Laser-Induced Periodic Surface Structures on Layered GaSe Crystals: Structural Coloring and Infrared Antireflection.

We study structural and morphological transformations caused by multipulse femtosecond-laser exposure of Bridgman-grown ϵ-phase GaSe crystals, a van der Waals semiconductor promising for nonlinear optics and optoelectronics. We unveil, for the first time, the laser-driven self-organization regimes in GaSe allowing the formation of regular laser-induced periodic surface structures (LIPSSs) that originate from interference of the incident radiation and interface surface plasmon waves. LIPSSs formation causes transformation of the near-surface layer to amorphous Ga2Se3 at negligible oxidation levels, evidenced from comprehensive structural characterization. LIPSSs imprinted on both output crystal facets provide a 1.2-fold increase of the near-IR transmittance, while the ability to control local periodicity by processing parameters enables multilevel structural color marking of the crystal surface. Our studies highlight direct fs-laser patterning as a multipurpose application-ready technology for precise nanostructuring of promising van der Waals semiconductors, whose layered structure restricts application of common nanofabrication approaches.

Hierarchical anti-reflective laser-induced periodic surface structures (LIPSSs) on amorphous Si films for sensing applications.

Here, we applied direct laser-induced periodic surface structuring to drive the phase transition of amorphous silicon (a-Si) into nanocrystalline (nc) Si imprinted as regular arrangement of Si nanopillars passivated with a SiO2 layer. By varying the laser beam scanning speed at a fixed pulse energy, we successfully tailored the resulting unique surface morphology of the formed LIPSSs that change from ordered arrangement of conical protrusions to highly uniform surface gratings, where sub-wavelength scale ripples decorate the valleys between near-wavelength scale ridges. Along with the surface morphology, the nc-Si/SiO2 volume ratio can also be controlled via laser processing parameters allowing the tailoring of the optical properties of the produced textured surfaces to achieve anti-reflection performance or partial transmission in the visible spectral range. Diverse hierarchical LIPSSs can be fabricated and replicated over large-scale areas opening a pathway for various applications including optical sensors, nanoscale temperature management, and solar light harvesting. By taking advantage of good wettability, enlarged surface area and remarkable light-trapping characteristics of the produced hierarchical morphologies, we demonstrated the first LIPSS-based surface enhanced fluorescent sensor that allowed the identification of metal cations providing a sub-nM detection limit unachievable by conventional fluorescence measurements in solutions.

Silicon microprotrusions with tailored chirality enabled by direct femtosecond laser ablation.

Here, we report on formation of nanoprotrusions on the surface of a bulk crystalline silicon wafer under femtosecond-laser ablation with a donut-shaped laser beam. By breaking circular symmetry of the irradiating donut-shaped fs-pulse beam, a switch in geometry of the formed surface nanoprotrusions from regular to chiral was demonstrated. The chirality of the obtained Si nanostructures was promoted with an asymmetry degree of the laser beam. An uneven helical flow of laser-melted Si caused by asymmetry of the initial intensity and temperature pattern on the laser-irradiated Si surface explains this phenomenon. Chirality of the formed protrusions was confirmed by visualizing cross-sectional cuts produced by focused ion beam milling as well as Raman activity of these structures probed by circularly polarized light with opposite handedness. Our results open a pathway towards easy-to-implement inexpensive fabrication of chiral all-dielectric nanostructures for advanced nanophotonic applications and sensing of chiral molecules.

Refractive twisted microaxicons.

Complex-shaped light fields with specially designed intensity, phase, and polarization distributions are highly demanded for various applications including optical tweezers, laser material processing, and lithography. Here, we propose a novel (to the best of our knowledge) optical element formed by the twisting of a conic surface, a twisted microaxicon, allowing us to controllably generate high-quality spiral-shaped intensity patterns. Performance of the proposed element was analyzed both analytically and numerically using ray approximation and the rigorous finite difference time domain (FDTD) solution of Maxwell's equation. The main geometric parameters, an apex cone angle and a degree of twisting, were considered to control and optimize the generated spiral-shaped intensity patterns. The three-dimensional structure of such a microaxicon cannot be described by an unambiguous height function; therefore, it has no diffraction analogue in the form of a thin optical element. Such an element can be produced via direct laser ablation of transparent targets with structured laser beams or direct laser writing via two-photon photopolymerization and can be used in various micro- and nano-optical applications.

Tailoring spontaneous infrared emission of HgTe quantum dots with laser-printed plasmonic arrays.

Chemically synthesized near-infrared to mid-infrared (IR) colloidal quantum dots (QDs) offer a promising platform for the realization of devices including emitters, detectors, security, and sensor systems. However, at longer wavelengths, the quantum yield of such QDs decreases as the radiative emission rate drops following Fermi's golden rule, while non-radiative recombination channels compete with light emission. Control over the radiative and non-radiative channels of the IR-emitting QDs is crucially important to improve the performance of IR-range devices. Here, we demonstrate strong enhancement of the spontaneous emission rate of near- to mid-IR HgTe QDs coupled to periodically arranged plasmonic nanoantennas, in the form of nanobumps, produced on the surface of glass-supported Au films via ablation-free direct femtosecond laser printing. The enhancement is achieved by simultaneous radiative coupling of the emission that spectrally matches the first-order lattice resonance of the arrays, as well as more efficient photoluminescence excitation provided by coupling of the pump radiation to the local surface plasmon resonances of the isolated nanoantennas. Moreover, coupling of the HgTe QDs to the lattice plasmons reduces the influence of non-radiative decay losses mediated by the formation of polarons formed between QD surface-trapped carriers and the IR absorption bands of dodecanethiol used as a ligand on the QDs, allowing us to improve the shape of the emission spectrum through a reduction in the spectral dip related to this ligand coupling. Considering the ease of the chemical synthesis and processing of the HgTe QDs combined with the scalability of the direct laser fabrication of nanoantennas with tailored plasmonic responses, our results provide an important step towards the design of IR-range devices for various applications.

Plasmonic Nanolenses Produced by Cylindrical Vector Beam Printing for Sensing Applications.

Interaction of complex-shaped light fields with specially designed plasmonic nanostructures gives rise to various intriguing optical phenomena like nanofocusing of surface waves, enhanced nonlinear optical response and appearance of specific low-loss modes, which can not be excited with ordinary Gaussian-shaped beams. Related complex-shaped nanostructures are commonly fabricated using rather expensive and time-consuming electron- and ion-beam lithography techniques limiting real-life applicability of such an approach. In this respect, plasmonic nanostructures designed to benefit from their excitation with complex-shaped light fields, as well as high-performing techniques allowing inexpensive and flexible fabrication of such structures, are of great demand for various applications. Here, we demonstrate a simple direct maskless laser-based approach for fabrication of back-reflector-coupled plasmonic nanorings arrays. The approach is based on delicate ablation of an upper metal film of a metal-insulator-metal (MIM) sandwich with donut-shaped laser pulses followed by argon ion-beam polishing. After being excited with a radially polarized beam, the MIM configuration of the nanorings permitted to realize efficient nanofocusing of constructively interfering plasmonic waves excited in the gap area between the nanoring and back-reflector mirror. For optimized MIM geometry excited by radially polarized CVB, substantial enhancement of the electromagnetic near-fields at the center of the ring within a single focal spot with the size of 0.37λ2 can be achieved, which is confirmed by Finite Difference Time Domain calculations, as well as by detection of 100-fold enhanced photoluminescent signal from adsorbed organic dye molecules. Simple large-scale and cost-efficient fabrication procedure offering also a freedom in the choice of materials to design MIM structures, along with remarkable optical and plasmonic characteristics of the produced structures make them promising for realization of various nanophotonic and biosensing platforms that utilize cylindrical vector beam as a pump source.

Si1-xGex nanoantennas with a tailored Raman response and light-to-heat conversion for advanced sensing applications.

Active light-emitting all-dielectric nanoantennas recently have demonstrated great potential as highly efficient nanoscale light sources owing to their strong luminescent and Raman responses. However, their large-scale fabrication faces a number of problems related to productivity limits of existing lithography techniques. Thus, high-throughput fabrication strategies allowing in a facile way to tailor of the nanoantenna emission and thermal properties in the process of their fabrication are highly desirable for various applications. Here, we propose a cost-effective approach to large-scale fabrication of Si1-xGex alloyed Mie nanoresonators possessing an enhanced inherent Raman response which can be simply tailored via tuning the Ge concentration. Moreover, by tailoring the relative Ge composition one can gradually change a complex refractive index of the produced Si1-xGex alloy, which affects the ratio between radiative and nonradiative losses in Si1-xGex nanoantennas, which is crucial for optimization of their optical heating efficiency. Composition-tunable Si1-xGex nanoantennas with an optimized size, light-to-heat conversion and Raman response are implemented for non-invasive sensing of 4-aminothiophenol molecules with a temperature feedback modality and high subwavelength spatial resolution. The results are important for advanced multichannel optical sensing, providing information on analyte's composition, analyte-nanoantenna temperature response and spatial position.

Symmetry-wise nanopatterning and plasmonic excitation of ring-like gold nanoholes by structured femtosecond laser pulses with different polarizations.

Low- and ultralow-energy tightly focused 200 fs, 515 nm donut-shaped laser pulses at 0.25 and 0.65 NA focusing were used for single-shot ablative pulse-energy scalable nanopatterning of 50 nm thick gold film and the following plasmonic excitation of dye monolayer photoluminescence (PL) in the fabricated nanostructures, respectively. The same pulses at much lower, non-ablative nanojoule energies, and the same focusing and linear, azimuthal, or radial polarizations provided efficient spectrally and symmetry-matched excitation of both localized and delocalized surface electromagnetic modes in the separate, ring-like through holes and their arrays in the film envisioned by our modeling, thus resulting in a polarization-sensitive yield of rhodamine 6G dye PL. The demonstrated consistency between the symmetries of the donut-shaped low-energy photo-exciting laser beam, its polarization state, and the donut-shaped gold nanostructures, produced by the same beam at high, ablative pulse energies, paves the way to smart, self-consistent nanofabrication and plasmonic sensing, when the structured light interacts with the consistently structured matter.

10-million-elements-per-second printing of infrared-resonant plasmonic arrays by multiplexed laser pulses.

We report on high-quality infrared (IR)-resonant plasmonic nanoantenna arrays fabricated on a thin gold film by tightly focused femtosecond (fs) laser pulses coming at submegahertz repetition rates at a printing rate of 10 million elements per second. To achieve this, the laser pulses were spatially multiplexed by fused silica diffractive optical elements into 51 identical submicrometer-sized laser spots arranged into a linear array at periodicity down to 1 µm. The demonstrated high-throughput nanopatterning modality indicates fs laser maskless microablation as an emerging robust, flexible, and competitive lithographic tool for advanced fabrication of IR-range plasmonic sensors for environmental sensing, chemosensing, and biosensing.

Ultrafast laser printing of self-organized bimetallic nanotextures for multi-wavelength biosensing.

Surface-enhanced spectroscopy (SES) techniques, including surface-enhanced photoluminescence (SEPL), Raman scattering (SERS) and infrared absorption (SEIRA), represent powerful biosensing modalities, allowing non-invasive label-free identification of various molecules and quantum emitters in the vicinity of nanotextured surfaces. Enhancement of multi-wavelength (vis-IR) excitation of analyte molecules of interest atop a single textured substrate could pave the way toward ultimate chemosensing performance and further widespread implementation of the SES-based approaches in various crucial areas, such as point-ofcare diagnostics. In this paper, an easy-to-implement ultrafast direct laser printing via partial spallation of thermally-thick silver films and subsequent large-scale magnetron deposition of nanometer-thick Au layers of variable thickness was implemented to produce bimetallic textured surfaces with the cascaded nanotopography. The produced bimetallic textures demonstrate the strong broadband plasmonic response over the entire visible spectral range. Such plasmonic performance was confirmed by convenient spectroscopy-free Red-Green-Blue (RGB) color analysis of the dark-field (DF) scattering images supported by numerical calculations of the electromagnetic (EM) "near-fields", as well as comprehensive DF spectroscopic characterization. Bimetallic laser-printed nanotextures, which can be easily printed at ultrafast (square millimeters per second) rate, using galvanometric scanning, exhibited strong enhancement of the SEPL (up to 75-fold) and SERS (up to 106 times) yields for the organic dye molecules excited at various wavelengths. Additionally, comprehensive optical and sensing characterization of the laser-printed bimetallic surface structures allows substantiating the convenient spectroscopy-free RGB color analysis as a valuable tool for predictive assessment of the plasmonic properties of the various irregularly and quasi-periodically nanotextured surfaces.

Chemically non-perturbing SERS detection of a catalytic reaction with black silicon.

All-dielectric resonant micro- and nano-structures made of high-index dielectrics have recently emerged as a promising surface-enhanced Raman scattering (SERS) platform which can complement or potentially replace the metal-based counterparts in routine sensing measurements. These unique structures combine the highly-tunable optical response and high field enhancement with the non-invasiveness, i.e. chemically non-perturbing the analyte, simple chemical modification and recyclability. Meanwhile, commercially competitive fabrication technologies for mass production of such structures are still missing. Here, we attest a chemically inert black silicon (b-Si) substrate consisting of randomly-arranged spiky Mie resonators for a true non-invasive (chemically non-perturbing) SERS identification of the molecular fingerprints at low concentrations. Based on the comparative in situ SERS tracking of the para-aminothiophenol (PATP)-to-4,4'-dimercaptoazobenzene (DMAB) catalytic conversion on the bare and metal-coated b-Si, we justify the applicability of the metal-free b-Si for ultra-sensitive non-invasive SERS detection at a concentration level as low as 10-6 M. We performed supporting finite-difference time-domain (FDTD) calculations to reveal the electromagnetic enhancement provided by an isolated spiky Si resonator in the visible spectral range. Additional comparative SERS studies of the PATP-to-DMAB conversion performed with a chemically active bare black copper oxide (b-CuO) substrate as well as SERS detection of the slow daylight-driven PATP-to-DMAB catalytic conversion in the aqueous methanol solution loaded with colloidal silver nanoparticles (Ag NPs) confirm the non-invasive SERS performance of the all-dielectric crystalline b-Si substrate. A proposed SERS substrate can be fabricated using the easy-to-implement scalable technology of plasma etching amenable on substrate areas over 10 × 10 cm2 making such inexpensive all-dielectric substrates promising for routine SERS applications, where the non-invasiveness is of high importance.

Mapping the refractive index with single plasmonic nanoantenna.

As the size of the state-of-the-art optical devices shrinks to nanoscale, the need for tools allowing mapping the local optical properties at deep sub-diffraction resolution increases. Here we demonstrate successful mapping the variations of the refractive index of a smooth dielectric surface by detecting spectral response of a single spherical-shape Ag nanoparticle optically aligned with a supporting optical fiber axicon microlens. We propose and examine various excitation schemes of the plasmonic nanoantenna to provide efficient interaction of its dipolar and quadrupolar modes with the underlying sample surface and to optimize the mapping resolution and sensitivity. Moreover, we demonstrate an lithography-free approach for fabrication of the scanning probe combining the high-quality fiber microaxicon with the Ag spherical nanoparticle atop. Supporting finite-difference time-domain calculations are undertaken to tailor the interaction of the plasmonic nanoantenna and the underlying dielectric substrate upon various excitation conditions demonstrating good agreement with our experimental findings and explaining the obtained results.

Zero-orbital-angular-momentum laser printing of chiral nanoneedles.

Laser irradiation of various materials including metals, polymers, and semiconductors with vortex beams was previously shown to "twist" transiently molten matter providing the direct easy-to-implement way to obtain chiral surface relief. Specifically for metals, this effect was attributed to transfer of an orbital angular momentum (OAM) carried by a vortex beam. In this Letter, we report the formation of twisted metallic nanoneedles on surfaces of silver and gold films under their irradiation by a zero-OAM laser beam with a spiral-shaped intensity distribution. Our comparative experiments clearly demonstrate, for the first time to the best of our knowledge, that the formation of the chiral nanoneedles on the noble-metal films is mainly governed by the temperature-gradient-induced chiral thermocapillary mass transfer, rather than by OAM-driven rotation of the molten matter.

Multi-beam pulsed-laser patterning of plasmonic films using broadband diffractive optical elements.

Multi-sector broadband diffractive optical elements (DOEs) were designed and fabricated from fused silica for high-efficiency multiplexing of femtosecond and nanosecond Gaussian laser beams into multiple (up to one 100) optically tunable microbeams with increased high-numerical aperture (NA) focal depths. Various DOE-related issues, such as high-NA laser focusing, laser pulsewidth, and DOE symmetry-dependent heat conduction effects, as well as the corresponding spatial resolution, were discussed in the context of high-throughput laser patterning. The increased focal depths provided by such DOEs, their high multiplexing efficiency and damage threshold, as well as easy-to-implement optical shaping of output microbeams provide advanced opportunities for direct, mask-free, and vacuum-free high-throughput subtractive (ablative) and displacive pulsed-laser patterning of various nanoplasmonic films for surface-enhanced spectroscopy, sensing, and light control.

Direct laser printing of chiral plasmonic nanojets by vortex beams.

Donut-shaped laser radiation, carrying orbital angular momentum, namely optical vortex, was recently shown to provide vectorial mass transfer, twisting transiently molten material and producing chiral micro-scale structures on surfaces of different bulk materials upon their resolidification. In this paper, we show that at high-NA focusing nanosecond laser vortices can produce chiral nanoneedles (nanojets) of variable size on thin films of such plasmonic materials, as silver and gold films, covering thermally insulating substrates. Main geometric parameters of the produced chiral nanojets, such as height and aspect ratio, were shown to be tunable in a wide range by varying metal film thickness, supporting substrates, and the optical size of the vortex beam. Donut-shaped vortex nanosecond laser pulses, carrying two vortices with opposite handedness, were demonstrated to produce two chiral nanojets twisted in opposite directions. These results suggest optical interference of the incident and reflected laser beams as a source of complex surface intensity distributions in metal films, possessing spiral components and driving both center-symmetric and spiral thermocapillary melt flows to yield in frozen nanoneedles with their pre-determined spiral nanocarving.

Laser printing of resonant plasmonic nanovoids.

Hollow reduced-symmetry resonant plasmonic nanostructures possess pronounced tunable optical resonances in the UV-vis-IR range, being a promising platform for advanced nanophotonic devices. However, the present fabrication approaches require several consecutive technological steps to produce such nanostructures, making their large-scale fabrication rather time-consuming and expensive. Here, we report on direct single-step fabrication of large-scale arrays of hollow parabolic- and cone-shaped nanovoids in silver and gold thin films, using single-pulse femtosecond nanoablation at high repetition rates. The lateral and vertical size of such nanovoids was found to be laser energy-tunable. Resonant light scattering from individual nanovoids was observed in the visible spectral range, using dark-field confocal microspectroscopy, with the size-dependent resonant peak positions. These colored geometric resonances in far-field scattering were related to excitation and interference of transverse surface plasmon modes in nanovoid shells. Plasmon-mediated electromagnetic field enhancement near the nanovoids was evaluated via finite-difference time-domain calculations for their model shapes simulated by three-dimensional molecular dynamics, and experimentally verified by means of photoluminescence microscopy and Raman spectroscopy.

Flash-imprinting of intense femtosecond surface plasmons for advanced nanoantenna fabrication.

In this work, we demonstrate an all-laser method of fabrication of optical nanoantennas (ONAs) with an additional coupling/focusing diffractive element. This method is based on double-shot femtosecond laser nanoablation of a thin supported metallic film, inducing a sequence of electrodynamic (surface plasmon-polariton [SPP] excitation and interference), thermal (melting, ablation and ultrafast cooling), and hydrodynamic processes. In particular, the thermal and hydrodynamic processes are important for ONA formation after the first laser shot, while second spatially shifted laser shot via an induced SPP wave results in a radial surface grating near the nanoantenna. Such gratings provide efficient coupling between incident laser radiation and SPP waves, thus significantly improving the ONA efficiency.

Formation of crownlike and related nanostructures on thin supported gold films irradiated by single diffraction-limited nanosecond laser pulses.

A type of laser-induced surface relief nanostructure-the nanocrown-on thin metallic films was studied both experimentally and theoretically. The nanocrowns, representing a thin corrugated rim of resolidified melt and resembling well-known impact-induced water-crown splashes, were produced by single diffraction-limited nanosecond laser pulses on thin gold films of variable thickness on low-melting copper and high-melting tungsten substrates, providing different transient melting and adhesion conditions for these films. The proposed model of the nanocrown formation, based on a hydrodynamical (thermocapillary Marangoni) surface instability and described by a Kuramoto-Sivashinsky equation, envisions key steps of the nanocrown appearance and gives qualitative predictions of the acquired nanocrown parameters.

High-quality fiber microaxicons fabricated by a modified chemical etching method for laser focusing and generation of Bessel-like beams.

The fabrication method of the high-quality fiber microaxicons (FMAs) on the endface of the optical fiber was developed. Using several types of the commercially available optical fibers we experimentally demonstrated the fabrication of a high-quality FMA focusing a laser beam into a tiny spot with a FWHM≈0.6λ and Bessel-like field distribution. It was also demonstrated that choosing the appropriate chemical composition of the etching solution makes it possible to change the shape of the FMA tip from conical to hemispherical. This allows one to change the spatial distribution of the output laser beam, which can represent both the Bessel-like beam with a depth of focus of up to 49λ and a very tiny focal spot close to the diffraction limit size. Experimentally measured focusing characteristics of the fabricated FMAs obtained using a homemade collection-mode scanning near-field optical microscope setup demonstrate good agreement with numerical simulations based on the 3D finite-difference time-domain simulations.

Through nanohole formation in thin metallic film by single nanosecond laser pulses using optical dielectric apertureless probe.

Separate nanoholes with the minimum size down to 35 nm (~λ/15) and nanohole arrays with the hole size about 100 nm (~λ/5) were fabricated in a 50 nm optically "thick" Au/Pd film, using single 532 nm pump nanosecond laser pulses focused to diffraction-limited spots by a specially designed apertureless dielectric fiber probe. Nanohole fabrication in the metallic film was found to result from lateral heat diffusion and center-symmetrical lateral expulsion of the melt by its vapor recoil pressure. The optimized apertureless dielectric microprobe was demonstrated to enable laser fabrication of deep through nanoholes.