations, as deduced from the T-dependence of (1/T₁T)=C/(T−θ)^1/2.     

Hyperfine quantum beat of short-lived beta-emitter8Li polarized by the tilted foil technique

To disclose the basic mechanisms of nuclear polarization creation realized by the tilted foil technique, hyperfine quantum beats of the nuclear polarization of the short-lived beta-emitter⁸Li(I =2⁺,T _1/2=840 ms) were measured as a function of the distance between two tilted foils. From the observed beats of the⁸Li nuclear polarization, it was found that the Fermi-contact interaction of the⁸Li nucleus with the ground 1s-electron in LiIII plays a main role in the final stage of polarization transfer from polarized orbital electrons to the⁸Li nucleus.     

NMR studies of magnetic superconductor RuSr2RECu2O8 (RE=Gd, Eu and Y)

We have carried out ^99/101Ru and ^63/65Cu nuclear magnetic resonance experiments in order to investigate magnetic and electronic properties of the magnetic superconductor RuSr₂RECu₂O₈ (RE=Gd, Eu and Y). The two kinds of ^99/101Ru signals were observed in the magnetically ordered state for each system, suggesting a charge segregation of Ru⁵⁺ (S=3/2) and Ru⁴⁺ (S=1) ions in the RuO₂ layers. The internal field at the Cu sites is revealed to be of the order of kilo Oe, indicating weak magnetic interactions between the CuO₂ and RuO₂ planes. The temperature dependence of nuclear spin-lattice relaxation time T₁ of ⁶³Cu in RE=Y shows a ‘spin gap’ like behavior, suggesting the system is under-doped.     

Microscopic evidence for co-ionic conductivity in (Na,Li) β-alumina

Measurements of nuclear spin-lattice relaxation times T₁ as a function of temperature are reported for ⁷Li in Liβ-alumina and mixed (Na,Li) β-alumina at several frequencies. In the mixed case the T₁ data exhibit a nearly symmetric minimum below room temperature. For Liβ-alumina the T₁ curve has, in addition, a high-temperature “shoulder” or unresolved secondary minimum which corresponds to the activation energy and attempt frequency obtained from tracer diffusion and Raman spectroscopy, respectively. We conclude that the addition of Na eliminates this high-barrier diffusional motion of the Li ions, in accord with electrochemical studies. Our results are discussed in terms of competing models which describe nuclear spin-lattice relaxation.     

Low-temperature spin-lattice relaxation of8Li in the glass Li2O·2SiO2

Nuclear spin-lattice relaxation in Li₂0·2Si0₂ glass below 200 K has been studied using the asymmetric Β-decay radiation of polarized⁸Li (T_1/2=0.Bs) nuclei produced by capture of polarized neutrons. Transients of the⁸Li polarization follow an exp(?√E/T₁) law. The dependence of the spin-lattice relaxation rate ⊥_¯1 ¹ on temperature T and magnetic field B can roughly be described by T_¯1 ¹～T/B. The interpretation is based on the assumption that for⁸Li, contrary to⁷Li in the same glass, spin-diffusion is absent and that each probe nucleus is coupled by quadrupolar interaction to an individual distribution of nearby centres typical of glasses. The fluctuation of these centres causing relaxation may be induced by either a multi-phonon or a thermally activated motional process.     

Mechanism of 3He-mediated nuclear spin-lattice relaxation at surfaces

We measured the nuclear spin-lattice relaxation time T₁, of several surface-bound nuclei, ¹H, ¹⁹F, ¹¹B, ¹³C, ²⁹Si, and ²H, immersed in liquid ³He over the temperature range 0.01 K ⩽ T < 1 K. The Larmor frequencies of these nuclei in a 3.39 T field extended from 22 to 144 MHz. All T₁ values were temperature-independent and ranged from a few seconds to several hours, depending on the particular nucleus and the surface geometry of the sample. The results indicate that the coupled relaxation of surface spins is a phenomenon occurring in all solids immersed in ³He and thus provides a general mechanism for obtaining high nuclear polarization in solids, that the relaxation is controlled by direct dipole-dipole interactions between the surface spins and ³He in the first surface layer, that the ³He motion dynamics do not change appreciably from one surface to another, and that measurements of T₁ may thus be useful for determining the structure of surfaces.     

Nuclear spin lattice relaxation of58CoFe and60CoFe measured by the thermal cycling method

Thermal cycling of thin foil samples is used to measure nuclear spin lattice relaxation of dilute⁵⁸Co and⁶⁰Co in iron at polarizing fields up to 1.3 T. The relaxation rates for the two isotopes differ by a factor of 7.1; the good agreement between the high field values for ² C ₂, (2.93±0.15)·10¹⁵ K·s^–1·T^–2 (⁵⁸Co) and (3.01±0.06)·10¹⁵K·s^–1·T^–2 (⁶⁰Co) verifies the reliability of the experimental method. An enhancement factor model is introduced and shown to give an excellent reproduction of the observed field dependence of the relaxation.     

Mechanical detection of nuclear spin relaxation in a micron-size crystal

A room temperature nuclear magnetic resonance force microscope (MRFM), fitted in a 1 tesla electromagnet, has been used to measure the nuclear spin relaxation of ¹H in a micron-size (70 ng) crystal of ammonium sulfate. NMR sequences, combining both pulsed and continuous wave radio-frequency fields, have allowed us to measure mechanically T₂ and T₁, the transverse and longitudinal spin relaxation times. Because two spin species with different T₁ values are measured in our 7 μm thick crystal, magnetic resonance imaging of their spatial distribution inside the sample section have been performed. To understand quantitatively the measured signal, we carefully study the influence of spin-lattice relaxation and non-adiabaticity of the continuous-wave sequence on the intensity and time dependence of the detected signal. Received 23 February 2000     

Interaction between chemisorbed N2 and Li promoter atoms: A comparison between the stepped Ru(1 0 9) and the atomically smooth Ru(0 0 1) surfaces

We present a direct side-by-side comparison of the interaction of Li atoms and N₂ molecules on the atomically stepped Ru(1 0 9) single crystal surface and on the atomically smooth Ru(0 0 1) single crystal surface using infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD). At low adsorbate coverages there is spectroscopic evidence for the formation of a Li_x(N₂)_y complex on the Ru(1 0 9) surface, whereas no such complex is observed on the Ru(0 0 1) surface. This complex is due to local interactions between an adsorbed Li atom and N₂ adsorbed on the atomic steps of Ru(1 0 9). The short range interaction near the atomic steps is characterized by the development of several highly red-shifted ν(N₂) modes in the region of ∼2130 cm⁻¹ in the IR spectra. Adsorbed N₂ molecules on both Ru(1 0 9) and Ru(0 0 1) also are influenced by the long range electrostatic field produced by Li adsorbate atoms, causing a red shift in the uncomplexed N₂ species, which monotonically increases as the Li coverage in increased. On the Ru(0 0 1) surface, small coverages of N₂ influenced by the long range effect of Li are initially chemisorbed parallel to the surface resulting in the absence of infrared activity. In addition we have also found that Li does not cause N-N bond scission on Ru(0 0 1) below 250 K.     

NMR study of pure and doped β-LiAl

The NMR spin-lattice relaxation time, T_I, has been measured as a function of temperature for both ⁷Li and ²⁷Al in pure and doped β-LiAl alloys. Compositions with ⁷Li concentration in the range 48.3–54.5% and doping in the form Li₅₀Al_50?xM_x, where M = Ag or In, were studied. The relaxation rates T₁^?1 for the ²⁷Li and the ²⁷Al resonances were found to be peaked functions of temperature with the maxima for ⁷Li appearing at composition dependent temperatures. The ²⁷Al maxima always appeared at a lower temperature, independent of composition, and the ²⁷Al maximum relaxation rate was a strong function of composition in contrast with ⁷Li where the maximum rate was only weakly dependent on composition. The principle relaxation mechanisms are identified as dipole-dipole coupling in the ⁷Li and coupling of the ²⁷Al quadrupole moment to electric field gradients. The temperature dependence of these rates is attributed to the thermally activated diffusion of vacancies of a non-thermal origin in the Li sub-lattice. These vacancies are also responsible for the fluctuating electric field gradients. The results have been analyzed to give the Li diffusion coefficients with associated activation energies and estimates of the vacancy concentration as functions of alloy composition.     

NMR observation of critical dynamics in the (TMTSF)2PF6 organic superconductor

We have studied the organic superconductor (TMTSF)₂PF₆ using ¹H nuclear magnetic resonance. The spin-lattice (T₁) and the spin-spin relaxation time (T₂) measurements manifested a divergence associated with a structural phase transition at 160 K.     

Nuclear Spin-Lattice Relaxation of 82BrFe

The field dependence of the nuclear spin-lattice relaxation (SLR) of cold implanted ⁸²Br (T ≤ 25 mK) in α-Fe single crystals was investigated with nuclear magnetic resonance of oriented nuclei (NMR/ON) at low temperatures as experimental technique. The SLR at the lattice sites with the hyperfine fields found by earlier NMR/ON experiments was measured as a function of the applied external magnetic field B _ext parallel to the three principle axes [100], [110] and [111] of the iron single crystal. The data were evaluated with the full relaxation formalism in the single impurity limit and for comparison also with the often employed model of a single exponential function with an effective relaxation time T ₁′. With a phenomenological model the high field values of the relaxation rates r _{∞, [100]′} = 6.6(2) · 10⁻¹⁵ T²sK⁻¹, r _{∞, [110]} = 5.4(2) · 10⁻¹⁵ T²sK⁻¹ and r _{∞, [111]} = 5.2(1) · 10⁻¹⁵ T²sK⁻¹ were obtained.     

Hyperfine interactions of short-lived β-emitter 8Li in ferromagnetic Ni

Hyperfine interactions of ⁸Li impurity nucleus imbedded in ferromagnetic Ni metal were studied using the β-NMR technique. Two kinds of hyperfine fields B₈₂ were found, corresponding to two different final sites of Li atoms in the Ni lattice. The nuclear spin-lattice relaxation times T₁ of ⁸Li in Ni were also determined for each field. Temperature dependencies of B₈₂ and T₁ were observed to deduce these values at T=0 K that can be compared with those calculated recently by Akai et al. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase transition and relaxation processes by 87Rb and 39K nuclear magnetic measurements of RbKSO4 single crystals

⁸⁷Rb and ³⁹K nuclear magnetic resonance (NMR) spectra of RbKSO₄ single crystals were measured at room temperature. ⁸⁷Rb central line has the angular dependences of second-order quadrupolar shifts. From these results, the quadrupole coupling constant and the asymmetry parameter were determined at room temperature. In addition, the spin–lattice relaxation rate, 1/T₁, and the spin–spin relaxation rate, 1/T₂, were measured as a function of temperature. The values of 1/T₁ for the ⁸⁷Rb and ³⁹K nuclei were found to increase with increasing temperature, and 1/T₁ was determined to be proportional to Tⁿ. Therefore, for the ⁸⁷Rb and ³⁹K nuclei, Raman processes with n=2 are more significantly in nuclear quadrupole relaxation than direct processes.     

Nuclear spin dependence of polarization enhancement by multi-tilted foils studied by short-lived beta-emitters8B and12B

In order to study the basic mechanism of polarization enhancement realized by the multitilted foil technique, nuclear polarization of short-lived beta-emitter⁸B(T_1/2=769 ms,I =2⁺) was induced. Utilizing up to ten tilted foils, the polarization enhancement was measured as a function of the foil numbers. The observed enhancement for⁸B was combined with the previous results for¹²B(I =1⁺,T _1/2=20 ms) which has the same atomic configurations but different nuclear spin. Analyzing these results in the framework of the classical vector model, the essential features of the enhancement depending on the nuclear spin was disclosed.     

Ion-beam-assisted MBE growth of semi-spherical SiGe/Si nano-structures

Semi-spherical SiGe/Si nano-structures of a new type are presented. Epitaxial islands of 30–40 nm in base diameter and 11 nm in height and having a density of about 6×10¹⁰ cm^-2 were produced on (001) Si by molecular beam epitaxial growth of Si/Si_0.5Ge_0.5 layers with in situ implantation of 1-keV As⁺ ions. It was found by cross-section transmission electron microscopy that the islands have a complicated inner structure and consist of a micro-twin nucleus and semi-spherical nano-layers of various SiGe compositions. The nature of the surface patterning is interpreted by stress relaxation through implantation-induced defects. Received: 12 July 2001 / Accepted: 4 September 2001 / Published online: 2 October 2001     

Li and K NMR relaxation study of a LiKSO4 single crystal

The ⁷Li and ³⁹K NMR relaxations in a LiKSO₄ single crystal grown by the slow evaporation method were investigated by employing a pulse NMR spectrometer. From the experimental data, the quadrupole coupling constant and asymmetry parameter were determined at the temperatures of 180 and 300 K. The relaxation processes of ⁷Li and ³⁹K were studied for the LiKSO₄ crystal, and the relaxation times for the ⁷Li and ³⁹K nuclei exhibit remarkable changes near T_c2 (=190 K). The activation energies for ⁷Li and ³⁹K were determined in phases I and III. The large change in the activation energy at 190 K indicates that the Li and K ions are significantly affected during this transition. The correlation time of the ⁷Li calculated from the spin-lattice relaxation time and quadrupole parameters was larger than that of the ³⁹K calculated using the same method. The reason for this is that the Li ion undergoes molecular motion as in the LiO₄ groups.