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.

A modular optical honeycomb breadboard realized with 3D-printable building bricks and industrial aluminum extrusions.

Optical breadboards with honeycomb structure provide a solid surface with mounting hole grids for building optical assemblies, sub-systems and experiments in the fields of quantum-optics and photonics. Performance criteria are the ability to resist bending under load (stiffness) and the ability to dissipate induced vibrations to the board (damping). The hardware presented in this paper deals with the possibility of assembling optical breadboards using 3D-printed building bricks with honeycomb structure, so-called 'breadboard bricks', and industrial aluminum extrusions, so-called 'breadboard profiles'. With this do-it-yourself approach, it is possible to make changes to the breadboard, such as making an opening, changing its shape or increasing the mounting surface whenever needed. Furthermore, the breadboard is automatically compatible with industrially relevant mechanical design platforms. Aluminum extrusions and the PLA thermoplastic filament provide mechanical stiffness and damping, respectively. Further characteristics are low costs and a modular design. All this makes it especially suited for agile prototyping of (laser) optical assemblies in many engineering processes.

The role of cations in hydrothermal synthesis of nonlinear optical sodium niobate nanocrystals.

The usability of the alkali niobates with their ferroelectric and photorefractive properties could be expanded if the development of synthesis methods would allow to obtain small, preferably monodispersed, crystals in the sub-µm to nanometer regime. Of all the possible synthesis methods, the most reliable is currently hydrothermal synthesis to generate small crystallite sizes of these materials. Although the products of sodium niobate are polydisperse and partially agglomerated, they show a significant SHG signal that is unexpectedly comparable to that of potassium niobate. A view on the hydrothermal synthesis of sodium niobate reveals that the incorporation of cations in the crystalline lattice of the niobium educt plays a part in the formation of the product. The occurrence of distinct different phases, as in the case of potassium niobate, is not observed. Instead, it is shown that a clear assignment of the crystalline phase cannot be made here. This indicates that crystallization of the alkali niobates in hydrothermal synthesis depends on the stoichiometry, the niobium starting material and the cation used.

Inspection of Trivalent Chromium Conversion Coatings Using Laser Light: The Unexpected Role of Interference on Cold-Rolled Aluminium.

Laser-based inspection of trivalent chromium conversion coatings on rough, cold-rolled aluminium substrates is studied from a basic physics perspective by means of angle and wavelength dependent measurements. As a result, we show that the correlation between the scattered laser light and the coating weight of the conversion layer is dominated by the phenomenon of interference. The combined experimental and numerical approach of our study is based on an appropriate layer model which was developed from a set of reference measurements of confocal microscopy, electron microscopy and X-ray photoelectron spectroscopy. The aluminium alloy AA3003 with a trivalent chromium conversion coating serves as an example. Our derived model is capable to reconstruct the reflectance of a laser beam at grazing incidence even for a pronounced surface roughness of R q ≈ 300   n m , for different coating thicknesses less than 70 n m corresponding to coating weights between zero and 0.5 g / m 2 and for laser wavelengths from 405 n m to 785 n m . In our discussion we outline the possibility to transfer the results to other aluminium alloys and/or other metallic substrates, as well as their potential for industrial applications such as 100% inline-capability, costs, velocity and ruggedness.

Combining photoinduced linkage isomerism and nonlinear optical properties in ruthenium nitrosyl complexes.

The complex trans-[RuNO(NH3)4F]SiF6 was synthesized in quantitative yield and the structure was characterized by X-ray diffraction and spectroscopic methods. The complex crystallizes in the non-centrosymmetric space group Pn. Hirshfeld surface analysis revealed that the dominant intermolecular interactions are of types H...F and F...O, which are likely to be responsible for the packing of the molecules in a non-centrosymmetric structure. Irradiation with blue light leads to the formation of Ru-ON (metastable state MS1) and Ru-η2-(NO) (metastable state MS2) bond isomers, as shown by IR and UV-Vis spectroscopy. The structural features of the MS1 isomer were elucidated by photocrystallography. The complex exhibits exceptionally good thermal stability of the metastable state MS1, such that it can be populated by light at 290-300 K, which is important for potential applications. The second harmonic (SH) emission can be generated by femtosecond-pulsed irradiation of the complex. The generated SH is rather efficient and stable under long-term exposure. Finally, since both metastable states and harmonic generation can be generated at room temperature, an attempt to drive the SH response by photoisomerization of the nitrosyl ligand was made and is discussed.

Nonlinear optical organic-inorganic crystals: synthesis, structural analysis and verification of harmonic generation in tri-(o-chloroanilinium nitrate).

The structural and nonlinear optical properties of a new anilinium hybrid crystal of chemical formula (C6H7NCl+·NO3-)3 have been investigated. The crystal structure was determined from single-crystal X-ray diffraction measurements performed at a temperature of 100 K which show that the compound crystallizes in a noncentrosymmetric space group (Pna21). The structural analysis was coupled with Hirshfeld surface analysis to evaluate the contribution of the different intermolecular interactions to the formation of supramolecular assemblies in the solid state that exhibit nonlinear optical features. This analysis reveals that the studied compound is characterized by a three-dimensional network of hydrogen bonds and the main contributions are provided by the O...H, C...H, H...H and Cl...H interactions, which alone represent ∼85% of the total contributions to the Hirshfeld surfaces. It is noteworthy that the halogen...H contributions are quite comparable with those of the H...H contacts. The nonlinear optical properties were investigated by nonlinear diffuse femtosecond-pulse reflectometry and the obtained results were compared with those of the reference material LiNbO3. The hybrid crystals exhibit notable second (SHG) and third (THG) harmonic generation which confirms its polarity is generated by the different intermolecular interactions. These measurements also highlight that the THG signal of the new anilinium compound normalized to its SHG counterpart is more pronounced than for LiNbO3.

Dynamic-grating-assisted energy transfer between ultrashort laser pulses in lithium niobate.

Energy redistribution between two subpicosecond laser pulses of 2.5 eV photon energy is observed and studied in congruent, nominally undoped LiNbO3, aiming to reveal the underlying coupling mechanisms. The dependences of pulse amplification on intensity, frequency detuning and pulse duration point to two different contributions of coupling, both based on self-diffraction from a recorded dynamic grating. The first one is caused by a difference in pulse intensities (transient energy transfer) while the second one originates from a difference in pulse frequencies. The latter appears when chirped pulses are mutually delayed in time. A quite high coupling efficiency has been observed in a 280 µm thin crystal: one order of magnitude energy amplification of a weak pulse and nearly 10% net energy enhancement of one pulse for the case of equal input intensities.

Nonlinear optical potassium niobate nanocrystals as harmonic markers: the role of precursors and stoichiometry in hydrothermal synthesis.

Nanocrystals of alkaline niobates are currently being discussed for various applications because of their diverse and remarkable properties. Although the growth of bulk niobate crystals is well established, little is known about respective nanocrystals and the optical properties of niobates below 100 nm. A systematic view of the hydrothermal synthesis of potassium niobate with respect to the precursor species reveals the sensitive dependence of the resulting crystalline phases and sizes on the educt modifications. With a variation of stoichiometry of the procedure, the product modification and crystallite size can be changed. By means of second harmonic generation, nanocrystalline potassium niobate offers the possibility for use as an optical marker in high resolution nonlinear microscopy. Redispersed particles show a significant second harmonic generation signal throughout the visible spectral range.

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.

Atomic insight to lattice distortions caused by carrier self-trapping in oxide materials.

We gain hitherto missing access to the spatio-temporal evolution of lattice distortions caused by carrier self-trapping in the class of oxide materials - and beyond. The joint experimental/theoretical tool introduced combines femtosecond mid-infrared probe spectroscopy with potential landscape modeling and is based on the original approach that the vibration mode of a biatomic molecule is capable to probe strongly localized, short-lived lattice distortions in its neighborhood. Optically generated, small, strong-coupling polarons in lithium niobate, mediated by OH- ions present as ubiquitous impurities, serve as a prominent example. Polaron trapping is found to result in an experimentally determined redshift of the OH- stretching mode amounting to Δνvib = -3 cm-1, that is successfully modeled by a static Morse potential modified by Coulomb potential changes due to the displacements of the surrounding ions and the trapped charge carrier. The evolution of the trapping process can also be highlighted by monitoring the dynamics of the vibrational shift making the method an important tool for studying various systems and applications.

Optical Riblet Sensor: Beam Parameter Requirements for the Probing Laser Source.

Beam parameters of a probing laser source in an optical riblet sensor are studied by considering the high demands on a sensors' precision and reliability for the determination of deviations of the geometrical shape of a riblet. Mandatory requirements, such as minimum intensity and light polarization, are obtained by means of detailed inspection of the optical response of the riblet using ray and wave optics; the impact of wavelength is studied. Novel measures for analyzing the riblet shape without the necessity of a measurement with a reference sample are derived; reference values for an ideal riblet structure obtained with the optical riblet sensor are given. The application of a low-cost, frequency-doubled Nd:YVO4 laser pointer sufficient to serve as a reliable laser source in an appropriate optical riblet sensor is discussed.

Interference and holography with femtosecond laser pulses of different colours.

Interferometry and holography are two domains that are based on observation and recording of interference fringes from two light beams. While the aim of the first technique is to reveal and map the phase difference of two wave fronts, the main task of the second technique is to reconstruct one of the two recording waves via diffraction of the other wave from the recorded fringe pattern (hologram). To create fringes, mutually coherent waves from the same laser are commonly used. It is shown here that fringes can be observed and holograms can be recorded with ultrashort, sub-picosecond pulses even of different colour, generated in our experiment with two parametric amplifiers seeded, both by the same mode-locked Ti-sapphire laser. The appearance of permanent and transient gratings is confirmed by recording of an image-bearing hologram, by observation of two-beam coupling gain in a pump-probe experiment and by frequency conversion in Raman-Nath self-diffraction from a moving grating.

Explaining the success of Kogelnik's coupled-wave theory by means of perturbation analysis: discussion.

The problem of diffraction of an electromagnetic wave by a thick hologram grating can be solved by the famous Kogelnik's coupled-wave theory (CWT) to a very high degree of accuracy. We confirm this finding by comparing the CWT and the exact result for a typical example and propose an explanation in terms of perturbation theory. To this end we formulate the problem of diffraction as a matrix problem following similar well-known approaches, especially rigorous coupled-wave theory (RCWT). We allow for a complex permittivity modulation and a possible phase shift between refractive index and absorption grating and explicitly incorporate appropriate boundary conditions. The problem is solved numerically exact for the specific case of a planar unslanted grating and a set of realistic values of the material's parameters and experimental conditions. Analogously, the same problem is solved for a two-dimensional truncation of the underlying matrix that would correspond to a CWT approximation but without the usual further approximations. We verify a close coincidence of both results even in the off-Bragg region and explain this result by means of a perturbation analysis of the underlying matrix problem. Moreover, the CWT is found not only to coincide with the perturbational approximation in the in-Bragg and the extreme off-Bragg cases, but also to interpolate between these extremal regimes.

Holographic Spectroscopy: Wavelength-Dependent Analysis of Photosensitive Materials by Means of Holographic Techniques.

Holographic spectroscopy is highlighted as a powerful tool for the analysis of photosensitive materials with pronounced alterations of the complex permittivity over a broad range in the visible spectrum, due to the advances made both in the fields of advanced holographic media and highly tunable lasers systems. To analytically discuss consequences for in- and off-Bragg reconstruction, we revised Kogelnik's coupled wave theory strictly on the basis of complex permittivities. We extended it to comply with modern experimental parameters such as out-of-phase mixed holograms and highly modulated gratings. A spatially modulated, wavelength-dependent permittivity that superimposes a spatially homogeneous wavelength-dependent ground state spectrum is taken into account for signal wave reconstruction with bulky elementary mixed gratings as an example. The dispersion characteristics of the respective diffraction efficiency is modelled for color-center-absorption and absorption of strongly localized carriers. As an example for the theoretical possibilities of our newly derived set of equations, we present a quantitative analysis of the Borrmann effect connected to out-of-phase gratings, providing easier and more intuitive methods for the derivation of their grating parameters.

Transition Metal Compounds Towards Holography.

We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal-ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications.