Magnetization-recovery experiments for static and MAS-NMR of I=3/2 nuclei

Multifrequency pulsed NMR experiments on quadrupole-perturbed I=3/2 spins in single crystals are shown to be useful for measuring spin-lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of (71)Ga and (69)Ga (both I=3/2) spin-lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I=3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process (T(1Q1)) and a double-quantum process (T(1Q2)), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process (T(1M)). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal (71)Ga data alone. The (69)Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to (71)Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T(1Q1) and T(1Q2) were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74 degrees ) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin-lattice relaxation. Comparison of (71)Ga and (69)Ga MAS-NMR saturation-recovery curves with both central and satellite transitions completely saturated by a train of 90 degrees pulses incommensurate with the rotor period provides the simplest means of assessing the contribution from magnetic relaxation, and yields results for the quadrupolar mechanism contribution that are consistent with those obtained from the film sample.     

Electrical and ionic conductivity effects on magic-angle spinning nuclear magnetic resonance parameters of CuI

We investigate experimentally and theoretically the effects of two different types of conductivity, electrical and ionic, upon magic-angle spinning NMR spectra. The experimental demonstration of these effects involves (63)Cu, (65)Cu, and (127)I variable temperature MAS-NMR experiments on samples of γ-CuI, a Cu(+)-ion conductor at elevated temperatures as well as a wide bandgap semiconductor. We extend previous observations that the chemical shifts depend very strongly upon the square of the spinning-speed as well as the particular sample studied and the magnetic field strength. By using the (207)Pb resonance of lead nitrate mixed with the γ-CuI as an internal chemical shift thermometer we show that frictional heating effects of the rotor do not account for the observations. Instead, we find that spinning bulk CuI, a p-type semiconductor due to Cu(+) vacancies in nonstoichiometric samples, in a magnetic field generates induced AC electric currents from the Lorentz force that can resistively heat the sample by over 200 °C. These induced currents oscillate along the rotor spinning axis at the spinning speed. Their associated heating effects are disrupted in samples containing inert filler material, indicating the existence of macroscopic current pathways between micron-sized crystallites. Accurate measurements of the temperature-dependence of the (63)Cu and (127)I chemical shifts in such diluted samples reveal that they are of similar magnitude (ca. 0.27 ppm/K) but opposite sign (being negative for (63)Cu), and appear to depend slightly upon the particular sample. This relationship is identical to the corresponding slopes of the chemical shifts versus square of the spinning speed, again consistent with sample heating as the source of the observed large shift changes. Higher drive-gas pressures are required to spin samples that have higher effective electrical conductivities, indicating the presence of a braking effect arising from the induced currents produced by rotating a conductor in a homogeneous magnetic field. We present a theoretical analysis and finite-element simulations that account for the magnitude and rapid time-scale of the resistive heating effects and the quadratic spinning speed dependence of the chemical shift observed experimentally. Known thermophysical properties are used as inputs to the model, the sole adjustable parameter being a scaling of the bulk thermal conductivity of CuI in order to account for the effective thermal conductivity of the rotating powdered sample. In addition to the dramatic consequences of electrical conductivity in the sample, ionic conductivity also influences the spectra. All three nuclei exhibit quadrupolar satellite transitions extending over several hundred kilohertz that reflect defects perturbing the cubic symmetry of the zincblende lattice. Broadening of these satellite transitions with increasing temperature arises from the onset of Cu(+) ion jumps to sites with different electric field gradients, a process that interferes with the formation of rotational echoes. This broadening has been quantitatively analyzed for the (63)Cu and (65)Cu nuclei using a simple model in the literature to yield an activation barrier of 0.64 eV (61.7 kJ/mole) for the Cu(+) ion jumping motion responsible for the ionic conductivity that agrees with earlier results based on (63)Cu NMR relaxation times of static samples.     

Distributions of conduction electrons as manifested in MAS NMR of gallium nitride

A strategy is demonstrated for identifying unambiguously and characterizing quantitatively the effects of distributions of conduction electron concentrations arising from intentional or unintentional dopants in semiconductors by magic-angle spinning (MAS) NMR. The 71Ga MAS NMR spectra of a number of chemically synthesized GaN samples with no intentional doping show inhomogeneously broadened absorptions to high frequency of the main peak. These broad signals are shown, from spin-lattice relaxation time measurements as a function of shift position in a single sample, to be due to Knight shifts arising from degenerate conduction electrons. For a GaN sample with Ge as an intentional dopant at the 0.13% (wt) level, the spectrum is dramatically broadened and shifted to high frequency by up to several hundred parts per million. Analysis of the inhomogeneously broadened line shape yields a quantitative probability density function for electron carrier concentration in the bulk sample that reflects significant compositional heterogeneity due to a variety of possible sources.     

Depth-resolved X-ray determination of surface strain in free-standing films of HVPE-grown GaN and <Superscript>71</Superscript>Ga NMR characterization

Free-standing GaN films grown by hydride vapor phase epitaxy (HVPE) on c-plane sapphire have been studied for in-plane anisotropic strain. Lattice parameters are obtained from high-resolution X-ray diffraction data and the film quality is determined by measuring the rocking curves and by ⁷¹Ga nuclear magnetic resonance (NMR). The in-plane strain was determined using grazing incidence X-ray diffraction and conventional X-ray measurements. It is found that the in-plane lattice parameter varies with depth and has estimated surface strain anisotropy of 4.0791×10^-3 up to a thickness of 0.3 μm. The ⁷¹Ga NMR experiments reveal different degrees of inhomogeneity amongst the three samples. This is shown by the appearance of an additional broad central-transition peak shifted to higher frequency by a Knight shift from conduction electrons in sample regions having high carrier concentrations. PACS 72.80.Ey; 61.10.-i; 61.72.Hh