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We investigate spin and optical properties of individual nitrogen-vacancy centers located within 1-10 nm from the diamond surface. We observe stable defects with a characteristic optically detected magnetic resonance spectrum down to lowest depth. We also find a small, but systematic spectral broadening for defects shallower than about 2 nm. This broadening is consistent with the presence of a surface paramagnetic impurity layer [Tisler et al., ACS Nano 3, 1959] largely decoupled by motional averaging. The observation of stable and well-behaved defects very close to the surface is critical for single-spin sensors and devices requiring nanometer proximity to the target.

We report a demonstration of two-dimensional (2D) terahertz (THz) magnetic resonance spectroscopy using the magnetic fields of two time-delayed THz pulses. We apply the methodology to directly reveal the nonlinear responses of collective spin waves (magnons) in a canted antiferromagnetic crystal. The 2D THz spectra show all of the third-order nonlinear magnon signals including magnon spin echoes, and 2-quantum signals that reveal pairwise correlations between magnons at the Brillouin zone center. We also observe second-order nonlinear magnon signals showing resonance-enhanced second-harmonic and difference-frequency generation. Numerical simulations of the spin dynamics reproduce all of the spectral features in excellent agreement with the experimental 2D THz spectra. DOI: 10.1103/PhysRevLett.118.207204 Nonlinear manipulation of spins is the basis for all advanced methods in magnetic resonance including multidimensional nuclear magnetic resonance and electron spin resonance (ESR) spectroscopies [1,2], magnetic resonance imaging, and, in recent years, quantum control over individual spins [3]. The methodology is facilitated by the ease with which the regime of strong coupling can be reached between radio frequency or microwave magnetic fields and nuclear or electron spins, respectively, typified by sequences of magnetic pulses that control the magnetic moment directions [1][2][3]. The capabilities meet a bottleneck, however, for far-infrared magnetic resonances characteristic of correlated electron materials, molecular magnets, and metalloproteins.ESR in the terahertz (THz) frequency region can reveal rich information content in chemistry, biology, and materials science [1,2,[4][5][6][7]. In molecular complexes and metalloproteins, THz-frequency zero-field splittings (ZFS) of high-spin transition-metal and rare-earth ions show exquisite sensitivity to ligand geometries, providing mechanistic insight into molecular magnetic properties [4] and protein catalytic function [5]. With strong applied magnetic fields (∼10 T), resonances of unpaired electron spins in molecular complexes can be shifted from the usual microwave regime into the THz range, drastically improving the resolution due to enhanced spectral splittings [2,6,7]. In many ferromagnetic (FM) and antiferromagnetic (AFM) materials, intrinsic magnetic fields in the same range put collective spin waves (magnons) in the THz range. Current ESR spectroscopy remains limited at THz frequencies because the weak sources used only permit measurements of free-induction decay (FID) signals that are linearly proportional to the excitation magnetic field strength. In some cases, including most proteins, even linear THz-frequency ESR signals may not be measurable because the THz spectrum includes much stronger absorption features due to low-frequency motions of polar segments [8]. However, the fast dephasing of such motions ensures that they would not compete with nonlinear spin echo signals [9]. Two-dimensional (2D) THz ESR spectroscopy, like 2D ESR at lower frequenci...

Materials research with a focus on enhancing the minority-carrier lifetime of the light-absorbing semiconductor is key to advancing solar energy technology for both early-stage and mature material platforms alike. Tin sulfide (SnS) is an absorber material with several clear advantages for manufacturing and deployment, but the record power conversion efficiency remains below 5%. We report measurements of bulk and interface minority-carrier recombination rates in SnS thin films using optical-pump, terahertz (THz)-probe transient photoconductivity (TPC) measurements. Post-growth thermal annealing in H2S gas increases the minority-carrier lifetime, and oxidation of the surface reduces the surface recombination velocity. However, the minoritycarrier lifetime remains below 100 ps for all tested combinations of growth technique and postgrowth processing. Significant improvement in SnS solar cell performance will hinge on finding and mitigating as-yet-unknown recombination-active defects. We describe in detail our methodology for TPC experiments, and we share our data analysis routines in the form freelyavailable software.For a more sophisticated solar cell figure of merit, we consider the dimensionless ratio (FPV) of minority-carrier diffusion length to optical absorption length:D is the minority carrier diffusivity,  is the bulk minority-carrier lifetime, and  is the optical absorption coefficient. In Figure 1b we present compiled data for FPV and solar cell efficiency, including results for wafer-based silicon technologies. With the exception of silicon, all of the materials represented strongly absorb light at energies above their respective band gaps. For each material we calculate FPV using  as measured at the knee the curve of log10((E)). For the thin film materials we require that lifetime, diffusivity, absorption coefficient, and device measurements were reported for samples that were synthesized in the same laboratory and using as close to the same procedure as is reasonably possible. This requirement greatly reduces the number of data points compared to Figure 1a. For crystalline silicon we assume the values D = 30 cm 2 s -1 and  = 300 cm -1 .SnS is an absorber with several inherent advantages compared to materials that are widely used in solar cells, but its demonstrated efficiency is too low for commercial relevance. It is composed of non-toxic, Earth-abundant and inexpensive elements. SnS is an inert and waterinsoluble semiconducting mineral (Herzenbergite) with an indirect bandgap of 1.1 eV, strong light absorption for photons with energy above 1.4 eV ( > 10 4 cm -1 ), and intrinsic p-type conductivity with carrier concentration in the range 10 15 -10 17 cm -3 . 5-7 SnS evaporates congruently and is phase-stable up to 600 °C. 8,9 This means that SnS thin films can be deposited by thermal evaporation and its high-speed cousin, closed space sublimation (CSS), as is employed in the manufacture of CdTe solar cells. It also means that SnS phase control is simpler than for most thin film PV materials, nota...

Complex systems, which consist of a large number of interacting constituents, often exhibit universal behavior near a phase transition. A slowdown of certain dynamical observables is one such recurring feature found in a vast array of contexts. This phenomenon, known as critical slowing down, is well studied mostly in thermodynamic phase transitions. However, it is less understood in highly nonequilibrium settings, where the time it takes to traverse the phase boundary becomes comparable to the timescale of dynamical fluctuations. Using transient optical spectroscopy and femtosecond electron diffraction, we studied a photo-induced transition of a model charge-densitywave (CDW) compound, LaTe3. We observed that it takes the longest time to suppress the order parameter at the threshold photoexcitation density, where the CDW transiently vanishes. This finding can be quantitatively captured by generalizing the time-dependent Landau theory to a system far from equilibrium. The experimental observation and theoretical understanding of dynamical slowing down may offer insight into other general principles behind nonequilibrium phase transitions in many-body systems.In a second-order symmetry-breaking phase transition, the spatial extent of fluctuating regions diverges close to the critical temperature, T c . Correspondingly, the relaxation time of these fluctuations tends to infinity, a phenomenon known as critical slowing down [1,2]. The phenomenology of slowing dynamics near a critical point is much more general: it has been observed in first-order transitions [3,4], glasses [5,6], dynamical systems [7], and even microbial communities [8]. Its common occurrence makes it a robust signature of phase transitions in a vast array of complex systems [9].Close to equilibrium, critical slowing down has been well characterized in condensed matter systems. Theoretically, it is described by a dynamical critical exponent, whose value depends on the dynamic universality class [2]. Experimentally, the evidence comes from a vanishing rate of change in the order parameter close to T c , with early reports in refs. [3,10,11]. While these measurements probe the slowing dynamics in the time domain, it can be observed in the frequency domain as well. For example, inelastic neutron scattering has revealed a narrowing quasi-elastic peak along the energy axis as T c is approached, indicating a suppressed relaxation rate of critical fluctuations [12][13][14]. Moreover, if there is a collective mode associated with the phase transition, the mode softening in the vicinity of T c is also taken as a signature of critical slowing down [15].For symmetry-breaking phase transitions in a highly nonequilibrium setting, the dynamics are much less understood. Recent studies have found important features in nonequilibrium transitions, such as topological defects, which are absent in their equilibrium counterparts [16][17][18]. Despite the differences, a slowdown in dynamics is thought to carry over to systems far from equilibrium. For example, in a rapid...

Multidimensional spectroscopy at visible and infrared frequencies has opened a window into the transfer of energy and quantum coherences at ultrafast time scales. For these measurements to be performed in a manageable amount of time, one spectral axis is typically recorded in a single laser shot. An analogous rapid-scanning capability for THz measurements will unlock the multidimensional toolkit in this frequency range. Here, we first review the merits of existing single-shot THz schemes and discuss their potential in multidimensional THz spectroscopy. We then introduce improved experimental designs and noise suppression techniques for the two most promising methods: frequency-to-time encoding with linear spectral interferometry and angle-to-time encoding with dual echelons. Both methods, each using electro-optic detection in the linear regime, were able to reproduce the THz temporal waveform acquired with a traditional scanning delay line. Although spectral interferometry had mediocre performance in terms of signal-to-noise, the dual echelon method was easily implemented and achieved the same level of signal-to-noise as the scanning delay line in only 4.5% of the laser pulses otherwise required (or 22 times faster). This reduction in acquisition time will compress day-long scans to hours and hence provides a practical technique for multidimensional THz measurements.

Intermolecular vibrations of amino acid crystals occur in the THz, or far-infrared, region of the electromagnetic spectrum. We have measured the THz and Raman spectra of DL-leucine as well as two polymorphs of DL-valine, the spectroscopic properties of which have not previously been compared. Theoretical modeling of intermolecular vibrations in hydrophobic amino acids is challenging because the van der Waals interactions between molecules are not accounted for in standard density functional theory. Therefore, to calculate the vibrational modes, we used a recently developed approach that includes these nonlocal electron correlation forces. We discuss methods for comparing results from different theoretical models using metrics other than calculated vibrational frequency and intensity, and we also report a new approach enabling concise comparison of vibrational modes that involve complicated mixtures of inter- and intramolecular displacements.

Key insights in materials at extreme temperatures and pressures can be gained by accurate measurements that determine the electrical conductivity. Free-electron laser pulses can ionize and excite matter out of equilibrium on femtosecond time scales, modifying the electronic and ionic structures and enhancing electronic scattering properties. The transient evolution of the conductivity manifests the energy coupling from high temperature electrons to low temperature ions. Here we combine accelerator-based, high-brightness multi-cycle terahertz radiation with a single-shot electro-optic sampling technique to probe the evolution of DC electrical conductivity using terahertz transmission measurements on sub-picosecond time scales with a multi-undulator free electron laser. Our results allow the direct determination of the electron-electron and electron-ion scattering frequencies that are the major contributors of the electrical resistivity.