Defects and impurities in nanodiamonds: EPR, NMR and TEM study

EPR, ¹³C NMR and TEM study of ultradisperse diamond (UDD) samples is reported. The compounds show a high concentration of paramagnetic centers (up to 10²⁰ spin/g), which are due to structural defects (dangling C-C bonds) on the diamond cluster surface. The anomalous reduction in the spin-lattice relaxation time of ¹³C (from several hours in natural diamond to ∼150 ms in UDD clusters) is attributed to the interaction between the unpaired electrons of the paramagnetic centers and nuclear spins. ¹³C NMR line-width reflects the fact that the structure of the UDD surface is distorted in comparison to the ‘bulk’ diamond structure.     

F NMR and EPR study of fluorinated buckminsterfullerene C60F58

Solid state ¹⁹F NMR in the temperature range from 96 to 366 K and room temperature EPR studies of fluorinated buckminsterfullerene C₆₀F₅₈ have been carried out. The temperature dependence of the line width and the spin-lattice relaxation time show hindered molecular motion with the activation energy of ΔE_a=1.9 kcal/mol. Neither phase transition nor random rotation of C₆₀F₅₈ have been obtained. The spin-lattice relaxation rate is strongly affected by the presence of paramagnetic centers, namely, dangling C-C bonds yielding localized unpaired electrons. Such broken bonds are caused by C-C bond rupture in a cage-opened structure of hyperfluorinated species.     

Cs nuclear magnetic resonance study in CsZnCl3 single crystals of perovskite ABX3 type

CsZnCl₃ single crystals were grown by the slow evaporation method, and the spin-lattice relaxation rates and resonance lines of the ¹³³Cs nuclei in the resulting crystals were investigated using FT NMR spectrometry. The temperature dependence of the relaxation rate of the ¹³³Cs nuclei in the CsZnCl₃ crystals was found to be continuous near T_C (=366 K), and was not affected by this phase transition. Our results for CsZnCl₃ are compared with those obtained previously for other CsBCl₃ (B=Mn, Cu, and Cd) perovskite crystals. The Cs relaxation time of CsCdCl₃ is longer than that of CsMnCl₃. The differences between the atomic weights of Mn, Cu, Zn, and Cd are responsible for the differences between the spin-lattice relaxation times of these single crystals. The influence of paramagnetic ions is also important in these crystals. The differences between the spin-lattice relaxation times of these crystals could also be due to differences between the electron structures of their metal ions, in particular the structures of the d electrons.     

Proton NMR and susceptibility measurements on the magnetic core of ferritin

We report an investigation of the magnetic core of the biomolecule ferritin by means of proton nuclear magnetic resonance (NMR) and relaxation, magnetic susceptibility and scanning electron microscope (SEM) measurements. SEM images show that the outer protein shell is taken out completely by an appropriate chemical treatment and indicate particle sizes ranging from 10² to 10⁴ nm. Susceptibility measurements show a maximum in the zero-field-cooled data which is strongly field-dependent and can be ascribed to superparamagnetic behavior, whereas the hysteresis curve is different from normal ferritin. Proton NMR and spin-lattice relaxation data as a function of temperature at 4.7 T suggest the presence of an antiferromagnetic transition around 100 K.     

19F nuclear spin relaxation and spin diffusion effects in the single-ion magnet LiYF4:Ho3+

Temperature and magnetic field dependences of the ¹⁹F nuclear spin-lattice relaxation in a single crystal of LiYF₄ doped with holmium are described by an approach based on a detailed consideration of the magnetic dipole-dipole interactions between nuclei and impurity paramagnetic ions and nuclear spin diffusion processes. The observed non-exponential long time recovery of the nuclear magnetization after saturation at intermediate temperatures is in agreement with predictions of the spin-diffusion theory in a case of the diffusion limited relaxation. At avoided level crossings in the spectrum of electron-nuclear states of Ho^{3 +} ions, rates of nuclear spin-lattice relaxation increase due to quasi-resonant energy exchange between nuclei and paramagnetic ions in contrast to the predominant role played by electronic cross-relaxation processes in the low-frequency ac-susceptibility.     

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     

Study of synthetic diamonds by dynamic nuclear polarization-enhanced13C nuclear magnetic resonance spectroscopy

Four I_b-type synthetic diamond crystals were studied by dynamic nuclear polarization (DNP)-enhanced high resolution solid state¹³C nuclear magnetic resonance (NMR) spectroscopy. The home built DNP magic-angle-spinning (MAS) NMR spectrometer operates at a field strength of 1.9 T and the highest DNP enhancement factor of synthetic diamonds came near to 10³. Comparing with I_b-type natural diamonds, the¹³C NMR linewidths of synthetic diamonds in static spectra are broader. The¹³C spin-lattice relaxation time and DNP polarization time of synthetic diamond are shorter than those of I_b-type natural diamond. From the hyperfine structure of the DNP enhancement curve, four kinds of nitrogen-centred free radicals could be identified in synthetic diamond.     

Density functional calculations of dangling bonds for CN and SiN films

Hyperfine interaction constants (HFICs) of dangling bonds for CN and SiN films were calculated by density-functional theory. The averaged ¹⁴N isotropic HFICs for C dangling bonds are almost equal to those for Si dangling bonds. The anisotropic ¹⁴N HFICs calculated for C dangling bonds are larger than those for Si dangling bonds by a factor 2. The calculated results were compared with experimental results obtained by electron spin resonance and electron nuclear double resonance. It was indicated that the carbon dangling bonds are located such that they avoid N atoms in CN films.     

Nuclear magnetic resonance study of the relaxation mechanisms of the Be, Al, and Si nuclei in Cr-doped Be3Al2Si6O18 crystals

The variations with temperature of the relaxation mechanisms of the ⁹Be, ²⁷Al, and ²⁹Si nuclei in emerald (Be₃Al₂Si₆O₁₈:Cr³⁺) single crystals were investigated by using a pulse NMR spectrometer. The values of the spin-lattice relaxation rates for the three nuclei are different, and these differences are attributed to the differences between their Larmor frequencies and their local nuclear environments. The relaxation rates of the ⁹Be and ²⁷Al nuclei undergo no abrupt changes within the temperature range 180-400 K, which indicates that there are no phase transitions within this temperature range. The spin-lattice relaxation rates of ⁹Be and ²⁷Al were found to be proportional to temperature. Therefore, the nuclear spin-lattice relaxation processes of these two nuclei proceed via single-phonon processes.     

X-ray absorption spectroscopy study of pulsed-laser-evaporated amorphous carbon films

Amorphous carbon (a-C) films obtained by pulsed-laser ablation of graphite have been investigated by X-ray Absorption Spectroscopy (XAS). The onset of 1s ^* transitions in the films lies in the gap between the ^* and ^* bands in graphite and very close to the absorption edge of diamond, indicating a high content ofsp ³ hybridization. A sharp feature at this onset is observed and assigned to a core exciton insp ³-hybridized disordered C atoms. Its shift of 0.5 eV with respect to the core exciton in diamond is probably due to a higher localization of the excited electron induced by disorder. A small peak coming from C–H bonds at the surface is observed and its intensity inereases with the amount ofsp ³-hybridized atoms in the sample. This can be easily explained by associating a higher amount of dangling bonds at the surface to a highersp ³ content. Polarization-dependent XAS measurements show that the angular distribution of these C–H bonds has a mean value close to the normal to the surface.     

Nuclear spin-lattice relaxation in ferromagnetic amorphous alloys Fe81Co3B16 andFe70Co10B20 measured by NMR and Nuclear orientation

The nuclear spin-lattice relaxation of⁵⁹Co in amorphous Fe-Co-B alloys was studied by NMR andthe results were compared with nuclear orientation measurements. The NMR relaxation rates were evaluated taking into account the electric quadrupole interaction. Then the results of both methods are in good agreement. It was confirmed that the spin-lattice relaxation is independent of the external magnetic field in the magnetically saturated samples andit was found that it does not depend on Co concentration.     

Nuclear magnetic relaxation by regularly distributed dense paramagnetic ions in a quasi-two-dimensional system

The ¹H nuclear spin-lattice relaxation behavior was characterized in the perovskite-type layered structure quasi-two-dimensional Heisenberg paramagnets, (C_nH_2n+1NH₃)₂MnCl₄,with different chain lengths (n=8, 10, and 12). In contrast to the case of the short-chain compound with n=8, the nuclear spin diffusion to the electron spin system alone is not able to fully account for the spin-lattice relaxation in the compounds with longer chain lengths. Our results are discussed in light of the nuclear magnetic relaxation by the regularly distributed dense paramagnetic ions.     

Study of the Interaction Between Trypanocide 3-Nitrobenzaldehyde Guanyl Hydrazone and Bovine Serum Albumin by Equilibrium Dialysis and Nmr

Equilibrium dialysis and NMR spin-lattice relaxation time (T¹) studies of the interaction of the trypanocidal drug 3-nitrobenzaldehyde guanyl hydrazone (3NBGH) with bovine serum albumin (BSA) were used to show that this interaction is weak and nonspecific, making 3NBGH a potential agent for the prophylaxis of Trypanosoma cruzi infected blood.     

Locations of implanted 19F* atoms in Si,Ge and diamond studied through their nuclear quadrupole interactions

The Hartree-Fock cluster procedure was used to obtain the associated electronic distributions for ¹⁹F^* (I = 5/2, E ^x = 197 KeV excited nuclear state of the ¹⁹F atom) at possible sites in crystalline Si, Ge and diamond and to calculate nuclear quadrupole coupling constants v _Q and the asymmetry parameter η of the electric field gradient at the modelled sites. Lattice relaxation effects have been incorporated by employing a geometry optimization method to obtain minimum energy configurations for the clusters modelling each site. The intrabond (IB), antibonding (AB) and substitutional (S) sites in the bulk and the atop site on the surface were studied. From a comparison with v _Q and η values observed in time differential perturbed angular distribution (TDPAD) measurements we were able to identify the high frequency component in Si and Ge with ¹⁹F^* at the intrabond site. In diamond two high frequency components are observed. These are identified with ¹⁹F^* at intrabond and substitutional sites. For the low frequency site in Si and Ge the assignment is made to ¹⁹F^* implants at dangling bonds in the bulk resulting from implantation damage. In diamond none of the sites studied could provide lower frequency nuclear quadrupole parameters close to the observed ones. This revised version was published online in August 2006 with corrections to the Cover Date.     

35Cl NQR and2H NMR analysis of the critical dynamics close to the displacive normal-incommensurate phase transition in an organic crystal

Nuclear magnetic resonance (NMR) experiments,³⁵C1 nuclear quadrupole resonance (NQR) and²H NMR, have been performed close to the displacive normal-incommensurate phase transition in the organic crystal of bis-(4-chlorophenyl)-sulfone. Calculations using coherent neutron scattering results show that the soft-mode contribution cannot explain the rapid increase of the spin-lattice relaxation rates close to the transition temperature. Calculations of the spectral densities taking into account the existence of a central-peak phenomenon describe both³⁵C1 NQR and²H NMR spin-lattice relaxation rates on approaching the phase transition. In this way, the width of the central peak can be estimated to be in the range of several gigahertz.     

Proton NMR study of α-MnH0.06

Proton nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates for the solid solution α-MnH_0.06 have been measured over the temperature range 11-297 K and the resonance frequency range 20-90 MHz. A considerable shift and broadening of the proton NMR line and a sharp peak of the spin-lattice relaxation rate are observed near 130 K. These effects are attributed to the onset of antiferromagnetic ordering below the Néel temperature T_N≈130 K. The proton NMR line does not disappear in the antiferromagnetic phase; this suggests a small magnitude of the local magnetic fields at H-sites in α-MnH_0.06. The spin-lattice relaxation rate in the paramagnetic phase is dominated by the effects of spin fluctuations.     

Local composition and carrier concentration in Pb0.7Ge0.3Te and Pb0.5Ge0.5Te alloys from Te NMR and microscopy

Pb_0.7Ge_0.3Te and Pb_0.5Ge_0.5Te alloys, (i) quenched from 923 K or (ii) quenched and annealed at 573 K for 2 h, have been studied by ¹²⁵Te NMR, X-ray diffraction, electron and optical microscopy, as well as energy dispersive spectroscopy. Depending on the composition and thermal treatment history, ¹²⁵Te NMR spectra exhibit different resonance frequencies and spin-lattice relaxation times, which can be assigned to different phases in the alloy. Quenched and annealed Pb_0.7Ge_0.3Te alloys can be considered as solid solutions but are shown by NMR to have components with various carrier concentrations. Quenched and annealed Pb_0.5Ge_0.5Te alloys contain GeTe- and PbTe-based phases with different compositions and charge carrier concentrations. Based on the analysis of non-exponential ¹²⁵Te NMR spin-lattice relaxation, the fractions and carrier concentrations of the various phases have been estimated. Our data show that alloying of PbTe with Ge results in the formation of chemically and electronically inhomogeneous systems. ¹²⁵Te NMR can be used as an efficient probe to detect the local composition in equilibrium as well as non-equilibrium states, and to determine the local carrier concentrations in complex multiphase tellurides.     

Simultaneous interaction of methyl radicals and atomic hydrogen with amorphous hydrogenated carbon films, as investigated with optical in situ diagnostics

Methyl radicals (CH₃) and atomic hydrogen (H) are dominant radicals in low-temperature plasmas from methane. The surface reactions of these radicals are believed to be key steps leading to deposition of amorphous hydrogenated carbon (a-C:H) films or polycrystalline diamond in these discharges. The underlying growth mechanism is studied, by exposing an a-C:H film to quantified radical beams of H and CH₃. The deposition or etching rate is monitored via ellipsometry and the variation of the stoichiometry is monitored via isotope labeling and infrared spectroscopy. It was shown recently that, at 320 K, methyl radicals have a sticking coefficient of 10^-4 on a-C:H films, which rises to 10^-2 if an additional flux of atomic hydrogen is present. This represents a synergistic growth mechanism between H and CH₃. From the interpretation of the infrared data, a reaction scheme for this type of film growth is developed: atomic hydrogen creates dangling bonds by abstraction of bonded hydrogen within a surface layer corresponding to the range of H in a-C:H films. These dangling bonds serve at the physical surface as adsorption sites for incoming methyl radicals and beneath the surface as radicalic centers for polymerization reactions leading to carbon–carbon bonds and to the formation of a dense a-C:H film. Received: 18 July 2000 / Accepted: 12 December 2000 / Published online: 3 April 2001     

Optorelaxers: Achieving real-time control of NMR relaxation

We present an approach to increase the detection sensitivity of NMR by shortening the spin-lattice relaxation time using transient paramagnetic species created by light irradiation of “optorelaxer” molecules. In the ultimate implementation of this concept, not yet realized here, these transient species are absent during the detection period, thereby avoiding the loss of spectral resolution caused by inhomogeneous broadening from paramagnetic species. Real-time control of NMR relaxation by visible light is demonstrated with Fe(II)(ptz)₆(BF₄)₂, (ptz = 1-propyltetrazole), abbreviated FePTZ. Illumination of FePTZ at 30 K results in a decrease of the ¹H NMR spin-lattice relaxation time T₁ due to formation of a high spin photoexcited state. The ¹H NMR of polystyrene containing a low concentration of FePTZ molecules shows a similar reduction in T₁, establishing that FePTZ can act as an optorelaxer for the protons of a matrix. Numerical modeling of the spin-diffusion processes from the protons in a FePTZ core to those in a shell of polystyrene accounts for the observed T₁ effects under both dark and light conditions. Additionally, ¹H MAS (magic-angle spinning) NMR results for pure FePTZ provide information on the isotropic and anisotropic portions of the electron-nuclear hyperfine interactions.     

Temperature dependence of the spin-lattice relaxation time for quadrupole nuclei under conditions of NMR line saturation

The contributions of different mechanisms of nuclear spin-lattice relaxation are experimentally separated for ⁶⁹Ga and ⁷¹Ga nuclei in GaAs crystals (nominally pure and doped with copper and chromium), ²³Na nuclei in a nominally pure NaCl crystal, and ²⁷Al nuclei in nominally pure and lightly chromium-doped Al₂O₃ crystals in the temperature range 80–300 K. The contribution of impurities to spin-lattice relaxation is separated under the condition of additional stationary saturation of the nuclear magnetic resonance (NMR) line in magnetic and electric resonance fields. It is demonstrated that, upon suppression of the impurity mechanism of spin-lattice relaxation, the temperature dependence of the spin-lattice relaxation time T₁ for GaAs and NaCl crystals is described within the model of two-phonon Raman processes in the Debye approximation, whereas the temperature dependence of T₁ for corundum crystals deviates from the theoretical curve for relaxation due to the spin-phonon interaction.