Multiscale Supercrystal Meta-atoms.

Meta-atoms are the building blocks of metamaterials, which are employed to control both generation and propagation of light as well as provide novel functionalities of localization and directivity of electromagnetic radiation. In many cases, simple dielectric or metallic resonators are employed as meta-atoms to create different types of electromagnetic metamaterials. Here, we fabricate and study supercrystal meta-atoms composed of coupled perovskite quantum dots. We reveal that these multiscale structures exhibit specific emission properties, such as spectrum splitting and polaritonic effects. We believe that such multiscale supercrystal meta-atoms will provide novel functionalities in the design of many novel types of active metamaterials and metasurfaces.

Multifunctional and Transformative Metaphotonics with Emerging Materials.

Future technologies underpinning multifunctional physical and chemical systems and compact biological sensors will rely on densely packed transformative and tunable circuitry employing nanophotonics. For many years, plasmonics was considered as the only available platform for subwavelength optics, but the recently emerged field of resonant metaphotonics may provide a versatile practical platform for nanoscale science by employing resonances in high-index dielectric nanoparticles and metasurfaces. Here, we discuss the recently emerged field of metaphotonics and describe its connection to material science and chemistry. For tunabilty, metaphotonics employs a variety of the recently highlighted materials such as polymers, perovskites, transition metal dichalcogenides, and phase change materials. This allows to achieve diverse functionalities of metasystems and metasurfaces for efficient spatial and temporal control of light by employing multipolar resonances and the physics of bound states in the continuum. We anticipate expanding applications of these concepts in nanolasers, tunable metadevices, metachemistry, as well as a design of a new generation of chemical and biological ultracompact sensing devices.

Giant and Tunable Excitonic Optical Anisotropy in Single-Crystal Halide Perovskites.

During the last years, giant optical anisotropy has demonstrated its paramount importance for light manipulation. In spite of recent advances in the field, the achievement of continuous tunability of optical anisotropy remains an outstanding challenge. Here, we present a solution to the problem through the chemical alteration of halogen atoms in single-crystal halide perovskites. As a result, we manage to continually modify the optical anisotropy by 0.14. We also discover that the halide perovskite can demonstrate optical anisotropy up to 0.6 in the visible range─the largest value among non-van der Waals materials. Moreover, our results reveal that this anisotropy could be in-plane and out-of-plane depending on perovskite shape─rectangular and square. As a practical demonstration, we have created perovskite anisotropic nanowaveguides and shown a significant impact of anisotropy on high-order guiding modes. These findings pave the way for halide perovskites as a next-generation platform for tunable anisotropic photonics.

Direct LiF imaging diagnostics on refractive X-ray focusing at the EuXFEL High Energy Density instrument.

The application of fluorescent crystal media in wide-range X-ray detectors provides an opportunity to directly image the spatial distribution of ultra-intense X-ray beams including investigation of the focal spot of free-electron lasers. Here the capabilities of the micro- and nano-focusing X-ray refractive optics available at the High Energy Density instrument of the European XFEL are reported, as measured in situ by means of a LiF fluorescent detector placed into and around the beam caustic. The intensity distribution of the beam focused down to several hundred nanometers was imaged at 9 keV photon energy. A deviation from the parabolic surface in a stack of nanofocusing Be compound refractive lenses (CRLs) was found to affect the resulting intensity distribution within the beam. Comparison of experimental patterns in the far field with patterns calculated for different CRL lens imperfections allowed the overall inhomogeneity in the CRL stack to be estimated. The precise determination of the focal spot size and shape on a sub-micrometer level is essential for a number of high energy density studies requiring either a pin-size backlighting spot or extreme intensities for X-ray heating.

Damage threshold of LiF crystal irradiated by femtosecond hard XFEL pulse sequence.

Here we demonstrate the results of investigating the damage threshold of a LiF crystal after irradiating it with a sequence of coherent femtosecond pulses using the European X-ray Free Electron Laser (EuXFEL). The laser fluxes on the crystal surface varied in the range ∼ 0.015-13 kJ/cm2 per pulse when irradiated with a sequence of 1-100 pulses (tpulse ∼ 20 fs, Eph = 9 keV). Analysis of the surface of the irradiated crystal using different reading systems allowed the damage areas and the topology of the craters formed to be accurately determined. It was found that the ablation threshold decreases with increasing number of X-ray pulses, while the depth of the formed craters increases non-linearly and reaches several hundred nanometers. The obtained results have been compared with data already available in the literature for nano- and picosecond pulses from lasers in the soft X-ray/VUV and optical ranges. A failure model of lithium fluoride is developed and verified with simulation of material damage under single-pulse irradiation. The obtained damage threshold is in reasonably good agreement with the experimentally measured one.

Polaron-Enhanced Polariton Nonlinearity in Lead Halide Perovskites.

Exciton-polaritons offer a versatile platform for realization of all-optical integrated logic gates due to the strong effective optical nonlinearity resulting from the exciton-exciton interactions. In most of the current excitonic materials there exists a direct connection between the exciton robustness to thermal fluctuations and the strength of the exciton-exciton interaction, making materials with the highest levels of exciton nonlinearity applicable at cryogenic temperatures only. Here, we show that strong polaronic effects, characteristic for perovskite materials, allow overcoming this limitation. Namely, we demonstrate a record-high value of the nonlinear optical response in the nanostructured organic-inorganic halide perovskite MAPbI3, experimentally detected as a 19.7 meV blueshift of the polariton branch under femtosecond laser irradiation. This is substantially higher than characteristic values for the samples based on conventional semiconductors and monolayers of transition-metal dichalcogenides. The observed strong polaron-enhanced nonlinearity exists for both tetragonal and orthorhombic phases of MAPbI3 and remains stable at elevated temperatures.

Enhanced Multiphoton Processes in Perovskite Metasurfaces.

Multiphoton absorption and luminescence are fundamentally important nonlinear processes for utilizing efficient light-matter interaction. Resonant enhancement of nonlinear processes has been demonstrated for many nanostructures; however, it is believed that all higher-order processes are always much weaker than their corresponding linear processes. Here, we study multiphoton luminescence from structured surfaces and, combining multiple advantages of perovskites with the concept of metasurfaces, we demonstrate that the efficiency of nonlinear multiphoton processes can become comparable to the efficiency of the linear process. We reveal that the perovskite metasurface can enhance substantially two-photon stimulated emission with the threshold being comparable with that of the one-photon process. Our modeling of free-carrier dynamics and exciton recombination upon nonlinear photoexcitation uncovers that this effect can be attributed to the local field enhancement in structured media, a substantial increase of the mode overlap, and the selection rules of two-photon absorption in perovskites.

Directional Lasing from Nanopatterned Halide Perovskite Nanowire.

Halide perovskite nanowire-based lasers have become a powerful tool for modern nanophotonics, being deeply subwavelength in cross-section and demonstrating low-threshold lasing within the whole visible spectral range owing to the huge gain of material even at room temperature. However, their emission directivity remains poorly controlled because of the efficient outcoupling of radiation through their subwavelength facets working as pointlike light sources. Here, we achieve directional lasing from a single perovskite CsPbBr3 nanowire by imprinting a nanograting on its surface, which provides stimulated emission outcoupling to its vertical direction with a divergence angle around 2°. The nanopatterning is carried out by the high-throughput laser ablation method, which preserves the luminescent properties of the material that is typically deteriorated after processing via conventional lithographic approaches. Moreover, nanopatterning of the perovskite nanowire is found to decrease the number of the lasing modes with a 2-fold increase of the quality factor of the remaining modes.

Lasing Action from Anapole Metasurfaces.

We study active dielectric metasurfaces composed of two-dimensional arrays of split-nanodisk resonators fabricated in InGaAsP membranes with embedded quantum wells. Depending on the geometric parameters, such split-nanodisk resonators can operate in the optical anapole regime originating from an overlap of the electric dipole and toroidal dipole Mie-resonant optical modes, thus supporting strongly localized fields and high-Q resonances. We demonstrate room-temperature lasing from the anapole lattices of engineered active metasurfaces with low threshold and high coherence.

A 3-axis coil design for multichannel TMS arrays.

PURPOSE: Multichannel Transcranial Magnetic Stimulation (mTMS) arrays enable multiple sites to be stimulated simultaneously or sequentially under electronic control without moving the system's stimulation coils. Here, we build and characterize the performance of a novel modular 3-axis TMS coil that can be utilized as a unit element in large-scale multichannel TMS arrays. METHODS: We determined the basic physical characteristics of the 3-axis TMS coil x-, y- and z-elements using a custom 2-channel programmable stimulator prototype. We mapped the temporal rate-of-change of the induced magnetic field (dB/dt) on a 2D plane parallel to the coil surface (including an extended line for full spatial coverage) and compared those values with predictions from magnetic field simulations. Temperature measurements were carried out to assess the incorporated air-cooling method. We measured the mutual and self-inductances of the x/y/z-elements to assess coupling between them. Additionally, we measured and calculated the coupling between z-elements in the array configuration. Finally, we performed electric field simulations to evaluate the stimulation intensity and focality of the coil and compared the results to conventional TMS coils as well as demonstrated suitability of the 3-axis coil for a multichannel array configuration. RESULTS: The experimentally obtained dB/dt values validated the computational model of the 3-axis coil and therefore confirmed that both the coil and stimulator system are operating as intended. The air-cooling system was effective for brief high-frequency pulse trains and extended single- and paired-pulse TMS protocols. The electromagnetic simulations suggested that an array of the 3-axis coils would have comparable stimulation intensity to conventional TMS coils, therefore enabling clearly suprathreshold stimulation of the human brain. The recorded coil coupling between the x/y/z-elements was < 1% and the maximal coupling between z-elements in the array configuration was 1.8% and 3.4% for the measured and calculated values, respectively. CONCLUSION: We presented a 3-axis coil intended for multichannel TMS arrays. The electromagnetic measurements and simulations verified that the coil fabrication met the desired specifications and that the inductive coupling between the elements was negligible. The air-cooled 3-axis TMS coil appears suitable to be used as an element in multichannel TMS arrays.

Rapid computation of TMS-induced E-fields using a dipole-based magnetic stimulation profile approach.

BACKGROUND: TMS neuronavigation with on-line display of the induced electric field (E-field) has the potential to improve quantitative targeting and dosing of stimulation, but present commercially available solutions are limited by simplified approximations. OBJECTIVE: Developing a near real-time method for accurate approximation of TMS induced E-fields with subject-specific high-resolution surface-based head models that can be utilized for TMS navigation. METHODS: Magnetic dipoles are placed on a closed surface enclosing an MRI-based head model of the subject to define a set of basis functions for the incident and total E-fields that define the subject's Magnetic Stimulation Profile (MSP). The near real-time speed is achieved by recognizing that the total E-field of the coil only depends on the incident E-field and the conductivity boundary geometry. The total E-field for any coil position can be obtained by matching the incident field of the stationary dipole basis set with the incident E-field of the moving coil and applying the same basis coefficients to the total E-field basis functions. RESULTS: Comparison of the MSP-based approximation with an established TMS solver shows great agreement in the E-field amplitude (relative maximum error around 5%) and the spatial distribution patterns (correlation >98%). Computation of the E-field took ~100 ms on a cortical surface mesh with 120k facets. CONCLUSION: The numerical accuracy and speed of the MSP approximation method make it well suited for a wide range of computational tasks including interactive planning, targeting, dosing, and visualization of the intracranial E-fields for near real-time guidance of coil positioning.

Opto-thermally controlled beam steering in nonlinear all-dielectric metastructures.

Reconfigurable metasurfaces have recently gained a lot of attention in applications such as adaptive meta-lenses, hyperspectral imaging and optical modulation. This kind of metastructure can be obtained by an external control signal, enabling us to dynamically manipulate the electromagnetic radiation. Here, we theoretically propose an AlGaAs device to control the second harmonic generation (SHG) emission at nanoscale upon optimized optical heating. The asymmetric shape of the used meta-atom is selected to guarantee a predominant second harmonic (SH) emission towards the normal direction. The proposed structure is concurrently excited by a pump beam at a fundamental wavelength of 1540 nm and by a continuous wave (CW) control signal above the semiconductor band gap. The optical tuning is achieved by a selective optimization of meta-atoms SH phase, which is modulated by the control signal intensity. We numerically demonstrate that the heating induced in the meta-atoms by the CW pump can be used to dynamically tune the device properties. In particular, we theoretically demonstrate a SH beam steering of 8° with respect to the vertical axis for an optimized device with average temperature increase even below 90° C.

Lewis Superacidic Tellurenyl Cation-Induced Electrophilic Activation of an Inert Carborane.

The aryltellurenyl cation [2-(tBuNCH)C6 H4 Te]+ , a Lewis super acid, and the weakly coordinating carborane anion [CB11 H12 ]- , an extremely weak Brønsted acid (pKa =131.0 in MeCN), form an isolable ion pair complex [2-(tBuNCH)C6 H4 Te][CB11 H12 ], in which the Brønsted acidity (pKa 7.4 in MeCN) of the formally hydridic B-H bonds is dramatically increased by more than 120 orders of magnitude. The electrophilic activation of B-H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12- and 7-[2-(tBuN{H}CH)C6 H4 Te(CB11 H11 )] in ratios ranging from 62 : 38 to 80 : 20.

Stimulated Raman Scattering from Mie-Resonant Subwavelength Nanoparticles.

Resonant dielectric structures have emerged recently as a new platform for subwavelength nonplasmonic photonics. It was suggested and demonstrated that magnetic and electric Mie resonances can enhance substantially many effects at the nanoscale including spontaneous Raman scattering. Here, we demonstrate stimulated Raman scattering (SRS) for isolated crystalline silicon (c-Si) nanoparticles and observe experimentally a transition from spontaneous to stimulated scattering manifested in a nonlinear growth of the signal intensity above a certain pump threshold. At the Mie resonance, the light gets confined into a low volume of the resonant mode with enhanced electromagnetic fields inside the c-Si nanoparticle due to its high refractive index, which leads to an overall strong SRS signal at low pump intensities. Our finding paves the way for the development of efficient Raman nanolasers for multifunctional photonic metadevices.

Light-Emitting Nanophotonic Designs Enabled by Ultrafast Laser Processing of Halide Perovskites.

Nanophotonics based on resonant nanostructures and metasurfaces made of halide perovskites have become a prospective direction for efficient light manipulation at the subwavelength scale in advanced photonic designs. One of the main challenges in this field is the lack of large-scale low-cost technique for subwavelength perovskite structures fabrication preserving highly efficient luminescence. Here, unique properties of halide perovskites addressed to their extremely low thermal conductivity (lower than that of silica glass) and high defect tolerance to apply projection femtosecond laser lithography for nanofabrication with precise spatial control in all three dimensions preserving the material luminescence efficiency are employed. Namely, with CH3 NH3 PbI3 perovskite highly ordered nanoholes and nanostripes of width as small as 250 nm, metasurfaces with periods less than 400 nm, and nanowire lasers as thin as 500 nm, corresponding to the state-of-the-art in multistage expensive lithographical methods are created. Remarkable performance of the developed approach allows to demonstrate a number of advanced optical applications, including morphology-controlled photoluminescence yield, structural coloring, optical- information encryption, and lasing.

Soft X-ray diffraction patterns measured by a LiF detector with sub-micrometre resolution and an ultimate dynamic range.

The unique diagnostic possibilities of X-ray diffraction, small X-ray scattering and phase-contrast imaging techniques applied with high-intensity coherent X-ray synchrotron and X-ray free-electron laser radiation can only be fully realized if a sufficient dynamic range and/or spatial resolution of the detector is available. In this work, it is demonstrated that the use of lithium fluoride (LiF) as a photoluminescence (PL) imaging detector allows measuring of an X-ray diffraction image with a dynamic range of ∼107 within the sub-micrometre spatial resolution. At the PETRA III facility, the diffraction pattern created behind a circular aperture with a diameter of 5 µm irradiated by a beam with a photon energy of 500 eV was recorded on a LiF crystal. In the diffraction pattern, the accumulated dose was varied from 1.7 × 105 J cm-3 in the central maximum to 2 × 10-2 J cm-3 in the 16th maximum of diffraction fringes. The period of the last fringe was measured with 0.8 µm width. The PL response of the LiF crystal being used as a detector on the irradiation dose of 500 eV photons was evaluated. For the particular model of laser-scanning confocal microscope Carl Zeiss LSM700, used for the readout of the PL signal, the calibration dependencies on the intensity of photopumping (excitation) radiation (λ = 488 nm) and the gain have been obtained.

Evaluation of RF interactions between a 3T birdcage transmit coil and transcranial magnetic stimulation coils using a realistically shaped head phantom.

PURPOSE: Multichannel transcranial magnetic stimulation (TMS)1 is an emerging technology that allows multiple sites to be stimulated simultaneously or sequentially under electronic control without movement of the coils. A multichannel TMS/MRI head coil array for 3 Tesla is currently under development to mitigate challenges of concurrent TMS/fMRI as well as enable potential new applications. The influence of the multichannel TMS system on the MR image quality and safety must be carefully investigated. METHODS: A standard birdcage volume coil for 3 Tesla systems was simulated using a commercial numerical electromagnetic solver. Two setups, consisting of 1) a MR-compatible TMS coil, and 2) a 3-axis TMS coil array, were simulated to quantify changes in the transmit field B1+ and the SAR. A realistically shaped homogeneous head model was used in the computations. RESULTS: The stimulation coils produced enhancements and attenuations on the transmit field with effects greater than 5% up to 2.4 cm and 3.3 cm under the scalp for the MR-compatible TMS coil and 3-axis TMS coil array, respectively. The 10 g-SAR distribution did not change significantly in either of the cases; however, the nominal SAR maximum locus was shifted between existing hot spots. CONCLUSION: The simulated B1+ variations found near the TMS coils indicate the possibility of inducing sequence-dependent image artefacts predominatly limited to the vicinity of the coil(s). However, we conclude that neither the MR-compatible commercial TMS coil nor the 3-axis TMS coil array siginificantly elevate SAR in the head or neck beyond accepted safety limits.

One-Electron Reduction of 2-Mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian).

The electrochemical characteristics of 2-mono(2,6-diisopropylphenylimino)acenaphthene-1-one (dpp-mian) have been investigated. One-electron reduction of dpp-mian involves the iminoketone fragment, which is revealed by the EPR spectrum obtained after the electrolysis of the dpp-mian solution in tetrahydrofuran (THF). The reduction of dpp-mian with one equivalent of metallic potassium leads to a similar EPR spectrum. The sodium complex [(dpp-mian)Na(dme)]2 (1) produces an EPR signal with hyperfine coupling on the nitrogen atom of the iminoketone fragment of the dpp-mian ligand. Dpp-mian can also be reduced in a one-electron process by SnCl2 ×(dioxane). In this case, complex (dpp-mian)2 SnCl2 (2) is formed, with the tin atom displaying an oxidation state of +4. Tin(II) chloride dihydrate, SnCl2 ×2(H2 O), also reduces dpp-mian, but the two ligands bound to tin in the product form a new carbon-carbon bond between the ketone moieties of the dpp-mian monoanions to form complex (bis-dpp-mian)HSnCl3 (3). Metallic tin reduces dpp-mian to form the (bis-dpp-mian)2 Sn (4) species. Compounds 1-4 were characterized by X-ray diffraction.

Electronic structure of CsPbBr3-xClx perovskites: synthesis, experimental characterization, and DFT simulations.

All-inorganic lead halide perovskites of various compositions have emerged as a prospective family of materials for light-emitting devices and photonic applications. However, a comprehensive study of their structural and electronic properties is still missing. Moreover, thin film fabrication of these perovskites comprising heterohalide anions by wet chemistry approaches also remains challenging. Here we fabricate high-quality CsPbBr3-xClx perovskite thin films using a wet chemical method accompanied by a chemical vapor anion exchange procedure, which allows rigorously studying their optical and structural properties at different compositions. Namely, we present both the numerical and experimental studies of the electronic properties of all-inorganic mixed-halide perovskites, showing their optical absorption, excitonic photoluminescence and exciton binding energy, phase, chemical composition, and band structure and the band gap evolution with a gradual change in x in CsPbBr3-xClx. The results reveal that as Cl ions substitute for Br ones in the perovskite crystal lattice the room-temperature phase does not change its orthorhombic symmetry, whereas the energy of the direct electronic transition from the valence to conduction band at the Γ-point increases nonlinearly. By using the experimentally derived nonlinear dependence it is easy to accurately predict the band gap for any CsPbBr3-xClx perovskite thin film consisting of grains with sizes beyond the quantum confinement regime.

Tunable Hybrid Fano Resonances in Halide Perovskite Nanoparticles.

Halide perovskites are known to support excitons at room temperatures with high quantum yield of luminescence that make them attractive for all-dielectric resonant nanophotonics and meta-optics. Here we report the observation of broadly tunable Fano resonances in halide perovskite nanoparticles originating from the coupling of excitons to the Mie resonances excited in the nanoparticles. Signatures of the photon-exciton (" hybrid") Fano resonances are observed in dark-field spectra of isolated nanoparticles, and also in the extinction spectra of aperiodic lattices of such nanoparticles. In the latter case, chemical tunability of the exciton resonance allows reversible tuning of the Fano resonance across the 100 nm bandwidth in the visible frequency range, providing a novel approach to control optical properties of perovskite nanostructures. The proposed method of chemical tuning paves the way to an efficient control of emission properties of on-chip-integrated light-emitting nanoantennas.