Efficient dynamic nuclear polarization at high magnetic fields

By applying a new technique for dynamic nuclear polarization involving simultaneous excitation of electronic and nuclear transitions, we have enhanced the nuclear polarization of the nitrogen nuclei in 15N@C60 by a factor of 10(3) at a fixed temperature of 3 K and a magnetic field of 8.6 T, more than twice the maximum enhancement reported to date. This methodology will allow the initialization of the nuclear qubit in schemes exploiting N@C60 molecules as components of a quantum information processing device.     

Proton polarization with p-terphenyl crystal by integrated solid effect on photoexcited triplet state

We have carried out the experiments for polarizing protons in single crystals of p-terphenyl doped with 0.1 mol% pentacene. The experiments have been performed in a magnetic field of 3 kG at room temperature or at 77 K. We obtained the polarization of 1.3% for protons in bulk at room temperature by using a pulsed dye-laser with the wavelength of 590 nm, the average power of 150 mW, and the repetition rate of 50 Hz. The polarization at 77 K reached 18% by irradiation with the dye-laser of 500 mW, 50 Hz and the same wavelength. The polarization of protons was measured by the neutron transmission method also. The result was consistent with that measured by the nuclear magnetic resonance.     

Spectroscopic issues in optical polarization of 3He gas for Magnetic Resonance Imaging of human lungs

The Magnetic Resonance Imaging (MRI) of human lungs for diagnostic purposes became possible by using nuclear spin hyperpolarized noble gases, such as ³He. One of the methods to polarize ³He is the Metastability Exchange Optical Pumping (MEOP), which up to now has been performed at low pressure of about 1 mbar and in low magnetic field below 0.1 T (standard conditions). The equilibrium nuclear polarization can reach up to 80%, but it is dramatically reduced during the subsequent gas compression to the atmospheric pressure that is necessary for the lungs examination. Further polarization losses occur during the transportation of the gas to the hospital scanner. It was shown recently that up to 50% polarization can be obtained at elevated pressure exceeding 20 mbar, by using magnetic field higher than 0.1 T (nonstandard conditions). Therefore, following the construction of the low-field MEOP polarizer located in the lab, a dedicated portable unit was developed, which uses the magnetic field of the 1.5 T MR medical scanner and works in the continuous-flow regime. The first in Poland MRI images of human lungs in vivo were obtained on the upgraded to ³He resonance frequency Siemens Sonata medical scanner. An evident improvement in the image quality was achieved when using the new technique. The paper shows how spectroscopic measurements of ³He carried out in various experimental conditions led both to useful practical results and to significant progress in understanding fundamental processes taking place during MEOP.     

High-frequency dynamic nuclear polarization in the nuclear rotating frame

A proton dynamic nuclear polarization (DNP) NMR signal enhancement (epsilon) close to thermal equilibrium, epsilon = 0.89, has been obtained at high field (B(0) = 5 T, nu(epr) = 139.5 GHz) using 15 mM trityl radical in a 40:60 water/glycerol frozen solution at 11 K. The electron-nuclear polarization transfer is performed in the nuclear rotating frame with microwave irradiation during a nuclear spin-lock pulse. The growth of the signal enhancement is governed by the rotating frame nuclear spin-lattice relaxation time (T(1rho)), which is four orders of magnitude shorter than the nuclear spin-lattice relaxation time (T(1n)). Due to the rapid polarization transfer in the nuclear rotating frame the experiment can be recycled at a rate of 1/T(1rho) and is not limited by the much slower lab frame nuclear spin-lattice relaxation rate (1/T(1n)). The increased repetition rate allowed in the nuclear rotating frame provides an effective enhancement per unit time(1/2) of epsilon(t) = 197. The nuclear rotating frame-DNP experiment does not require high microwave power; significant signal enhancements were obtained with a low-power (20 mW) Gunn diode microwave source and no microwave resonant structure. The symmetric trityl radical used as the polarization source is water-soluble and has a narrow EPR linewidth of 10 G at 139.5 GHz making it an ideal polarization source for high-field DNP/NMR studies of biological systems.     

Spin polarization of the neutral exciton in a single quantum dot

While efficient nuclear polarization has earlier been reported for the charged exciton in InAs/GaAs quantum dots at zero external magnetic field, we report here on a surprisingly high degree of circular polarization, up to ≈60%$\approx 60\%$, for the neutral exciton emission in individual InAs/GaAs dots. This high degree of polarization is explained in terms of the appearance of an effective nuclear magnetic field which stabilizes the electron spin. The nuclear polarization is manifested in experiments as a detectable Overhauser shift. In turn, the nuclei located inside the dot are exposed to an effective electron magnetic field, the Knight field. This nuclear polarization is understood as being due to the dynamical nuclear polarization by an electron localized in the QD. The high degree of polarization for the neutral exciton is also suggested to be due to separate in-time capture of electrons and holes into the QD.     

Dynamic nuclear polarization in silicon microparticles

We report record high 29Si spin polarization obtained using dynamic nuclear polarization in microcrystalline silicon powder. Unpaired electrons in this silicon powder are due to dangling bonds in the amorphous region of this intrinsically heterogeneous sample. 29Si nuclei in the amorphous region become polarized by forced electron-nuclear spin flips driven by off-resonant microwave radiation while nuclei in the crystalline region are polarized by spin diffusion across crystalline boundaries. Hyperpolarized silicon microparticles have long T1 relaxation times and could be used as tracers for magnetic resonance imaging.     

NMR at earth's magnetic field using para-hydrogen induced polarization

A method to achieve NMR of dilute samples in the earth's magnetic field by applying para-hydrogen induced polarization is presented. Maximum achievable polarization enhancements were calculated by numerically simulating the experiment and compared to the experimental results and to the thermal equilibrium in the earth's magnetic field. Simultaneous 19F and 1H NMR detection on a sub-milliliter sample of a fluorinated alkyne at millimolar concentration (～10(18) nuclear spins) was realized with just one single scan. A highly resolved spectrum with a signal/noise ratio higher than 50:1 was obtained without using an auxiliary magnet or any form of radio frequency shielding.     

Huge transverse magnetic polarization in the field-induced phase of the antiferromagnetic molecular wheel CsFe(8)

The 1H NMR spectrum and nuclear relaxation rate T(1)(-1) in the antiferromagnetic wheel CsFe8 were measured to characterize the previously observed magnetic field-induced low-temperature phase around the level crossing at 8 T. The data show that the phase is characterized by a huge staggered transverse polarization of the electronic Fe spins, and the opening of a gap, providing microscopic evidence for the interpretation of the phase as a field-induced magnetoelastic instability.     

Nuclear relaxation in dynamic nuclear polarization

The behavior of nuclear polarization in a substance, i.e., a solution of the complex HMBA(Cr^V)Na⁺ in 1,2-propylene glycol used in polarized nuclear targets is experimentally investigated by magnetic spectroscopic methods under conditions of dynamic nuclear polarization at hv_S/kT=≈1.5−3.2. Nuclear polarization is measured and analyzed as a function of time at different values of the saturating microwave signal and temperature. It is shown that the process of decreasing the nuclear polarization involving free nuclear relaxation is described by a nonmonoexponential law with two damping decrements, which determine the time of reaching equilibrium between the Zeeman nuclear subsystem, the dipole-dipole pool, and the lattice. Specific features of dynamic processes proceeding in the electronic-nuclear system of the substance investigated are discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 363–366, May–June, 1997.     

Spin-labeled gel for the production of radical-free dynamic nuclear polarization enhanced molecules for NMR spectroscopy and imaging

Dynamic nuclear polarization (DNP) has recently received much attention as a viable approach to enhance the sensitivity of nuclear magnetic resonance (NMR) spectroscopy and the contrast of magnetic resonance imaging (MRI), where the significantly higher electron spin polarization of stable radicals is transferred to nuclear spins. In order to apply DNP-enhanced NMR and MRI signal to biological and in vivo systems, it is crucial to obtain highly polarized solution samples at ambient temperatures. As stable radicals are employed as the source for the DNP polarization transfer, it is also crucial that the highly polarized sample lacks residual radical concentration because the polarized molecules will be introduced to a biological system that will be sensitive to the presence of radicals. We developed an agarose-based porous media that is covalently spin-labeled with stable radicals. The loading of solvent accessible radical is sufficiently high and their mobility approximates that in solution, which ensures high efficiency for Overhauser mechanism induced DNP without physically releasing any measurable radical into the solution. Under ambient conditions at 0.35 T magnetic field, we measure the DNP enhancement efficiency of (1)H signal of stagnant and continuously flowing water utilizing immobilized stable nitroxide radicals that contain two or three ESR hyperfine splitting lines and compare them to the performance of freely dissolved radicals.     

Experiments with neutron polarization analysis

Neutron polarization analysis experiments of the past 25 years are reviewed. In that time the technique has progressed from a curiosity to being a useful tool to be used when needed. In early experiments, the polarization of the scattered beam was analysed in the same direction as the polarization of the incident beam but, in some later experiments, full three-dimensional polarization analysis has been employed. This article starts by writing down the interactions which the neutron has with condensed matter and deriving the cross-sections for scattering and final polarizations of the scattered beam. This is done displaying the spin state functions of the neutron explicitly. A variety of experiments is then reviewed, commencing with the elastic and inelastic scattering experiments performed by Moon, Riste and Koehler in the late 1960s. Elastic scattering experiments where it is important to separate nuclear and magnetic cross-sections such as antiferromagnetic defect scattering are reviewed together with separation out of the nuclear spin scattering for various purposes. Of particular interest are the fully three-dimensional analysis experiments which reveal more about the structure and domain populations of certain antiferromagnets. Inelastic experiments for which polarization analysis is vital are those on paramagnets at high temperatures where it is necessary to discriminate against phonon scattering. Spin glasses are treated as frozen paramagnets. Polarization analysis also has another role to play in the separation of magnetic modes in both paramagnets and ordered magnets, and several of these experiments are reviewed. Finally it is possible to tag the polarization of a neutron beam in time and space and to measure the result at another time and place and this through various techniques yields information about the change in neutron energy on scattering. The techniques of pseudo-random flipping time of flight, neutron spectral modulation and neutron spin-echo spectroscopy are briefly reviewed but the techniques of polarized-neutron-beam management are left to another review.     

Theoretical treatment of pulsed Overhauser dynamic nuclear polarization: Consideration of a general periodic pulse sequence

A general theoretical approach to pulsed Overhauser-type dynamic nuclear polarization (DNP) is presented. Dynamic nuclear polarization is a powerful method to create non-thermal polarization of nuclear spins, thereby enhancing their nuclear magnetic resonance signals. The theory presented can treat pulsed microwave irradiation of electron paramagnetic resonance transitions for periodic pulse sequences of general composition. Dynamic nuclear polarization enhancement is analyzed in detail as a function of the microwave pulse length for rectangular pulses and pulses with finite rise time. Characteristic oscillations of the DNP enhancement are found when the pulse-length is stepwise increased, originating from coherent motion of the electron spins driven by the pulses. Experimental low-field DNP data are in very good agreement with this theoretical approach.     

Optical measurement of <Superscript>3</Superscript>He nuclear polarization for metastable exchange optical pumping studies at high magnetic field

An accurate optical method to measure the nuclear polarization of ³He atoms in the 1¹S ground state is described. The absorption of a weak, probe laser beam is used to measure the relative populations of two hyperfine sublevels of the 2³S metastable state that are not addressed by the pumping laser beam. Since a common spin temperature between the ground and metastable states is established by metastable exchange collisions, the nuclear polarization can be derived from these absorption measurements. The method is highly sensitive, robust, and can be used to monitor the dynamics of optical pumping and relaxation processes without interfering with them. It was successfully implemented and tested in the 0.45–2.0 T magnetic field range at the ³He gas pressure up to 67 mbar.     

Pulsed magnetic field method for measuring polarization of radioactive beams

A new method has been developed for measuring the magnitude of nuclear spin polarization of a secondary, radioactive beam by making a pulsed magnetic field measurement that does not require advance knowledge of the nuclide's magnetic moment. Using a standard β NMR apparatus, a magnetic double ratio is determined from the counting rates in 0° and 180° β detectors for magnetic field on and off conditions. This ratio provides direct information on the induced spin polarization of a radioactive beam. A demonstration of the method was performed using spin polarized ¹²B nuclei produced by fragmentation of an 80 MeV/nucleon ¹⁸O beam in a Nb target. This revised version was published online in August 2006 with corrections to the Cover Date.     

Optical nuclear polarization in heavy-doped silicon

The unusual behaviour of the optical polarization degree of ²⁹Si nuclei as a function of the illumination time has been found in silicon single crystals heavily doped with gadolinium. The effect of an external magnetic field on the process of optical nuclear polarization has been studied. It has been shown that the presence of second phase precipitations in heavily doped silicon leads to the complex unexponential establishment of the optical nuclear polarization degree with illumination time.     

Microwave-induced optical nuclear polarization in Si:P:B

The first successful experiments of microwave-induced optical nuclear polarization in compensated silicon are presented. Bound holes are created at the boron sites using band-gap light of 1.047 μm. Subsequently, the high spin polarization of these bound holes is transferred to the ²⁹Si nuclei using microwave irradiation, resulting in an enhancement of the nuclear magnetic resonance signal. It is shown that a long lifetime of the nuclear spin polarization thus created is obtained, once the excitation light is shut off.     

Dynamic nuclear polarization and nuclear orientation in an antiferromagnet

Dynamic nuclear polarization is a well established technique which has been used to produce polarized targets for experiments in nuclear physics. This paper suggests experiments of a similar type but involving the nuclear magnetic resonance of two isotopes, one stable and the other radioactive. The substance is an antiferromagnet, dysprosium phosphate, at temperatures below the Néel point, where line widths are comparatively small. The effect may be detected through changes in the rate of gamma ray emission observed by a nuclear orientation experiment.     

Dynamics of nuclear polarization in InGaAs quantum dots in a transverse magnetic field

The time-resolved Hanle effect is examined for negatively charged InGaAs/GaAs quantum dots. Experimental data are analyzed by using an original approach to separate behavior of the longitudinal and transverse components of nuclear polarization. This made it possible to determine the rise and decay times of each component of nuclear polarization and their dependence on transverse magnetic field strength. The rise and decay times of the longitudinal component of nuclear polarization (parallel to the applied field) were found to be almost equal (approximately 5 ms). An analysis of the transverse component of nuclear polarization shows that the corresponding rise and decay times differ widely and strongly depend on magnetic field strength, increasing from a few to tens of milliseconds with an applied field between 20 and 100 mT. Current phenomenological models fail to explain the observed behavior of nuclear polarization. To find an explanation, an adequate theory of spin dynamics should be developed for the nuclear spin system of a quantum dot under conditions of strong quadrupole splitting.     

Dynamic nuclear polarization at 9T using a novel 250GHz gyrotron microwave source

In this communication, we report enhancements of nuclear spin polarization by dynamic nuclear polarization (DNP) in static and spinning solids at a magnetic field strength of 9T (250 GHz for g=2 electrons, 380 MHz for 1H). In these experiments, 1H enhancements of up to 170+/-50 have been observed in 1-13C-glycine dispersed in a 60:40 glycerol/water matrix at temperatures of 20K; in addition, we have observed significant enhancements in 15N spectra of unoriented pf1-bacteriophage. Finally, enhancements of approximately 17 have been obtained in two-dimensional 13C-13C chemical shift correlation spectra of the amino acid U-13C, 15N-proline during magic angle spinning (MAS), demonstrating the stability of the DNP experiment for sustained acquisition and for quantitative experiments incorporating dipolar recoupling. In all cases, we have exploited the thermal mixing DNP mechanism with the nitroxide radical 4-amino-TEMPO as the paramagnetic dopant. These are the highest frequency DNP experiments performed to date and indicate that significant signal enhancements can be realized using the thermal mixing mechanism even at elevated magnetic fields. In large measure, this is due to the high microwave power output of the 250 GHz gyrotron oscillator used in these experiments.     

170 nm nuclear magnetic resonance imaging using magnetic resonance force microscopy

We demonstrate one-dimensional nuclear magnetic resonance imaging of the semiconductor GaAs with 170 nm slice separation and resolve two regions of reduced nuclear spin polarization density separated by only 500 nm. This was achieved by force detection of the magnetic resonance, magnetic resonance force microscopy (MRFM), in combination with optical pumping to increase the nuclear spin polarization. Optical pumping of the GaAs created spin polarization up to 12 times larger than the thermal nuclear spin polarization at 5K and 4T. The experiment was sensitive to sample volumes of 50 microm(3) containing approximately 4 x 10(11)71 Ga/Hz. These results demonstrate the ability of force-detected magnetic resonance to apply magnetic resonance imaging to semiconductor devices and other nanostructures.