X-ray and UV Irradiation-Induced Reactive Oxygen Species Mediated Antibacterial Activity in Fe and Pt Nanoparticle-Decorated Si-Doped TiCaCON Films.

Bone implants with biocompatibility and the ability to biomineralize and suppress infection are in high demand. The occurrence of early infections after implant placement often leads to repeated surgical treatment due to the ineffectiveness of antibiotic therapy. Therefore, an extremely attractive solution to this problem would be the ability to initiate bacterial protection of the implant by an external influence. Here, we present a proof-of-concept study based on the generation of reactive oxygen species (ROS) by the implant surface in response to X-ray irradiation, including through a layer of 3 mm adipose tissue, providing bactericidal protection. The effect of UV and X-ray irradiation of the implant surface on the ROS formation and the associated bactericidal activity was compared. The focus of our study was light-sensitive Si-doped TiCaCON films decorated with Fe and Pt nanoparticles (NPs) with photoinduced antibacterial activity mediated by ROS. In the visible and infrared range of 300-1600 nm, the films absorb more than 60% of the incident light. The high light absorption capacity of TiO2/TiC and TiO2/TiN heterostructures was demonstrated by density functional theory calculations. After short-term (5-10 s) low-dose X-ray irradiation, the films generated significantly more ROS than after UV illumination for 1 h. The Fe/TiCaCON-Si films showed enhanced biomineralization capacity, superior cytocompatibility, and excellent antibacterial activity against multidrug-resistant hospital Escherichia coli U20 and K261 strains and methicillin-resistant Staphylococcus aureus MW2 strain. Our study clearly demonstrates that oxidized Fe NPs are a promising alternative to the widely used Ag NPs in antibacterial coatings, and X-rays can potentially be used in ROS-regulating therapy to suppress inflammation in case of postimplant complications.

Femtosecond Laser-Printed Gold Nanoantennas for Electrically Driven and Bias-Tuned Nanoscale Light Sources Operating in Visible and Infrared Spectral Ranges.

Nanoscale electrically driven light-emitting sources with tunable wavelength represent a milestone for implementation of integrated optoelectronic chips. Plasmonic nanoantennas exhibiting an enhanced local density of optical states (LDOS) and strong Purcell effect hold promise for fabrication of bright nanoscale light emitters. Here, we justify gold parabola-shaped nanobumps and their ordered arrays produced by direct ablation-free femtosecond laser printing as broadband plasmonic light sources electrically excited by a probe of scanning tunneling microscope (STM). I-V curves of the probe-nanoantenna tunnel junction reveal characteristic bias voltages correlating with visible-range localized (0.55 and 0.85 µm) and near-IR (1.65 and 1.87 µm) collective plasmonic modes of these nanoantennas. These multiband resonances confirmed by optical spectroscopy and full-wave simulations provide enhanced LDOS for efficient electrically driven and bias-tuned light emission. Additionally, our studies confirm remarkable applicability of STM for accurate study of optical modes supported by the plasmonic nanoantennas at nanoscale spatial resolution.

Noble-Metal Nanoparticle-Embedded Silicon Nanogratings via Single-Step Laser-Induced Periodic Surface Structuring.

Here, we show that direct femtosecond laser nanostructuring of monocrystalline Si wafers in aqueous solutions containing noble-metal precursors (such as palladium dichloride, potassium hexachloroplatinate, and silver nitrate) allows for the creation of nanogratings decorated with mono- (Pd, Pt, and Ag) and bimetallic (Pd-Pt) nanoparticles (NPs). Multi-pulse femtosecond-laser exposure was found to drive periodically modulated ablation of the Si surface, while simultaneous thermal-induced reduction of the metal-containing acids and salts causes local surface morphology decoration with functional noble metal NPs. The orientation of the formed Si nanogratings with their nano-trenches decorated with noble-metal NPs can be controlled by the polarization direction of the incident laser beam, which was justified, for both linearly polarized Gaussian and radially (azimuthally) polarized vector beams. The produced hybrid NP-decorated Si nanogratings with a radially varying nano-trench orientation demonstrated anisotropic antireflection performance, as well as photocatalytic activity, probed by SERS tracing of the paraaminothiophenol-to-dimercaptoazobenzene transformation. The developed single-step maskless procedure of liquid-phase Si surface nanostructuring that proceeds simultaneously with the localized reduction of noble-metal precursors allows for the formation of hybrid Si nanogratings with controllable amounts of mono- and bimetallic NPs, paving the way toward applications in heterogeneous catalysis, optical detection, light harvesting, and sensing.

3D and Inkjet Printing by Colored Mie-Resonant Silicon Nanoparticles Produced by Laser Ablation in Liquid.

Optically resonant silicon nanoparticles have emerged as a prospective platform for the structural coloration of surfaces because of their strong and spectrally selective light scattering. In this work, we developed colorful inks based on polymer mixed with monodisperse Mie-resonant silicon nanoparticles for 3D and inkjet printing. We applied a laser ablation method in a flow cell for the mass production of silicon nanoparticles in water and separated the resulting nanoparticles with different sizes by density-gradient centrifugation. Mixing the colorful nanoparticles with the polymer allows for the printing of 3D objects with various shapes and colors, which are rigid against environmental conditions.

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.

Gas Sensing of Laser-Produced Hybrid TiO2-ZnO Nanomaterials under Room-Temperature Conditions.

The preparation method can considerably affect the structural, morphological, and gas-sensing properties of mixed-oxide materials which often demonstrate superior photocatalytic and sensing performance in comparison with single-metal oxides. In this work, hybrids of semiconductor nanomaterials based on TiO2 and ZnO were prepared by laser ablation of Zn and Ti plates in water and then tested as chemiresistive gas sensors towards volatile organics (2-propanol, acetaldehyde, ethanol, methanol) and ammonia. An infrared millisecond pulsed laser with energy 2.0 J/pulse and a repetition rate of 5 Hz was applied to Zn and Ti metal targets in different ablation sequences to produce two nano-hybrids (TiO2/ZnO and ZnO/TiO2). The surface chemistry, morphology, crystallinity, and phase composition of the prepared hybrids were found to tune their gas-sensing properties. Among all tested gases, sample TiO2/ZnO showed selectivity to ethanol, while sample ZnO/TiO2 sensed 2-propanol at room temperature, both with a detection limit of ~50 ppm. The response and recovery times were found to be 24 and 607 s for the TiO2/ZnO sensor, and 54 and 50 s for its ZnO/TiO2 counterpart, respectively, towards 100 ppm of the target gas at room temperature.

Multigram-Scale Production of Hybrid Au-Si Nanomaterial by Laser Ablation in Liquid (LAL) for Temperature-Feedback Optical Nanosensing, Light-to-Heat Conversion, and Anticounterfeit Labeling.

Recent progress in hybrid optical nanomaterials composed of dissimilar constituents permitted an improvement in the performance and functionality of novel devices developed for optoelectronics, catalysis, medical diagnostics, and sensing. However, the rational combination of contrasting materials such as noble metals and semiconductors within individual hybrid nanostructures via a ready-to-use and lithography-free fabrication approach is still a challenge. Here, we report on a two-step synthesis of hybrid Au-Si microspheres generated by laser ablation of silicon in isopropanol followed by laser irradiation of the produced Si nanoparticles in the presence of HAuCl4. Thermal reduction of [AuCl4]- species to a metallic gold phase, along with its subsequent mixing with silicon under laser irradiation, creates a nanostructured material with a unique composition and morphology, as revealed by electron microscopy, tomography, and elemental analysis. A combination of basic plasmonic and nanophotonic materials such as gold and silicon within a single microsphere allows for efficient light-to-heat conversion, as well as single-particle SERS sensing with temperature-feedback modality and expanded functionality. Moreover, the characteristic Raman signal and hot-electron-induced nonlinear photoluminescence coexisting within the novel Au-Si hybrids, as well as the commonly criticized randomness of the nanomaterials prepared by laser ablation in liquid, were proved to be useful for the realization of anticounterfeiting labels based on a physically unclonable function approach.

Security labeling and optical information encryption enabled by laser-printed silicon Mie resonators.

Fighting against the falsification of valuable items remains a crucial social-threatening challenge stimulating a never-ending search for novel anti-counterfeiting strategies. The demanding security labels must simultaneously address multiple requirements (high density of the recorded information, high protection degree, etc.) and be realized via scalable and inexpensive technologies. Here, the direct reproducible femtosecond-laser patterning of thin glass-supported amorphous (α-)Si films is proposed for optical information encryption and the scalable and highly reproducible fabrication of security labels composed of Raman-active hemispherical Si nanoparticles (NPs). Laser printing conditions allow the precise control of the diameter of the formed NPs ensuring translation of their dipolar Mie resonance position within the entire visible spectral range. Two-temperature molecular dynamics simulations clarify the origin of α-Si NP formation by rupture of the molten Si layer driven by a negative GPa-range pressure near the liquid-solid interface. Arrangement of the laser-printed Mie-resonant NP allows the creation of hidden security labels offering several easy-to-realize information encryption strategies (for example, local laser-induced post-crystallization or mixing Mie-resonant and non-resonant NPs), additional protection modalities, facile Raman mapping readout and dense information recording (up to 60 000 dots per inch) close to the optical diffraction limit. The developed fabrication strategy is simple, inexpensive, and scalable and can be realized based on cheap Earth-abundant materials and commercially-available equipment justifying its practical applicability and attractiveness for anti-counterfeit and security applications.

Textured Stainless Steel as a Platform for Black Mg2Si/Si Heterojunction Solar Cells with Advanced Photovoltaic Performance.

This paper reports on a facile bottom-up method for the direct integration of a silicon (Si)-magnesium silicide (Mg2Si) heterojunction solar cell (HSC) with a textured rear reflector made of stainless steel (SS). Modified wet chemical etching and post processing of SS substrates resulted in the formation of both a rough surface texture and diffusion barrier layer, consisting of magnetite (Fe3O4) with reduced optical reflection. Then, Si, Mg2Si and CaSi2 layers were stepwise thermally evaporated onto the textured SS surface. No traces of Fe and Cr silicide phases were detected by Raman spectroscopy, confirming effective suppression of impurity diffusion from the SS to the upper layers at least at temperatures required for Si deposition, as well as Mg2Si and CaSi2 formation. The obtained black-SS/Fe3O4/Si/Mg2Si/CaSi2 sample preserved, to some extent, its underlying textured morphology and demonstrated an averaged reflection of 15% over the spectral range of 200-1800 nm, while its prototype HSC possessed a wideband photoresponse with a photoelectric conversion efficiency of 7.5% under AM1.5 illumination. Moreover, Si layers deposited alone onto a black-SS substrate demonstrated competitive antireflection properties compared with black Si (b-Si) obtained by traditional top-down etching approaches, and hybrid b-Si/textured-SS structures with a glue-bonded interlayer.

Nanomechanical and Morphological AFM Mapping of Normal Tissues and Tumors on Live Brain Slices Using Specially Designed Embedding Matrix and Laser-Shaped Cantilevers.

Cell and tissue nanomechanics has been intriguingly introduced into biomedical research, not only complementing traditional immunophenotyping and molecular analysis, but also bringing unexpected new insights for clinical diagnostics and bioengineering. However, despite the progress in the study of individual cells in culture by atomic force microscopy (AFM), its application for mapping live tissues has a number of technical limitations. Here, we elaborate a new technique to study live slices of normal brain tissue and tumors by combining morphological and nanomechanical AFM mapping in high throughput scanning mode, in contrast to the typically utilized force spectroscopy mode based on single-point probe application. This became possible due to the combined use of an appropriate embedding matrix for vibratomy and originally modified AFM probes. The embedding matrix composition was carefully developed by regulating the amounts of agar and collagen I to reach optimal viscoelastic properties for obtaining high-quality live slices that meet AFM requirements. AFM tips were rounded by irradiating them with focused nanosecond laser pulses, while the resulting tip morphology was verified by scanning electron microscopy. Live slices preparation and AFM investigation take only 55 min and could be combined with a vital cell tracer analysis or immunostaining, thus making it promising for biomedical research and clinical diagnostics.

Stability of Octadecyltrimethoxysilane-Based Coatings on Aluminum Alloy Surface.

Long-term stability in contact with water of organosilane layers formed by octadecyltrimethoxysilane (ODTMS) on polished aluminum alloy (AA2024) through dip-coating was studied by combining SEM, water contact angle measurements, and X-ray photoelectron spectroscopy. Similar organosilane layers were formed on AA2024 coated with permanganate conversion coating, 1,2-bis(triethoxysilyl)ethane (BTSE) and hydrated SiOx as under-layers, after which their long-term durability was also tested. During immersion in water for about one month, all the samples exhibited a decrease in hydrophobicity, implying the prepared organosilane layer was not stable over time, gradually hydrolyzing and letting water interact with the underlying layer. In parallel, SEM images of one-layer samples taken after immersion showed clear signs of local electrochemical corrosion, while XPS analysis confirmed a loss of silicon from the surface layer. The highest stability over time was demonstrated by a one-layer sample prepared in an ethanol/water bath for 5 min and by a similar ODTMS layer prepared on hydrated MnOx as an under-layer.

Tuning Collective Plasmon Resonances of Femtosecond Laser-Printed Metasurface.

The optical response of properly excited periodically arranged plasmonic nanostructures is known to demonstrate sharp resonance features associated with high-Q collective modes demanding for various applications in light-matter interaction, filtering and sensing. Meanwhile, practical realization and replication of plasmonic platforms supporting high-Q modes via scalable inexpensive lithography-free approach is still challenging. Here, we justify direct ablation-free irradiation of Si-supported thin Au film by nanojoule-energy femtosecond laser pulses as a single-step and scalable technology for realization of plasmonic metasurfaces supporting collective plasmonic response. Using an adjustable aperture to control and upscale the size of the fabricated nanostructures, nanobumps and nanojets, we demonstrated plasmonic metasurface supporting collective resonances with a moderately high Q-factor (up to 17) and amplitude (up to 45%) within expanded spectral range (1.4-4.5 µm). Vacuum deposition of thin films above the as-fabricated nanostructure arrays was demonstrated to provide fine tuning of the resonance position, also expanding the choice of available materials for realization of plasmonic designs with extended functionality.

Deep Subwavelength Laser-Induced Periodic Surface Structures on Silicon as a Novel Multifunctional Biosensing Platform.

Strong light localization inside the nanoscale gaps provides remarkable opportunities for creation of various medical and biosensing platforms stimulating an active search for inexpensive and easily scalable fabrication at a sub-100 nm resolution. In this paper, self-organized laser-induced periodic surface structures (LIPSSs) with the shortest ever reported periodicity of 70 ± 10 nm were directly imprinted on the crystalline Si wafer upon its direct femtosecond-laser ablation in isopropanol. Appearance of such a nanoscale morphology was explained by the formation of a periodic topography on the surface of photoexcited Si driven by interference phenomena as well as subsequent down-scaling of the imprinted grating period via Rayleigh-Taylor hydrodynamic instability. The produced deep subwavelength LIPSSs demonstrate strong anisotropic anti-reflection performance, ensuring efficient delivery of the incident far-field radiation to the electromagnetic "hot spots" localized in the Si nanogaps. This allows realization of various optical biosensing platforms operating via strong interactions of quantum emitters with nanoscale light fields. The demonstrated 80-fold enhancement of spontaneous emission from the attached nanolayer of organic dye molecules and in situ optical tracing of catalytic molecular transformations substantiate bare and metal-capped deep subwavelength Si LIPSSs as a promising inexpensive multifunctional biosensing platform.

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.

Black Au-Decorated TiO2 Produced via Laser Ablation in Liquid.

The rational combination of plasmonic and all-dielectric concepts within hybrid nanomaterials provides a promising route toward devices with ultimate performance and extended modalities. Spectral matching of plasmonic and Mie-type resonances for such nanostructures can only be achieved for their dissimilar characteristic sizes, thus making the resulting hybrid nanostructure geometry complex for practical realization and large-scale replication. Here, we produced amorphous TiO2 nanospheres decorated and doped with Au nanoclusters via single-step nanosecond-laser irradiation of commercially available TiO2 nanopowders dispersed in aqueous HAuCl4. Fabricated hybrids demonstrate remarkable light-absorbing properties (averaged value ≈96%) in the visible and near-IR spectral range mediated by bandgap reduction of the laser-processed amorphous TiO2 as well as plasmon resonances of the decorating Au nanoclusters. The findings are supported by optical spectroscopy, electron energy loss spectroscopy, transmission electron microscopy, and electromagnetic modeling. Light-absorbing and plasmonic properties of the produced hybrids were implemented to demonstrate catalytically passive SERS biosensor for identification of analytes at trace concentrations and solar steam generator that permitted to increase water evaporation rate by 2.5 times compared with that of pure water under identical 1 sun irradiation conditions.

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.

Preparation and Photocatalytic Properties of CdS and ZnS Nanomaterials Derived from Metal Xanthate.

In this paper, we report a new, simple method for the synthesis of CdS and ZnS nanoparticles (NPs) prepared in a basic aqueous medium using metal xanthate as the sulfur source. The structure, morphology, size distribution, optical band gap, and photocatalytic properties of the newly obtained nanomaterials were investigated by UV-Vis spectroscopy, X-ray diffraction, and transmission electron microscopy. The results show that both CdS and ZnS crystallized in cubic phase and formed NPs with average sizes of 7.0 and 4.2 nm for CdS and ZnS, respectively. A blue shift of UV-Vis absorbance band and higher energy band gap values were observed for both materials in comparison with their bulk counterparts, which is in accordance with the quantum confinement effect. The as-prepared nanomaterials were tested in visible-light driven photocatalytic decomposition of methylene blue (MB). After irradiation for 180 min, the degradation rate of MB with a concentration of 8 × 10-6 mol/L mixed with a photocatalyst (CdS or ZnS, both 10 mg in 100 mL solution of MB) was found to be 72% and 61%, respectively. The CdS NPs showed better photocatalytic activity than ZnS, which could be explained by their lower energy band gap and thus the ability to absorb light more efficiently when activated by visible-light irradiation.

Ultratrace Nitroaromatic Vapor Detection via Surface-Enhanced Fluorescence on Carbazole-Terminated Black Silicon.

Detection of nitroaromatic compounds (NACs) is an important applied task for environmental monitoring, medical diagnostics, and forensic analysis. However, detection of NAC vapors is challenging owing to their low vapor pressure and relatively weak sensitivity of the existing detection techniques. Here, we propose a novel concept to design fluorescence (FL) detection platforms based on chemical functionalization of nanotextured dielectric surfaces exhibiting resonant light absorption, trapping, and localization effects. We demonstrate highly-efficient NAC vapor sensor with selective FL-quenching response from monolayers of carbazole moieties covalently bonded to a spiky silicon surface, "black" silicon, produced over the centimeter-scale area using simple reactive ion etching. The sensor is shown to provide unprecedented ppt (10-12) range limits of detection for several NAC vapors. Easy-to-implement scalable fabrication procedure combined with simple and versatile functionalization techniques applicable to all-dielectric surfaces make the suggested concept promising for realization of various gas sensing systems for social and environmental safety applications.

Multi-Purpose Nanovoid Array Plasmonic Sensor Produced by Direct Laser Patterning.

We demonstrate a multi-purpose plasmonic sensor based on a nanovoid array fabricated via inexpensive and highly-reproducible direct femtosecond laser patterning of thin glass-supported Au films. The proposed nanovoid array exhibits near-IR surface plasmon (SP) resonances, which can be excited under normal incidence and optimised for specific applications by tailoring the array periodicity, as well as the nanovoid geometric shape. The fabricated SP sensor offers competitive sensitivity of ≈ 1600 nm/RIU at a figure of merit of 12 in bulk refractive index tests, as well as allows for identification of gases and ultra-thin analyte layers, making the sensor particularly useful for common bioassay experiments. Moreover, isolated nanovoids support strong electromagnetic field enhancement at lattice SP resonance wavelength, allowing for label-free molecular identification via surface-enhanced vibration spectroscopy.

Single-Mode Lasing from Imprinted Halide-Perovskite Microdisks.

Halide-perovskite microlasers have demonstrated fascinating performance owing to their low-threshold lasing at room temperature and low-cost fabrication. However, being synthesized chemically, controllable fabrication of such microlasers remains challenging, and it requires template-assisted growth or complicated nanolithography. Here, we suggest and implement an approach for the fabrication of microlasers by direct laser ablation of a thin film on glass with donut-shaped femtosecond laser beams. The fabricated microlasers represent MAPbBr xI y microdisks with 760 nm thickness and diameters ranging from 2 to 9 µm that are controlled by a topological charge of the vortex beam. As a result, this method allows one to fabricate single-mode perovskite microlasers operating at room temperature in a broad spectral range (550-800 nm) with Q-factors up to 5500. High-speed fabrication and reproducibility of microdisk parameters, as well as a precise control of their location on a surface, make it possible to fabricate centimeter-sized arrays of such microlasers. Our finding is important for direct writing of fully integrated coherent light sources for advanced photonic and optoelectronic circuitry.