Probing compositional engineering effects on lead-free perovskite-inspired nanocrystal thin films using correlative nonlinear optical microscopy.

We introduce the use of correlative third-harmonic generation and multiphoton-induced luminescence microscopy to investigate the impact of manganese (Mn) doping on bismuth (Bi)-based perovskite-inspired nanocrystal thin films. The technique was found to be extremely sensitive to the microscopic features of the perovskite film and its structural compositions, allowing the unambiguous detection of compositionally different emitters in the perovskite film and manipulation of their nonlinear optical responses. Our work unveils a new way to investigate, manipulate, and exploit perovskite-inspired functional materials for nonlinear optical conversion at the nanoscale.

Surface and optical properties of phase-pure silver iodobismuthate nanocrystals.

The study of surface defects is one of the forefronts of halide perovskite research. In the nanoscale regime, where the surface-to-volume ratio is high, the surface plays a key role in determining the electronic properties of perovskites. Perovskite-inspired silver iodobismuthates are promising photovoltaic absorbers. Herein, we demonstrate the colloidal synthesis of phase pure and highly crystalline AgBiI4 nanocrystals (NCs). Surface-sensitive spectroscopic techniques reveal the rich surface features of the NCs that enable their impressive long-term environmental and thermal stabilities. Notably, the surface termination and its passivation effects on the electronic properties of AgBiI4 are investigated. Our atomistic simulations suggest that a bismuth iodide-rich surface, as in the case of AgBiI4 NCs, does not introduce surface trap states within the band gap region of AgBiI4, unlike a silver iodide-rich surface. These findings may encourage the investigation of surfaces of other lead-free perovskite-inspired materials.

Lead-Free Cesium Titanium Bromide Double Perovskite Nanocrystals.

Double perovskites are a promising family of lead-free materials that not only replace lead but also enable new optoelectronic applications beyond photovoltaics. Recently, a titanium (Ti)-based vacancy-ordered double perovskite, Cs2TiBr6, has been reported as an example of truly sustainable and earth-abundant perovskite with controversial results in terms of photoluminescence and environmental stability. Our work looks at this material from a new perspective, i.e., at the nanoscale. We demonstrate the first colloidal synthesis of Cs2TiX6 nanocrystals (X = Br, Cl) and observe tunable morphology and size of the nanocrystals according to the set reaction temperature. The Cs2TiBr6 nanocrystals synthesized at 185 °C show a bandgap of 1.9 eV and are relatively stable up to 8 weeks in suspensions. However, they do not display notable photoluminescence. The centrosymmetric crystal structure of Cs2TiBr6 suggests that this material could enable third-harmonic generation (THG) responses. Indeed, we provide a clear evidence of THG signals detected by the THG microscopy technique. As only a few THG-active halide perovskite materials are known to date and they are all lead-based, our findings promote future research on Cs2TiBr6 as well as on other lead-free double perovskites, with stronger focus on currently unexplored nonlinear optical applications.

Maskless fabrication of plasmonic metasurfaces in polymer film using a spatial light modulator.

We demonstrate a high-speed optical technique to fabricate plasmonic metasurfaces in a polymer film. The technique is based on a programmable spatial light modulator, which is used to spatially control the photoreduction sites of gold ions in a polyvinyl alcohol film doped with a gold precursor. After irradiation, annealing was used to induce the growth of nanoparticles, producing plasmonic microstructures. Using a 473 nm excitation wavelength, microscopic plasmonic gratings, and meta-atom arrays with arbitrary orientations, an effective nanostructure size of ∼700nm and constituent nanoparticles with average size of ∼37nm were created. The technique enables a cost-effective and straightforward light-based approach to fabricate plasmonic metasurfaces with tunable properties.

Unveiling structured domains of persistent luminescent microparticles using second-harmonic generation microscopy.

We introduce the use of second-harmonic generation microscopy to investigate individual persistent luminescent microparticles that are either embedded in glass or as prepared. Three-dimensional mapping of the second-harmonic generation from monoclinic dysprosium- and europium-doped strontium aluminates, a popular persistent luminescent material, allows us to unambiguously visualize and reveal for the first time the presence of micrometer-sized structured domains from such microparticles. The technique was found to have high potential for studying noninvasively a wide range of individual persistent luminescent entities that are embedded in a variety of glass matrices.

Plasmonic mode conversion in individual tilted 3D nanostructures.

We investigate mode conversion in 3D asymmetric nanocones using angle-dependent linear optical spectroscopy and second-harmonic generation microscopy supported by corresponding simulations. The results prove the efficient excitation of the plasmonic out-of-plane mode that enhances the electric near-field at the sharp tip. Furthermore, we introduce two advanced fabrication processes including either etch mask transfer by tilted etching into a metallic layer or tilted electron-beam lithography followed by tilted evaporation and lift-off. These processes enable the fabrication of tilted nanostructures which can be optimized for a given purpose. The combination of the optical properties and the introduced fabrication processes enables a new design of plasmonic nanostructures for ultra-compact sensors or photon sources.

Resonant harmonic generation in AlGaAs nanoantennas probed by cylindrical vector beams.

We investigate second- and third-harmonic generation from individual AlGaAs nanoantennas using far-field mapping with radially- and azimuthally-polarized cylindrical vector beams. Due to the unique polarization structure of these beams, we are able to determine the crystal orientation of the nanoantenna in a single scanning map. Our method thus provides a novel and versatile optical tool to study the crystal properties of semiconductor nanoantennas. We also demonstrate the influence of cylindrical vector beam excitation on the resonant enhancement of second- and third-harmonic generation driven by electric and magnetic anapole-like modes, despite falling in the strong absorption regime of AlGaAs. In particular, we observe a greater nonlinear conversion efficiency from a single nanoantenna excited with a radially-polarized beam as compared to an azimuthally polarized cylindrical vector beam. The fundamental field of the radially-polarized beam strongly couples to the multipoles increasing the near-field enhancement of the nanoantenna. Our work introduces new ways to study individual nanostructures and to tailor the efficiencies of nonlinear phenomena at the nanoscale using non-conventional optical techniques.

Demonstration of longitudinally polarized optical needles.

Longitudinally polarized optical needles are beams that exhibit ultra-long depth of field, subwavelength transverse confinement, and polarization oriented along the longitudinal direction. Although several techniques have been proposed to generate such needles, their scarce experimental observations have been indirect and incomplete. Here, we demonstrate the creation and full three-dimensional verification of a longitudinally polarized optical needle. This needle is produced by generating a radially polarized Bessel-Gauss beam at the focus of a high numerical aperture microscope objective. Using three-dimensional spatial mapping of second-harmonic generation from a single vertically aligned GaAs nanowire, we directly verify such a longitudinally polarized optical needle's properties, which are formed at the focus. The needle exhibits a dominant polarization, which is oriented along the longitudinal direction, an ultra-long depth of field (30 λ), and high spatial homogeneity. These are in agreement with corresponding focal field calculations that use vector diffraction theory. Our findings open new opportunities for manipulation and utilization of longitudinally polarized optical needles.

Collective Effects in Second-Harmonic Generation from Plasmonic Oligomers.

We investigate collective effects in plasmonic oligomers of different symmetries using second-harmonic generation (SHG) microscopy with cylindrical vector beams (CVBs). The oligomers consist of gold nanorods that have a longitudinal plasmon resonance close to the fundamental wavelength that is used for SHG excitation and whose long axes are arranged locally such that they follow the distribution of the transverse component of the electric field of radially or azimuthally polarized CVBs in the focal plane. We observe that SHG from such rotationally symmetric oligomers is strongly modified by the interplay between the polarization properties of the CVB and interparticle coupling. We find that the oligomers with radially oriented nanorods exhibit small coupling effects. In contrast, we find that the oligomers with azimuthally oriented nanorods exhibit large coupling effects that lead to silencing of SHG from the whole structure. Our experimental results are in very good agreement with numerical calculations based on the boundary element method. The work describes a new route for studying coupling effects in complex arrangements of nano-objects and thereby for tailoring the efficiency of nonlinear optical effects in such structures.

Nonlinear microscopy using cylindrical vector beams: Applications to three-dimensional imaging of nanostructures.

The three-dimensional (3D) optical fields that arise from the focusing of cylindrical vector beams (CVB) with radial and azimuthal polarizations provide new sources of contrast for optical microscopy of nano-objects. So far, these demonstrations have been restricted to two-dimensional transversal scanning, i.e., along the focal plane of interest, or use of point-like objects, i.e., single molecules and nanoparticles. Here, we demonstrate the first application of CVBs for 3D imaging of 3D nano-objects. This technique is done by acquiring 3D image scans of the second-harmonic generation signal from vertically-aligned semiconductor nanowires, whose second-order response is primarily driven by the longitudinal electric field, i.e., the field component along the nanowire axis. Our technique provides a new way to study individual nano-objects in three dimensions through the unique combination of nonlinear microscopy and CVBs.

Nonlinear imaging of nanostructures using beams with binary phase modulation.

We demonstrate nonlinear microscopy of oriented nanowires using excitation beams with binary phase modulation. A simple and intuitive optical scheme comprising a spatial light modulator gives us the possibility to control the phase across an incident Hermite-Gaussian beam of order (1,0) (HG10 mode). This technique allows us to gradually vary the spatial distribution of the longitudinal electric fields in the focal volume, as demonstrated by second-harmonic generation from vertically-aligned GaAs nanowires. These results open new opportunities for the full control of polarization in the focal volume to enhance light interaction with nanostructured materials.

Third-harmonic generation imaging of three-dimensional microstructures fabricated by photopolymerization.

We demonstrate the capability of polarized third-harmonic generation (THG) for high contrast imaging of three-dimensional microstructures fabricated by photopolymerization. Using circular polarization of fundamental light, background-free optically-sectioned THG images were obtained from laser-written photopolymerized microstructures. The technique has great potential for simple and noninvasive characterization of photopolymerized devices, which typically show poor contrast in conventional light microscopy.

Sub-micron scale patterning of fluorescent silver nanoclusters using low-power laser.

Noble metal nanoclusters are ultrasmall nanomaterials with tunable properties and huge application potential; however, retaining their enhanced functionality is difficult as they readily lose their properties without stabilization. Here, we demonstrate a facile synthesis of highly photostable silver nanoclusters in a polymer thin film using visible light photoreduction. Furthermore, the different stages of the nanocluster formation are investigated in detail using absorption and fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. A cost-effective fabrication of photostable micron-sized fluorescent silver nanocluster barcode is demonstrated in silver-impregnated polymer films using a low-power continuous-wave laser diode. It is shown that a laser power of as low as 0.75 mW is enough to write fluorescent structures, corresponding to the specifications of a commercially available laser pointer. The as-formed nanocluster-containing microstructures can be useful in direct labeling applications such as authenticity marking and fluorescent labeling.

Second-harmonic generation imaging of semiconductor nanowires with focused vector beams.

We use second-harmonic generation (SHG) with focused vector beams to investigate individual vertically aligned GaAs nanowires. Our results provide direct evidence that SHG from oriented nanowires is mainly driven by the longitudinal field along the nanowire growth axis. Consequently, focused radial polarization provides a superior tool to characterize such nanowires compared to linear polarization, also allowing this possibility in the native growth environment. We model our experiments by describing the SHG process for zinc-blende structure and dipolar bulk nonlinearity.

Polarized THG microscopy identifies compositionally different lipid droplets in mammalian cells.

Cells store excess lipids as two major compounds, triacylglycerols (TAGs) and cholesteryl esters (CEs), inside lipid droplets (LDs). The degree of lipid ordering is considered to play a major role in the mobility and enzymatic processing of lipids in LDs. Here, we provide evidence that polarized third-harmonic generation (THG) microscopy distinguishes between native TAG- and CE-enriched LDs in cells due to the different ordering of the two lipid species. We first demonstrate that the responses from synthetic TAG- and CE-enriched LDs using THG microscopy with linear and circular polarizations differ according to their different intrinsic ordering. We then employ simulations to dissect how polarization effects influence the THG from an isotropic LD. Finally, we induce TAG- and CE-enriched LDs in murine macrophages and demonstrate that polarized THG responses increase in a nonlinear fashion with increasing CE/TAG ratio. This suggests that with an increasing CE content, there is a rather sharp transition toward increased LD ordering. Our results demonstrate that polarized THG microscopy enables label-free quantitative analysis of LD ordering and discriminates between compositionally different LDs in intact mammalian cells.

Direct laser writing of photostable fluorescent silver nanoclusters in polymer films.

Metal nanoclusters consist of a few to a few hundred atoms and exhibit attractive molecular properties such as ultrasmall size, discrete energy levels, and strong fluorescence. Although patterning of these clusters down to the micro- or nanoscale could lead to applications such as high-density data storage, it has been reported only for inorganic matrices. Here we present submicron-scale mask-free patterning of fluorescent silver nanoclusters in an organic matrix. The nanoclusters were produced by direct laser writing in poly(methacrylic acid) thin films and exhibit a broadband emission at visible wavelengths with photostability that is superior to that of Rhodamine 6G dye. This fabrication method could open new opportunities for applications in nanophotonics like imaging, labeling, and metal ion sensing. We foresee that this method can be further applied to prepare other metal nanoclusters embedded in compositionally different polymer matrices.

Three-dimensional winged nanocone optical antennas.

We introduce 3D optical antennas based on winged nanocones. The antennas support particle plasmon oscillations with current distributions that facilitate transformation of transverse far-field radiation to strong longitudinal local fields near the cone apices. We characterize the optical responses of the antennas by their extinction spectra and by second-harmonic generation microscopy with cylindrical vector beams. The results demonstrate a new 3D polarization-controllable optical antenna for applications in apertureless near-field microscopy, spectroscopy, and plasmonic sensing.

Third- and second-harmonic generation microscopy of individual metal nanocones using cylindrical vector beams.

We demonstrate third- (THG) and second-harmonic generation (SHG) microscopy of individual silver nanocones using tightly focused cylindrical vector beams (CVBs). Although THG is expected to be a weaker process than SHG, the yield for THG with radial polarization was higher than for SHG. We also found an excellent correlation between the imaging properties of THG and SHG, suggesting that both are governed by the same overall features of the individual nanocone. We also found that the transverse spatial resolution of THG with CVBs, particularly RP, exceeds that of SHG. Our work establishes the potential of THG microscopy with CVBs for structure-sensitive imaging of three-dimensional (3D) metal nano-objects.

Second-harmonic generation imaging of metal nano-objects with cylindrical vector beams.

We introduce an imaging technique based on second-harmonic generation with cylindrical vector beams that is extremely sensitive to three-dimensional orientation and nanoscale morphology of metal nano-objects. Our experiments and second-harmonic field calculations based on frequency-domain boundary element method are in very good agreement. The technique provides contrast for structural features that cannot be resolved by linear techniques or conventional states of polarization and shows great potential for simple and cost-effective far-field optical imaging in plasmonics.

Optical trapping and surgery of living yeast cells using a single laser.

We present optical trapping and surgery of living yeast cells using two operational modes of a single laser. We used a focused laser beam operating in continuous-wave mode for noninvasive optical trapping and manipulation of single yeast cell. We verified that such operational mode of the laser does not cause any destructive effect on yeast cell wall. By changing the operation of the laser to femtosecond-pulsed mode, we show that a tightly focused beam dissects the yeast cell walls via nonlinear absorption. Lastly, using the combined technique of optical microsurgery and trapping, we demonstrate intracellular organelle extraction and manipulation from a yeast cell. The technique established here will be useful as an efficient method for both surgery and manipulation of living cells using a single laser beam.