Comparing transmission- and epi-BCARS: a round robin on solid-state materials.

Broadband coherent anti-Stokes Raman scattering (BCARS) is a powerful spectroscopy method combining high signal intensity with spectral sensitivity, enabling rapid imaging of heterogeneous samples in biomedical research and, more recently, in crystalline materials. However, BCARS encounters spectral distortion due to a setup-dependent non-resonant background (NRB). This study assesses BCARS reproducibility through a round robin experiment using two distinct BCARS setups and crystalline materials with varying structural complexity, including diamond, 6H-SiC, KDP, and KTP. The analysis compares setup-specific NRB correction procedures, detected and NRB-removed spectra, and mode assignment. We determine the influence of BCARS setup parameters like pump wavelength, pulse width, and detection geometry and provide a practical guide for optimizing BCARS setups for solid-state applications.

Impact of 3D Curvature on the Polarization Orientation in Non-Ising Domain Walls.

Ferroelectric domain boundaries are quasi-two-dimensional functional interfaces with high prospects for nanoelectronic applications. Despite their reduced dimensionality, they can exhibit complex non-Ising polarization configurations and unexpected physical properties. Here, the impact of the three-dimensional (3D) curvature on the polarization profile of nominally uncharged 180° domain walls in LiNbO3 is studied using second-harmonic generation microscopy and 3D polarimetry analysis. Correlations between the domain-wall curvature and the variation of its internal polarization unfold in the form of modulations of the Néel-like character, which we attribute to the flexoelectric effect. While the Néel-like character originates mainly from the tilting of the domain wall, the internal polarization adjusts its orientation due to the synergetic upshot of dipolar and monopolar bound charges and their variation with the 3D curvature. Our results show that curved interfaces in solid crystals may offer a rich playground for tailoring nanoscale polar states.

Brillouin and Raman imaging of domain walls in periodically-poled 5%-MgO:LiNbO3.

Recently, ferroelectric domain walls (DWs) have attracted considerable attention due to their intrinsic topological effects and their huge potential for optoelectronic applications. In contrast, many of the underlying physical properties and phenomena are not well characterized. In this regard, analyzing the vibrational properties, e.g. by Raman spectroscopy, provides direct access to the various local material properties, such as strains, defects or electric fields. While the optical phonon spectra of DWs have been widely investigated in the past, no reports on the acoustic phonon properties of DWs exist. In this work, we present a joint Raman and Brillouin visualization of ferroelectric DWs in the model ferroelectric lithium niobate. This is possible by using a combined Raman and virtually imaged phased array Brillouin setup. Here, we show that DWs can be visualized via frequency shifts observed in the acoustic phonons, as well. The observed contrast then is qualitatively explained by models adapted from Raman spectroscopy. This work, hence, provides a novel route to study ferroelectric DWs and their intrinsic mechanical properties.

Quantifying the refractive index of ferroelectric domain walls in periodically poled LiNbO3 single crystals by polarization-sensitive optical coherence tomography.

Domain walls (DWs) in ferroelectric (FE) and multiferroic materials possess an ever-growing potential as integrated functional elements, for instance in optoelectronic nanodevices. Mandatory, however, is the profound knowledge of the local-scale electronic and optical properties, especially at DWs that are still incompletely characterized to date. Here, we quantify the refractive index of individual FE DWs in periodically-poled LiNbO3 (PPLN) single crystals. When applying polarization-sensitive optical coherence tomography (PS-OCT) at 1300 nm using circular light polarization, we are able to probe the relevant electro-optical properties close to and at the DWs, including also their ordinary and extraordinary contributions. When comparing to numerical calculations, we conclude that the DW signals recorded for ordinary and extraordinary polarization stem from an increased refractive index of at least Δn > 2·10-3 that originates from a tiny region of < 30 nm in width. PS-OCT hence provides an extremely valuable tool to decipher and quantify subtle changes of refractive index profiles for both inorganic and biomedical nanomaterial systems.

Potassium Ion Conductivity in the Cubic Labyrinth of a Piezoelectric, Antiferromagnetic Oxoferrate(III) Tellurate(VI).

Orange-colored crystals of the oxoferrate tellurate K12+6x Fe6 Te4-x O27 [x=0.222(4)] were synthesized in a potassium hydroxide hydroflux with a molar water-base ratio n(H2 O)/n(KOH) of 1.5 starting from Fe(NO3 )3 ⋅ 9H2 O, TeO2 and H2 O2 at about 200 °C. By using (NH4 )2 TeO4 instead of TeO2 , a fine powder consisting of microcrystalline spheres of K12+6x Fe6 Te4-x O27 was obtained. K12+6x Fe6 Te4-x O27 crystallizes in the acentric cubic space group I 4 ‾ 3d. [FeIII O5 ] pyramids share their apical atoms in [Fe2 O9 ] groups and two of their edges with [TeVI O6 ] octahedra to form an open framework that consists of two loosely connected, but not interpenetrating, chiral networks. The flexibility of the hinged oxometalate network manifests in a piezoelectric response similar to that of LiNbO3 .The potassium cations are mobile in channels that run along the <111> directions and cross in cavities acting as nodes. The ion conductivity of cold-pressed pellets of ball-milled K12+6x Fe6 Te4-x O27 is 2.3×10-4 S ⋅ cm-1 at room temperature. Magnetization measurements and neutron diffraction indicate antiferromagnetic coupling in the [Fe2 O9 ] groups.

Tricyanidoferrates(-IV) and Ruthenates(-IV) with Non-Innocent Cyanido Ligands.

Exceptionally electron-rich, nearly trigonal-planar tricyanidometalate anions [Fe(CN)3 ]7- and [Ru(CN)3 ]7- were stabilized in LiSr3 [Fe(CN)3 ] and AE3.5 [M(CN)3 ] (AE=Sr, Ba; M=Fe, Ru). They are the first examples of group 8 elements with the oxidation state of -IV. Microcrystalline powders were obtained by a solid-state route, single crystals from alkali metal flux. While LiSr3 [Fe(CN)3 ] crystallizes in P63 /m, the polar space group P63 with three-fold cell volume for AE3.5 [M(CN)3 ] is confirmed by second harmonic generation. X-ray diffraction, IR and Raman spectroscopy reveal longer C-N distances (124-128 pm) and much lower stretching frequencies (1484-1634 cm-1 ) than in classical cyanidometalates. Weak C-N bonds in combination with strong M-C π-bonding is a scheme also known for carbonylmetalates. Instead of the formal notation [Fe-IV (CN- )3 ]7- , quantum chemical calculations reveal non-innocent intermediate-valent CN1.67- ligands and a closed-shell d10 configuration for Fe, that is, Fe2- .

Characterisation of width-dependent diffusion dynamics in rubidium-exchanged KTP waveguides.

Integrated χ(2) devices are a widespread tool for the generation and manipulation of light fields, since they exhibit high efficiency, a small footprint and the ability to interface them with fibre networks. Surprisingly, some commonly used material substrates are not yet fully understood, in particular potassium titanyl phosphate (KTP). A thorough understanding of the fabrication process of waveguides in this material and analysis of their properties is crucial for the realization and the engineering of high efficiency devices for quantum applications. In this paper we present our studies on rubidium-exchanged waveguides fabricated in KTP. Employing energy dispersive X-ray spectroscopy (EDX), we analysed a set of waveguides fabricated with different production parameters in terms of time and temperature. We find that the waveguide depth is dependent on their widths by reconstructing the waveguide depth profiles. Narrower waveguides are deeper, contrary to the theoretical model usually employed. Moreover, we found that the variation of the penetration depth with the waveguide width is stronger at higher temperatures and times. We attribute this behaviour to stress-induced variation in the diffusion process.

Shallow-etched thin-film lithium niobate waveguides for highly-efficient second-harmonic generation.

High-fidelity periodic poling over long lengths is required for robust, quasi-phase-matched second-harmonic generation using the fundamental, quasi-TE polarized waveguide modes in a thin-film lithium niobate (TFLN) waveguide. Here, a shallow-etched ridge waveguide is fabricated in x-cut magnesium oxide doped TFLN and is poled accurately over 5 mm. The high fidelity of the poling is demonstrated over long lengths using a non-destructive technique of confocal scanning second-harmonic microscopy. We report a second-harmonic conversion efficiency of up to 939 %.W-1 (length-normalized conversion efficiency 3757 %.W-1.cm-2), measured at telecommunications wavelengths. The device demonstrates a narrow spectral linewidth (1 nm) and can be tuned precisely with a tuning characteristic of 0.1 nm/°C, over at least 40 °C without measurable loss of efficiency.

Resource-Efficient Low-Temperature Synthesis of Microcrystalline Pb2 B5 O9 X (X = Cl, Br) for Surfaces Studies by Optical Second Harmonic Generation.

Optically nonlinear Pb2 B5 O9 X (X = Cl, Br) borate halides are an important group of materials for second harmonic generation (SHG). Additionally, they also possess excellent photocatalytic activity and stability in the process of dechlorination of chlorophenols, which are typical persistent organic pollutants. It would be of great interest to conduct in situ (photo-) catalysis investigations during the whole photocatalytic process by SHG when considering them as photocatalytic materials. In order to get superior photocatalytic efficiency and maximum surface information, small particles are highly desired. Here, a low-cost and fast synthesis route that allows growing microcrystalline optically nonlinear Pb2 B5 O9 X borate halides at large quantities is introduced. When applying the ionothermal growth process at temperatures between 130 and 170 °C, microcrystallites with an average size of about 1 µm precipitate with an orthorhombic hilgardite-like borate halide structure. Thorough examinations using powder X-ray diffraction and scanning electron microscopy, the Pb2 B5 O9 X microcrystals are indicated to be chemically pure and single-phased. Besides, the Pb2 B5 O9 X borate halides' SHG efficiencies are confirmed using confocal SHG microscopy. The low-temperature synthesis route thus makes these borate halides a highly desirable material for surface studies such as monitoring chemical reactions with picosecond time resolution and in situ (photo-) catalysis investigations.

High Quality Entangled Photon Pair Generation in Periodically Poled Thin-Film Lithium Niobate Waveguides.

A thin-film periodically poled lithium niobate waveguide was designed and fabricated which generates entangled photon pairs at telecommunications wavelengths with high coincidences-to-accidentals counts ratio CAR>67000, two-photon interference visibility V>99%, and heralded single-photon autocorrelation g_{H}^{(2)}(0)<0.025. Nondestructive in situ diagnostics were used to determine the poling quality in 3D. Megahertz rates of photon pairs were generated by less than a milliwatt of pump power, simplifying the pump requirements and dissipation compared to traditional spontaneous parametric down-conversion lithium niobate devices.

Optical diagnostic methods for monitoring the poling of thin-film lithium niobate waveguides.

We demonstrate two non-destructive methods of studying the gradual poling of thin-film lithium niobate waveguides by the application of a sequence of high-voltage pulses, and we show the transition from under-poling to over-poling and the identification of the optimal stopping point of the poling process. The first diagnostic method is based on changes in continuous-wave light transmission through a hybrid waveguide as it is gradually poled by using a second set of monitoring electrodes fabricated alongside the principal poling electrodes. The second method is based on confocal back-reflected second-harmonic microscopy by using femtosecond optical probe pulses. The results from the two methods are in agreement with each other and may be useful as non-destructive in situ diagnostic methods for optimized poling of integrated waveguides.

Impact of carbon-ion implantation on the nonlinear optical susceptibility of LiNbO3.

In this work we study the impact of ion implantation on the nonlinear optical properties in MgO:LiNbO3 via confocal second-harmonic microscopy. In detail, we spatially characterize the nonlinear susceptibility in carbon-ion implanted lithium niobate planar waveguides for different implantation energies and fluences, as well as the effect of annealing. In a further step, a computational simulation is used to calculate the implantation range of carbon-ions and the corresponding defect density distribution. A comparison between the simulation and the experimental data indicates that the depth profile of the second-order effective nonlinear coefficient is directly connected to the defect density that is induced by the ion irradiation. Furthermore it can be demonstrated that the annealing treatment partially recovers the second-order optical susceptibility.