Defect Emission and Its Dipole Orientation in Layered Ternary Znln2 S4 Semiconductor.

Defect engineering is promising to tailor the physical properties of 2D semiconductors for function-oriented electronics and optoelectronics. Compared with the extensively studied 2D binary materials, the origin of defects and their influence on physical properties of 2D ternary semiconductors are not clarified. Here, the effect of defects on the electronic structure and optical properties of few-layer hexagonal Znln2 S4 is thoroughly studied via versatile spectroscopic tools in combination with theoretical calculations. It is demonstrated that the Zn-In antistructural defects induce the formation of a series of donor and acceptor energy levels and sulfur vacancies induce donor energy levels, leading to rich recombination paths for defect emission and extrinsic absorption. Impressively, the emission of donor-acceptor pair in Znln2 S4 can be significantly tailored by electrostatic gating due to efficient tunability of Fermi level (Ef ). Furthermore, the layer-dependent dipole orientation of defect emission in Znln2 S4 is directly revealed by back focal plane imagining, where it presents obviously in-plane dipole orientation within a dozen-layer thickness of Znln2 S4 . These unique features of defects in Znln2 S4 including extrinsic absorption, rich recombination paths, gate tunability, and in-plane dipole orientation are definitely a benefit to the advanced orientation-functional optoelectronic applications.

Nano-antennas with decoupled transparent leads for optoelectronic studies.

Performing electrical measurements on single plasmonic nanostructures presents a challenging task due to the limitations in contacting the structure without disturbing its optical properties. In this work, we show two ways to overcome this problem by fabricating bow-tie nano-antennas with indium tin oxide leads. Indium tin oxide is transparent in the visible range and electrically conducting, but non-conducting at optical frequencies. The structures are prepared by electron beam lithography. Further definition, such as introducing small gaps, is achieved by focused helium ion beam milling. Dark-field reflection spectroscopy characterization of the dimer antennas shows typical unperturbed plasmonic spectra with multiple resonance peaks from mode hybridization.

Colloidal 2D Mo1-xWxS2 nanosheets: an atomic- to ensemble-level spectroscopic study.

Composition dependent tuning of electronic and optical properties in semiconducting two-dimensional (2D) transition metal dichalcogenide (TMDC) alloys is promising for tailoring the materials for optoelectronics. Here, we report a solution-based synthesis suitable to obtain predominantly monolayered 2D semiconducting Mo1-xWxS2 nanosheets (NSs) with controlled composition as substrate-free colloidal inks. Atomic-level structural analysis by high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDXS) depicts the distribution of individual atoms within the Mo1-xWxS2 NSs and reveals the tendency for domain formation, especially at low molar tungsten fractions. These domains cause a broadening in the associated ensemble-level Raman spectra, confirming the extrapolation of the structural information from the microscopic scale to the properties of the entire sample. A characterization of the Mo1-xWxS2 NSs by steady-state optical spectroscopy shows that a band gap tuning in the range of 1.89-2.02 eV (614-655 nm) and a spin-orbit coupling-related exciton splitting of 0.16-0.38 eV can be achieved, which renders colloidal methods viable for upscaling low cost synthetic approaches toward application-taylored colloidal TMDCs.

Electronic Structure of Colloidal 2H-MoS2 Mono and Bilayers Determined by Spectroelectrochemistry.

The electronic structure of mono and bilayers of colloidal 2H-MoS2 nanosheets synthesized by wet-chemistry using potential-modulated absorption spectroscopy (EMAS), differential pulse voltammetry, and electrochemical gating measurements is investigated. The energetic positions of the conduction and valence band edges of the direct and indirect bandgap are reported and observe strong bandgap renormalization effects, charge screening of the exciton, as well as intrinsic n-doping of the as-synthesized material. Two distinct transitions in the spectral regime associated with the C exciton are found, which overlap into a broad signal upon filling the conduction band. In contrast to oxidation, the reduction of the nanosheets is largely reversible, enabling potential applications for reductive electrocatalysis. This work demonstrates that EMAS is a highly sensitive tool for determining the electronic structure of thin films with a few nanometer thicknesses and that colloidal chemistry affords high-quality transition metal dichalcogenide nanosheets with an electronic structure comparable to that of exfoliated samples.

Accumulation and penetration behavior of hypericin in glioma tumor spheroids studied by fluorescence microscopy and confocal fluorescence lifetime imaging microscopy.

Glioblastoma WHO IV belongs to a group of brain tumors that are still incurable. A promising treatment approach applies photodynamic therapy (PDT) with hypericin as a photosensitizer. To generate a comprehensive understanding of the photosensitizer-tumor interactions, the first part of our study is focused on investigating the distribution and penetration behavior of hypericin in glioma cell spheroids by fluorescence microscopy. In the second part, fluorescence lifetime imaging microscopy (FLIM) was used to correlate fluorescence lifetime (FLT) changes of hypericin to environmental effects inside the spheroids. In this context, 3D tumor spheroids are an excellent model system since they consider 3D cell-cell interactions and the extracellular matrix is similar to tumors in vivo. Our analytical approach considers hypericin as probe molecule for FLIM and as photosensitizer for PDT at the same time, making it possible to directly draw conclusions of the state and location of the drug in a biological system. The knowledge of both state and location of hypericin makes a fundamental understanding of the impact of hypericin PDT in brain tumors possible. Following different incubation conditions, the hypericin distribution in peripheral and central cryosections of the spheroids were analyzed. Both fluorescence microscopy and FLIM revealed a hypericin gradient towards the spheroid core for short incubation periods or small concentrations. On the other hand, a homogeneous hypericin distribution is observed for long incubation times and high concentrations. Especially, the observed FLT change is crucial for the PDT efficiency, since the triplet yield, and hence the O2 activation, is directly proportional to the FLT. Based on the FLT increase inside spheroids, an incubation time > 30 min is required to achieve most suitable conditions for an effective PDT.

Substrate effects on the speed limiting factor of WSe2 photodetectors.

We investigate the time-resolved photoelectric response of WSe2 crystals on glass and flexible polyimide substrates to determine the effect of a changed dielectric environment on the speed of the photodetectors. We show that varying the substrate material can alter the speed-limiting mechanism: while the detectors on polyimide are RC limited, those on glass are limited by slower excitonic diffusion processes. We attribute this to a shortening of the depletion layer at the metal electrode/WSe2 interface caused by the higher dielectric screening of glass compared to polyimide. The photodetectors on glass show a tunable bandwidth, which can be increased to 2.6 MHz with increasing the electric field.

Monitoring tautomerization of single hypericin molecules in a tunable optical λ/2 microcavity.

Hypericin tautomerization that involves the migration of the labile protons is believed to be the primary photophysical process relevant to its light-activated antiviral activity. Despite the difficulty in isolating individual tautomers, it can be directly observed in single-molecule experiments. We show that the tautomerization of single hypericin molecules in free space is observed as an abrupt flipping of the image pattern accompanied with fluorescence intensity fluctuations, which are not correlated with lifetime changes. Moreover, the study can be extended to a λ/2 Fabry-Pérot microcavity. The modification of the local photonic environment by a microcavity is well simulated with a theoretical model that shows good agreement with the experimental data. Inside a microcavity, the excited state lifetime and fluorescence intensity of single hypericin molecules are correlated, and a distinct jump of the lifetime and fluorescence intensity reveals the temporal behavior of the tautomerization with high sensitivity and high temporal resolution. The observed changes are also consistent with time-dependent density functional theory calculations. Our approach paves the way to monitor and even control reactions for a wider range of molecules at the single molecule level.

Gradient SERS Substrates with Multiple Resonances for Analyte Screening: Fabrication and SERS Applications.

Surface-enhanced Raman spectroscopy (SERS) provides a strong enhancement to an inherently weak Raman signal, which strongly depends on the material, design, and fabrication of the substrate. Here, we present a facile method of fabricating a non-uniform SERS substrate based on an annealed thin gold (Au) film that offers multiple resonances and gap sizes within the same sample. It is not only chemically stable, but also shows reproducible trends in terms of geometry and plasmonic response. Scanning electron microscopy (SEM) reveals particle-like and island-like morphology with different gap sizes at different lateral positions of the substrate. Extinction spectra show that the plasmonic resonance of the nanoparticles/metal islands can be continuously tuned across the substrate. We observed that for the analytes 1,2-bis(4-pyridyl) ethylene (BPE) and methylene blue (MB), the maximum SERS enhancement is achieved at different lateral positions, and the shape of the extinction spectra allows for the correlation of SERS enhancement with surface morphology. Such non-uniform SERS substrates with multiple nanoparticle sizes, shapes, and interparticle distances can be used for fast screening of analytes due to the lateral variation of the resonances within the same sample.

Probing Bias-Induced Electron Density Shifts in Metal-Molecule Interfaces via Tip-Enhanced Raman Scattering.

Surface charging effects at metal-molecule interfaces, for example, charge transfer, charge transport, charge injection, and so on, have a strong impact on the performance of organic electronics. Only having molecules bound or adsorbed on different metals results in a doping-like behavior at the interface by the different work functions of the metals and creates hybrid surface states, which strongly affect the efficiencies. With the ongoing downsizing and thinning of the organic components, the impact of the interface will even further increase. However, most of the investigations only monitor the interface without the additional charging effects from applying a voltage to the interface. In this work we present a spectroscopic approach based on tip-enhanced Raman spectroscopy (TERS) to study metal-molecule interfaces with an applied voltage simulating the electric field strength in real devices. We monitor how an intrinsic inductive effect of partial functional groups in molecules can shift the molecular electron density (ED) distribution when a bias voltage is applied. Therefore, we choose two molecules as model systems, which are similar in size and binding condition to a smooth gold surface, but with different electronic structure. By placing the tip 1 nm over the molecular surface at a fixed position and changing the applied bias voltage, we record electric-field-dependent tip-enhanced Raman spectra. Specific vibrational bands exhibit voltage-dependent intensity changes related to the shift of the local ED inside the molecules. We believe this experiment is valuable to gain deeper insights into charged metal-molecule interfaces.

Scouting for strong light-matter coupling signatures in Raman spectra.

Strong coupling between vibrational transitions and a vacuum field of a cavity mode leads to the formation of vibrational polaritons. These hybrid light-matter states have been widely explored because of their potential to control chemical reactivity. However, the possibility of altering Raman scattering through the formation of vibrational polaritons has been rarely reported. Here, we present the Raman scattering properties of different molecules under vibrational strong coupling conditions. The polariton states are clearly observed in the IR transmission spectra of the coupled system for benzonitrile and methyl salicylate in liquid phase and for polyvinyl acetate in a solid polymer film. However, none of the studied systems exhibits a signature of the polariton states in the Raman spectra. For the solid polymer film, we have used cavities with different layer structures to investigate the influence of vibrational strong coupling on the Raman spectra. The only scenario where alterations of the Raman spectra are observed is for a thin Ag layer being in direct contact with the polymer film. This shows that, even though the system is in the vibrational strong coupling regime, changes in the Raman spectra do not necessarily result from the strong coupling, but are caused by the surface enhancement effects.

Hot carrier-mediated avalanche multiphoton photoluminescence from coupled Au-Al nanoantennas.

Avalanche multiphoton photoluminescence (AMPL) is observed from coupled Au-Al nanoantennas under intense laser pumping, which shows more than one order of magnitude emission intensity enhancement and distinct spectral features compared with ordinary metallic photoluminescence. The experiments are conducted by altering the incident laser intensity and polarization using a home-built scanning confocal optical microscope. The results show that AMPL originates from the recombination of avalanche hot carriers that are seeded by multiphoton ionization. Notably, at the excitation stage, multiphoton ionization is shown to be assisted by the local electromagnetic field enhancement produced by coupled plasmonic modes. At the emission step, the giant AMPL intensity can be evaluated as a function of the local field environment and the thermal factor for hot carriers, in accordance with a linear relationship between the power law exponent coefficient and the emitted photon energy. The dramatic change in the spectral profile is explained by spectral linewidth broadening mechanisms. This study offers nanospectroscopic evidence of both the potential optical damages for plasmonic nanostructures and the underlying physical nature of light-matter interactions under a strong laser field; it illustrates the significance of the emerging topics of plasmonic-enhanced spectroscopy and laser-induced breakdown spectroscopy.

Light-Controlled Near-Field Energy Transfer in Plasmonic Metasurface Coupled MoS2 Monolayer.

The energy transfer from plasmonic nanostructures to semiconductors has been extensively studied to enhance light-harvesting and tailor light-matter interactions. In this study, the efficient energy transfer from an Au metasurface to monolayered MoS2 within a near-field coupling regime is reported. The metasurface is designed and fabricated to demonstrate strong photoluminescence (PL) and cathodoluminescence (CL) emission spectra. In the coupled heterostructure of MoS2 with a metasurface, both the Raman shift and absorption spectral intensities of monolayered MoS2 are affected. The spectral profile and PL peak position can be tailored owing to the energy transfer between plasmonic nanostructures and semiconductors. This is confirmed by ultrafast lifetime measurement. A theoretical model of two coupled oscillators is proposed, where the expanded general solutions (EGS) of such a model result in a series of eigenvalues that correspond to the renormalization of energy levels in modulated MoS2. The model can predict the peak shift up to tens of nanometers in hybrid structures and hence provides an alternative method to describe energy transfer between metallic structures and two-dimensional (2D) semiconductors. A viable approach for studying light-matter interactions in 2D semiconductors via near-field energy transfer is presented, which may stimulate the applications of functional nanophotonic devices.

Tunable strong coupling of two adjacent optical λ/2 Fabry-Pérot microresonators.

Strong optical mode coupling between two adjacent λ/2 Fabry-Pérot microresonators consisting of three parallel silver mirrors is investigated experimentally and theoretically as a function of their detuning and coupling strength. Mode coupling can be precisely controlled by tuning the mirror spacing of one resonator with respect to the other by piezoelectric actuators. Mode splitting, anti-crossing and asymmetric modal damping are observed and theoretically discussed for the symmetric and antisymmetric supermodes of the coupled system. The spectral profile of the supermodes is obtained from the Fourier transform of the numerically calculated time evolution of the individual resonator modes, taking into account their resonance frequencies, damping and coupling constants, and is in excellent agreement with the experiments. Our microresonator design has potential applications for energy transfer between spatially separated quantum systems in micro optoelectronics and for the emerging field of polaritonic chemistry.

Nanoscale plasmonic phase sensor.

Using the localized surface plasmon resonance (LSPR) of gold nanoparticles for sensing applications has attracted considerable interest, since it can be very sensitive, even down to a single molecule, and selective for a specific analyte molecule with a suitable surface modification. LSPR sensing is usually based on the wavelength shift of the LSPR or a Fano resonance. Here, we present a new experimental approach based on the phase of the light scattered by a single gold nanoparticle by equipping a confocal microscope with an additional interferometer arm similar to a Michelson interferometer. The detected phase depends on the shape of the nanoparticle and the refractive index of the surrounding medium and can even be detected for off-resonant excitation. This can be used as a new and sensitive detection method in LSPR sensing, allowing the detection of changes to the local refractive index or the binding of molecules to the nanoparticle surface.

Hypericin: Single Molecule Spectroscopy of an Active Natural Drug.

Hypericin is one of the most efficient photosensitizers used in photodynamic tumor therapy (PDT). The reported treatments of this drug reach from antidepressive, antineoplastic, antitumor and antiviral activity. We show that hypericin can be optically detected down to a single molecule at ambient conditions. Hypericin can even be observed inside of a cancer cell, which implies that this drug can be directly used for advanced microscopy techniques (PALM, spt-PALM, or FLIM). Its photostability is large enough to obtain single molecule fluorescence, surface enhanced Raman spectra (SERS), fluorescence lifetime, antibunching, and blinking dynamics. Sudden spectral changes can be associated with a reorientation of the molecule on the particle surface. These properties of hypericin are very sensitive to the local environment. Comparison of DFT calculations with SERS spectra show that both the neutral and deprotonated form of hypericin can be observed on the single molecule and ensemble level.

Enhancement of the second harmonic signal of nonlinear crystals by self-assembled gold nanoparticles.

In second harmonic generation (SHG), the energy of two incoming photons, e.g., from a femtosecond laser, can be combined in one outgoing photon of twice the energy, e.g., by means of a nonlinear crystal. The SHG efficiency, however, is limited. In this work, the harvested signal is maximized by composing a hybrid system consisting of a nonlinear crystal with a dense coverage of plasmonic nanostructures separated by narrow gaps. The method of self-assembled diblock-copolymer-based micellar lithography with subsequent electroless deposition is employed to cover the whole surface of a lithium niobate (LiNbO3) crystal. The interaction of plasmonic nanostructures with light leads to a strong electric near-field in the adjacent crystal. This near-field is harnessed to enhance the near-surface SHG signal from the nonlinear crystal. At the plasmon resonance of the gold nanoparticles, a pronounced enhancement of about 60-fold SHG is observed compared to the bare crystal within the confocal volume of a laser spot.

Local Observation of Phase Segregation in Mixed-Halide Perovskite.

Mixed-halide perovskites have emerged as promising materials for optoelectronics due to their tunable band gap in the entire visible region. A challenge remains, however, in the photoinduced phase segregation, narrowing the band gap of mixed-halide perovskites under illumination thus restricting applications. Here, we use a combination of spatially resolved and bulk measurements to give an in-depth insight into this important yet unclear phenomenon. We demonstrate that photoinduced phase segregation in mixed-halide perovskites selectively occurs at the grain boundaries rather than within the grain centers by using shear-force scanning probe microscopy in combination with confocal optical spectroscopy. Such difference is further evidenced by light-biased bulk Fourier-transform photocurrent spectroscopy, which shows the iodine-rich domain as a minority phase coexisting with the homogeneously mixed phase during illumination. By mapping the surface potential of mixed-halide perovskites, we evidence the higher concentration of positive space charge near the grain boundary possibly provides the initial driving force for phase segregation, while entropic mixing dominates the reverse process. Our work offers detailed insight into the microscopic processes occurring at the boundary of crystalline perovskite grains and will support the development of better passivation strategies, ultimately allowing the processing of more environmentally stable perovskite films.

Unusual effects in single molecule tautomerization: hemiporphycene.

Parent hemiporphycene, a recently obtained constitutional isomer of porphyrin, exists in room temperature solutions and polymer matrices in the form of two trans tautomers interconverting via double hydrogen transfer. Using confocal fluorescence microscopy, it was possible to monitor tautomerization in single hemiporphycene molecules embedded in a PMMA film by monitoring the spectral and temporal evolution of their fluorescence spectra. The emission spectra of the two tautomeric forms are similar to those obtained from ensemble studies. However, the analysis of temporal spectral evolution reveals effects not detected in the bulk. For some single molecules, a large decrease of tautomerization rate was observed. This is interpreted as an indication of multidimensional character of the tautomerization coordinate and coupling of the reaction with the polymer relaxation processes. In addition, fluorescence lifetimes obtained for single molecules are significantly shorter than those measured for the bulk. It is proposed that the shortening is caused by environment-induced distortion of the molecule, which enhances the S0← S1 internal conversion rate by lowering the barrier to excited state single hydrogen transfer. This effect seems to reflect the specific morphology of thin (30 nm) polymer samples, because it is not observed in ensemble studies carried out using thick (tens of micrometers or more) PMMA films.

Low-Cost GRIN-Lens-Based Nephelometric Turbidity Sensing in the Range of 0.1-1000 NTU.

Turbidity sensing is very common in the control of drinking water. Furthermore, turbidity measurements are applied in the chemical (e.g., process monitoring), pharmaceutical (e.g., drug discovery), and food industries (e.g., the filtration of wine and beer). The most common measurement technique is nephelometric turbidimetry. A nephelometer is a device for measuring the amount of scattered light of suspended particles in a liquid by using a light source and a light detector orientated in 90° to each other. Commercially available nephelometers cost usually-depending on the measurable range, reliability, and precision-thousands of euros. In contrast, our new developed GRIN-lens-based nephelometer, called GRINephy, combines low costs with excellent reproducibility and precision, even at very low turbidity levels, which is achieved by its ability to rotate the sample. Thereby, many cuvette positions can be measured, which results in a more precise average value for the turbidity calculated by an algorithm, which also eliminates errors caused by scratches and contaminations on the cuvettes. With our compact and cheap Arduino-based sensor, we are able to measure in the range of 0.1-1000 NTU and confirm the ISO 7027-1:2016 for low turbidity values.

Second-harmonic generation in single CdSe nanowires by focused cylindrical vector beams.

Cylindrical vector beams with radial or azimuthal polarization have created great interest due to their unique focusing characteristics and focal components. In this Letter, we investigate second-harmonic general (SHG) of single CdSe nanowires (NWs) excited by tightly focused cylindrical vector beams of 150 fs pulses at 800 nm. With the specific polarizations in the focal region, we demonstrate a three-dimensional interaction between the focal electric field components and the NWs. The excitation anisotropy of the SHG can directly be derived from the imaging patterns with the cylindrical vector beams. The highest SHG excitation efficiency is observed when the polarization is parallel to the long axis of the NW, which is confirmed by the conventional linear polarization approach. Our work with cylindrical vector beams provides a new approach to study the nonlinear phenomenon of single semiconductor NWs in three dimensions and it could be applied to many other nanoscale systems.