Optical and Electrical Properties of A3[VS4] (A = Na, K) Synthesized via a Straightforward and Scalable Solid-State Method.

Two literature-known sulfido vanadates, Na3[VS4] and K3[VS4], were obtained through a straightforward and scalable synthetic method. Highly crystalline powders of both compounds were obtained from the homogeneous molten phases of starting materials via a─comparably rapid─solid-state technique. Low-temperature structure determination, ambient temperature powder diffraction, and solid-state NMR spectroscopy verify previous structural reports and indicate purity of the obtained samples. Both compounds show semiconductivity with the optical band gap values in the range of 2.1 to 2.3 eV. Experimental values of the ionic conductivity and dielectric constants are σ = 2.41·10-5 mS·cm-1, k = 76.52 and σ = 1.36·10-4 mS·cm-1, k = 103.67 at ambient temperature for Na3[VS4] and K3[VS4], respectively. It is demonstrated that Na3[VS4] depicts second-order nonlinear optical properties, i.e., second harmonic generation over a broad wavelength spectrum. The results introduce new aspects of sulfido vanadates as multifunctional candidates for potential optical and electrical applications.

Small electron polarons bound to interstitial tantalum defects in lithium tantalate.

The absorption features of optically generated, short-lived small bound electron polarons are inspected in congruent lithium tantalate, LiTaO3(LT), in order to address the question whether it is possible to localize electrons at interstitial TaV:VLidefect pairs by strong, short-range electron-phonon coupling. Solid-state photoabsorption spectroscopy under light exposure and density functional theory are used for an experimental and theoretical access to the spectral features of small bound polaron states and to calculate the binding energies of the small bound TaLi4+(antisite) and TaV4+:VLi(interstitial site) electron polarons. As a result, two energetically well separated (ΔE≈0.5 eV) absorption features with a distinct dependence on the probe light polarization and peaking at 1.6 eV and 2.1 eV are discovered. We contrast our results to the interpretation of a single small bound TaLi4+electron state with strong anisotropy of the lattice distortion and discuss the optical generation of interstitial TaV4+:VLismall polarons in the framework of optical gating of TaV4+:TaTa4+bipolarons. We can conclude that the appearance of carrier localization at TaV:VLimust be considered as additional intermediate state for the 3D hopping transport mechanisms at room temperature in addition to TaLi, as well, and, thus, impacts a variety of optical, photoelectrical and electrical applications of LT in nonlinear photonics. Furthermore, it is envisaged that LT represents a promising model system for the further examination of the small-polaron based photogalvanic effect in polar oxides with the unique feature of two, energetically well separated small polaron states.

Gap-Free Tuning of Second and Third Harmonic Generation in Mechanochemically Synthesized Nanocrystalline LiNb1-xTaxO3 (0 ≤ x ≤ 1) Studied with Nonlinear Diffuse Femtosecond-Pulse Reflectometry.

The tuning of second (SHG) and third (THG) harmonic emission is studied in the model system LiNb 1-xTa xO 3 (0≤x≤1, LNT) between the established edge compositions lithium niobate (LiNbO 3, x=0, LN) and lithium tantalate (LiTaO 3, x=1, LT). Thus, the existence of optical nonlinearities of the second and third order is demonstrated in the ferroelectric solid solution system, and the question about the suitability of LNT in the field of nonlinear and quantum optics, in particular as a promising nonlinear optical material for frequency conversion with tunable composition, is addressed. For this purpose, harmonic generation is studied in nanosized crystallites of mechanochemically synthesized LNT using nonlinear diffuse reflectometry with wavelength-tunable fundamental femtosecond laser pulses from 1200 nm to 2000 nm. As a result, a gap-free harmonic emission is validated that accords with the theoretically expected energy relations, dependencies on intensity and wavelength, as well as spectral bandwidths for harmonic generation. The SHG/THG harmonic ratio ≫1 is characteristic of the ferroelectric bulk nature of the LNT nanocrystallites. We can conclude that LNT is particularly attractive for applications in nonlinear optics that benefit from the possibility of the composition-dependent control of mechanical, electrical, and/or optical properties.

Remarkable Infrared Nonlinear Optical, Dielectric, and Strong Diamagnetic Characteristics of Semiconducting K3[BiS3].

The ternary sulfido bismuthate K3[BiS3] is synthesized in quantitative yields. The material exhibits nonlinear optical properties with strong second harmonic generation properties at arbitrary wavelengths in the infrared spectral range and a notable laser-induced damage threshold of 5.22 GW cm-2 for pulsed laser radiation at a wavelength of 1040 nm, a pulse duration of 180 fs, and a repetition rate of 12.5 kHz. K3[BiS3] indicates semiconductivity with a direct optical band gap of 2.51 eV. Dielectric and impedance characterizations demonstrate κ values in the range of 6-13 at 1 kHz and a high electrical resistivity. A strong diamagnetic behavior with a susceptibility of -2.73 × 10-4 m3 kg-1 at room temperature is observed. These results suggest it is a promising nonlinear optical candidate for the infrared region. The synergic physical characteristics of K3[BiS3] provide insight into the correlation of optical, electrical, and magnetic properties.

Ca2+-activated sphingomyelin scrambling and turnover mediate ESCRT-independent lysosomal repair.

Lysosomes are vital organelles vulnerable to injuries from diverse materials. Failure to repair or sequester damaged lysosomes poses a threat to cell viability. Here we report that cells exploit a sphingomyelin-based lysosomal repair pathway that operates independently of ESCRT to reverse potentially lethal membrane damage. Various conditions perturbing organelle integrity trigger a rapid calcium-activated scrambling and cytosolic exposure of sphingomyelin. Subsequent metabolic conversion of sphingomyelin by neutral sphingomyelinases on the cytosolic surface of injured lysosomes promotes their repair, also when ESCRT function is compromised. Conversely, blocking turnover of cytosolic sphingomyelin renders cells more sensitive to lysosome-damaging drugs. Our data indicate that calcium-activated scramblases, sphingomyelin, and neutral sphingomyelinases are core components of a previously unrecognized membrane restoration pathway by which cells preserve the functional integrity of lysosomes.

NIR-to-NIR Imaging: Extended Excitation Up to 2.2 µm Using Harmonic Nanoparticles with a Tunable hIGh EneRgy (TIGER) Widefield Microscope.

Near-infrared (NIR) marker-based imaging is of growing importance for deep tissue imaging and is based on a considerable reduction of optical losses at large wavelengths. We aim to extend the range of NIR excitation wavelengths particularly to values beyond 1.6 µm in order to profit from the low loss biological windows NIR-III and NIR-IV. We address this task by studying NIR-excitation to NIR-emission conversion and imaging in the range of 1200 up to 2400 nm at the example of harmonic Mg-doped lithium niobate nanoparticles (i) using a nonlinear diffuse femtosecond-pulse reflectometer and (ii) a Tunable hIGh EneRgy (TIGER) widefield microscope. We successfully demonstrate the existence of appropriate excitation/emission configurations in this spectral region taking harmonic generation into account. Moreover, NIR-imaging using the most striking configurations NIR-III to NIR-I, based on second harmonic generation (SHG), and NIR-IV to NIR-I, based on third harmonic generation (THG), is demonstrated with excitation wavelengths from 1.6-1.8 µm and from 2.1-2.2 µm, respectively. The advantages of the approach and the potential to additionally extend the emission range up to 2400 nm, making use of sum frequency generation (SFG) and difference frequency generation (DFG), are discussed.

Time evolution of Symmetry-forbidden Raman lines activated by photorefractivity.

Transmission Raman spectroscopy experiments were performed on iron doped congruent lithium niobate within two -in principle equivalent- configurations, namely Y(ZX)Y and Y(XZ)Y. While the former respects the Raman selection rules, the other configuration gives a time dependent spectrum that, after a transient time of several minutes, finally results in a mixture of expected and forbidden modes. This breaking of Raman selection rules is caused by the spontaneous conversion of a part of the ordinarily polarized pump beam into an extraordinarily polarized beam by photorefractive anisotropic self-scattering. A numerical modelling of the phenomenon is developed and fairly reproduces the time dependence of conversion energy.

The elusive role of NbLi bound polaron energy in hopping charge transport in Fe: LiNbO3.

Charge transport due to small polarons hopping among defective (bound polarons) and regular (free polarons) sites is shown to depend in a non-trivial way on the value of the stabilization energy provided by the lattice distortion surrounding the charge carriers. This energy, normally not directly accessible for bound polarons using spectroscopic techniques, is determined here by a combination of experimental and numerical methods for the important case of small electron polarons bound to [Formula: see text] defects in the prototype ferroelectric oxide lithium niobate. Our findings provide an estimation of the [Formula: see text] polaron stabilization energy [Formula: see text] and demonstrate that in lithium niobate both free and bound polarons contribute to charge transport at room temperature, explaining the fast decay of the light-induced bound polaron population observed by transient absorption spectroscopy.