Nuclear hyperpolarization in the liquid state by dynamic nuclear polarization (DNP) has been of great interest because of its potential use in NMR spectroscopy of small samples of biological and chemical compounds in aqueous media. Liquid state DNP generally requires microwave resonators in order to generate an alternating magnetic field strong enough to saturate electron spins in the solution. As a consequence, the sample size is limited to dimensions of the order of the wavelength, and this restricts the sample volume to less than 100 nL for DNP at 9 T (∼260 GHz). We show here a new approach that overcomes this sample size limitation. Large saturation of electron spins was obtained with a high-power (∼150 W) gyrotron without microwave resonators. Since high power microwaves can cause serious dielectric heating in polar solutions, we designed a planar probe which effectively alleviates dielectric heating. A thin liquid sample of 100 μm of thickness is placed on a block of high thermal conductivity aluminum nitride, with a gold coating that serves both as a ground plane and as a heat sink. A meander or a coil were used for NMR. We performed H DNP at 9.2 T (∼260 GHz) and at room temperature with 10 μL of water, a volume that is more than 100× larger than reported so far. TheH NMR signal is enhanced by a factor of about -10 with 70 W of microwave power. We also demonstrated the liquid state of P DNP in fluorobenzene containing triphenylphosphine and obtained an enhancement of ∼200.

An increase in Dynamic Nuclear Polarization (DNP) signal intensity is obtained with a tunable gyrotron producing frequency modulation around 260GHz at power levels less than 1W. The sweep rate of frequency modulation can reach 14kHz, and its amplitude is fixed at 50MHz. In water/glycerol glassy ice doped with 40mM TEMPOL, the relative increase in the DNP enhancement was obtained as a function of frequency-sweep rate for several temperatures. A 68 % increase was obtained at 15K, thus giving a DNP enhancement of about 80. By employing λ/4 and λ/8 polarizer mirrors, we transformed the polarization of the microwave beam from linear to circular, and achieved an increase in the enhancement by a factor of about 66% for a given power.

A 550-fold increase in the liquid state (13)C NMR signal of a 50μL sample was obtained by first hyperpolarizing the sample at 20K using a gyrotron (260GHz), then, switching its frequency in order to apply 100W for 1.5s so as to melt the sample, finally, turning off the gyrotron to acquire the (13)C NMR signal. The sample stays in its NMR resonator, so the sequence can be repeated with rapid cooling as the entire cryostat stays cold. DNP and thawing of the sample are performed only by the switchable and tunable gyrotron without external devices. Rapid transition from DNP to thawing in one second time scale was necessary especially in order to enhance liquid (1)H NMR signal.

We demonstrate opto-spintronics using Fe-doped Indium Phosphide (InP). The method is based on optical orientation of InP conduction electron spins which are electrically detected in planar InP/ oxide/Ni tunnel spin filters. We separate the optical excitation from electrical detection, avoiding thus additional interactions of photons with the ferromagnet. Interface engineering provides a surface iron accumulation and semiconducting Fe:In 2 O 3 in the oxide tunnel barrier. The spin filtering effect switches to positive or negative asymmetry, depending on the Fe concentration in Fe x :InP. With respect to the Fe-like electronic structure of these oxides, we can explain the opposite spin selection mechanisms as interface effects. In the temperature region where the InP mobility peaks, we find a maximum of spin-dependent asymmetry of ∼9% in semi-insulating Fe:InP (001), and show the electrical spin detection in hyperpolarized InP also at room temperature. Such robust electronic spin detection in an InP nanodevice is planned to complement dynamic nuclear polarization experiments.

260-GHz radiation is used for a quasi-optical electron spin resonance (ESR) spectrometer which features both field and frequency modulation. Free space propagation is used to implement Martin-Puplett interferometry with quasi-optical isolation, mirror beam focusing, and electronic polarization control. Computer-aided design and polarization pathway simulation lead to the design of a compact interferometer, featuring lateral dimensions less than a foot and high mechanical stability, with all components rated for power levels of several Watts suitable for gyrotron radiation. Benchmark results were obtained with ESR standards (BDPA, DPPH) using field modulation. Original high-field ESR of 4f electrons in Sm3+-doped Ceria was detected using frequency modulation. Distinct combinations of field and modulation frequency reach a signal-to-noise ratio of 35 dB in spectra of BDPA, corresponding to a detection limit of about 1014 spins.