Daniela Pagliero

Time-resolved, optically detected NMR of fluids at high magnetic field

We report on the use of optical Faraday rotation to monitor the nuclear-spin signal in a set of model (19)F- and (1)H-rich fluids. Our approach integrates optical detection with high-field, pulsed NMR so as to record the time-resolved evolution of nuclear-spins after rf excitation. Comparison of chemical-shift-resolved resonances allows us to set order-of-magnitude constrains on the relative amplitudes of hyperfine coupling constants for different bonding geometries. When evaluated against coil induction, the present detection modality suffers from poorer sensitivity, but improvement could be attained via multipass schemes. Because illumination is off-resonant i.e., the medium is optically transparent, this methodology could find extensions in a broad class of fluids and soft condensed matter systems.

Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

We use optical Faraday rotation (OFR) to probe nuclear spins in real time at high-magnetic field in a range of diamagnetic sample fluids. Comparison of OFR-detected NMR spectra reveals a correlation between the relative signal amplitude and the fluid Verdet constant, which we interpret as a manifestation of the variable detuning between the probe beam and the sample optical transitions. The analysis of chemical-shift-resolved, optically detected spectra allows us to set constraints on the relative amplitudes of hyperfine coupling constants, both for protons at chemically distinct sites and other lower-gyromagnetic-ratio nuclei including carbon, fluorine, and phosphorous. By considering a model binary mixture we observe a complex dependence of the optical response on the relative concentration, suggesting that the present approach is sensitive to the solvent-solute dynamics in ways complementary to those known in inductive NMR. Extension of these experiments may find application in solvent suppression protocols, sensitivity-enhanced NMR of metalloproteins in solution, the investigation of solvent-solute interactions, or the characterization of molecular orbitals in diamagnetic systems.

Recursive polarization of nuclear spins in diamond at arbitrary magnetic fields

We introduce an alternate route to dynamically polarize the nuclear spin host of nitrogen-vacancy (NV) centers in diamond. Our approach articulates optical, microwave and radio-frequency pulses to recursively transfer spin polarization from the NV electronic spin. Using two complementary variants of the same underlying principle, we demonstrate nitrogen nuclear spin initialization approaching 80% at room temperature both in ensemble and single NV centers. Unlike existing schemes, our approach does not rely on level anti-crossings and is thus applicable at arbitrary magnetic fields. This versatility should prove useful in applications ranging from nanoscale metrology to sensitivity-enhanced NMR.

Imaging nuclear spins weakly coupled to a probe paramagnetic center

Optically-detected paramagnetic centers in wide-bandgap semiconductors are emerging as a promising platform for nanoscale metrology at room temperature. Of particular interest are applications where the center is used as a probe to interrogate other spins that cannot be observed directly. Using the nitrogen-vacancy center in diamond as a model system, we propose a new strategy to determining the spatial coordinates of weakly coupled nuclear spins. The central idea is to label the target nucleus with a spin polarization that depends on its spatial location, which is subsequently revealed by making this polarization flow back to the NV for readout. Using extensive analytical and numerical modeling, we show that the technique can attain high spatial resolution depending on the NV lifetime and target spin location. No external magnetic field gradient is required, which circumvents complications resulting from changes in the direction of the applied magnetic field, and considerably simplifies the required instrumentation. Extensions of the present technique may be adapted to pinpoint the locations of other paramagnetic centers in the NV vicinity or to yield information on dynamical processes in molecules on the diamond surface.

Approach to high-frequency, cavity-enhanced Faraday rotation in fluids

Recent work demonstrating detection of nuclear spin magnetization via Faraday rotation in transparent fluids promises novel opportunities for magnetic resonance imaging and spectroscopy. Unfortunately, low sensitivity is a serious concern. With this motivation in mind, we explore the use of an optical cavity to augment the Faraday rotation experienced by a linearly polarized beam traversing a sample fluid. Relying on a setup that affords reduced sample size and high-frequency modulation, we demonstrate amplification of regular (i.e., nonnuclear) Faraday rotation of order 20. Extensions of the present methodology that take into account the geometric constraints imposed by a high-field magnet may open the way to high-sensitivity, optically-detected magnetic resonance in the liquid state.

Orientation-independent room temperature optical 13C hyperpolarization in powdered diamond

Shining light on diamond particles makes them MRI-“bright,” opening avenues for room temperature hyperpolarized liquids. Dynamic nuclear polarization via contact with electronic spins has emerged as an attractive route to enhance the sensitivity of nuclear magnetic resonance beyond the traditional limits imposed by magnetic field strength and temperature. Among the various alternative implementations, the use of nitrogen vacancy (NV) centers in diamond—a paramagnetic point defect whose spin can be optically polarized at room temperature—has attracted widespread attention, but applications have been hampered by the need to align the NV axis with the external magnetic field. We overcome this hurdle through the combined use of continuous optical illumination and a microwave sweep over a broad frequency range. As a proof of principle, we demonstrate our approach using powdered diamond with which we attain bulk 13C spin polarization in excess of 0.25% under ambient conditions. Remarkably, our technique acts efficiently on diamond crystals of all orientations and polarizes nuclear spins with a sign that depends exclusively on the direction of the microwave sweep. Our work paves the way toward the use of hyperpolarized diamond particles as imaging contrast agents for biosensing and, ultimately, for the hyperpolarization of nuclear spins in arbitrary liquids brought in contact with their surface.

Controlled growth of (100) or (111) CdTe epitaxial layers on (100) GaAs by molecular beam epitaxy and study of their electron spin relaxation times

The authors demonstrate control of the crystalline orientation [(100) or (111)] of molecular beam epitaxy-grown CdTe films on (100) ZnSe/GaAs substrates. Reflection high-energy electron diffraction is used to observe the nucleation of the epitaxial layers in situ during growth. X-ray diffraction and photoluminescence measurements indicate that in both cases, the CdTe film is of high structural quality despite the large lattice constant mismatch of 14.3% between CdTe and ZnSe. They also use time-resolved Kerr rotation to monitor the electron spin dynamics in these films. While the spin lifetime is found to depend on material quality, only (100) films show a clear temperature dependence, a peculiar feature they believe to arise from residual strain.

Spin dynamics of ZnSe-ZnTe nanostructures grown by migration enhanced molecular beam epitaxy

We study the spin dynamics of ZnSe layers with embedded type-II ZnTe quantum dots using time resolved Kerr rotation (TRKR). Three samples were grown with an increasing amount of Te, which correlates with increased quantum dot (QD) density. Samples with a higher quantum dot density exhibit longer electron spin lifetimes, up to ∼1 ns at low temperatures. Tellurium isoelectronic centers, which form in the ZnSe spacer regions as a result of the growth conditions, were probed via spectrally dependent TRKR. Temperature dependent TRKR results show that samples with high QD density are not affected by an electron-hole exchange dephasing mechanism.

Rapid prototyping of a liquid-core waveguide in a microfluidic polydimethylsiloxane channel for optical sensing

Abstract. This paper presents a simple fabrication method for a liquid-core optofluidic waveguide and demonstrates efficient light delivery and collection using optical fibers pressure-sealed into a polydimethylsiloxane matrix. Total optical loss as small as 3 dB from an input optical fiber with a core diameter of 9 μm to an output optical fiber with a core diameter of 62.5 μm connected one to another via a 2 cm long liquid-core optofluidic channel is achieved. This strategy allows rapid prototyping of optofluidic waveguides without requiring expensive microfabrication facilities and is suitable for applications that require an efficient optical sensing in a small liquid sample. As a demonstration, we examine the optical Faraday rotation of a fluid sample and identify advantages and limitations by comparison to a macroscopic system of similar length.