Wandering principal optical axes in van der Waals triclinic materials.

Nature is abundant in material platforms with anisotropic permittivities arising from symmetry reduction that feature a variety of extraordinary optical effects. Principal optical axes are essential characteristics for these effects that define light-matter interaction. Their orientation - an orthogonal Cartesian basis that diagonalizes the permittivity tensor, is often assumed stationary. Here, we show that the low-symmetry triclinic crystalline structure of van der Waals rhenium disulfide and rhenium diselenide is characterized by wandering principal optical axes in the space-wavelength domain with above π/2 degree of rotation for in-plane components. In turn, this leads to wavelength-switchable propagation directions of their waveguide modes. The physical origin of wandering principal optical axes is explained using a multi-exciton phenomenological model and ab initio calculations. We envision that the wandering principal optical axes of the investigated low-symmetry triclinic van der Waals crystals offer a platform for unexplored anisotropic phenomena and nanophotonic applications.

Exploring van der Waals materials with high anisotropy: geometrical and optical approaches.

The emergence of van der Waals (vdW) materials resulted in the discovery of their high optical, mechanical, and electronic anisotropic properties, immediately enabling countless novel phenomena and applications. Such success inspired an intensive search for the highest possible anisotropic properties among vdW materials. Furthermore, the identification of the most promising among the huge family of vdW materials is a challenging quest requiring innovative approaches. Here, we suggest an easy-to-use method for such a survey based on the crystallographic geometrical perspective of vdW materials followed by their optical characterization. Using our approach, we found As2S3 as a highly anisotropic vdW material. It demonstrates high in-plane optical anisotropy that is ~20% larger than for rutile and over two times as large as calcite, high refractive index, and transparency in the visible range, overcoming the century-long record set by rutile. Given these benefits, As2S3 opens a pathway towards next-generation nanophotonics as demonstrated by an ultrathin true zero-order quarter-wave plate that combines classical and the Fabry-Pérot optical phase accumulations. Hence, our approach provides an effective and easy-to-use method to find vdW materials with the utmost anisotropic properties.

Crystallinity as a factor of SERS stability of silver nanoparticles formed by Ar+ irradiation.

The plasmonic sensors based on silver nanoparticles are limited in application due to their relatively fast degradation in the ambient atmosphere. The technology of ion-beam modification for the creation of monocrystalline silver nanoparticles (NPs) with stable plasmonic properties will expand the application of silver nanostructures. In the present study, highly-stable monocrystalline NPs were formed on the basis of a thin silver film by low-energy ion irradiation. Combined with lithography, this technique allows the creation of nanoparticle ensembles in variant forms. The characterization of the nanoparticles formed by ion-beam modification showed long-term outstanding for Ag nanoparticles stability of their plasmonic properties due to their monocrystalline structure. According to optical spectroscopy data, the reliable plasmonic properties in the ambient atmosphere are preserved for up to 39 days. The mapping of crystal violet dye via surface-enhanced Raman spectroscopy (SERS) revealed a strong amplification factor sustaining at least thrice as long as the one of similarly sized polycrystalline silver NPs formed by annealing. The plasmonic properties sustain more than a month of storage in the ambient atmosphere. Thus, ion-beam modification of silver film makes it possible to fabricate NPs with stable plasmonic properties and form clusters of NPs for sensor technology and SERS applications.

Broadband optical properties of Ti3C2 MXene revisited.

The exceptional optical, electrical, and mechanical capabilities of layered transition metal carbides, nitrides, and carbonitrides, called MXenes, revolutionized materials science. Among them, Ti3C2 received the most attention owing to the developed synthesis and processing methods, high conductivity, and pronounced plasmonic response. The latter, however, remains controversial with the open question of whether the peak around 800 nm has plasmonic or interband transition origin. To address this issue, we combine spectroscopic ellipsometry and transmittance results with first-principle computations. Their combination reveals that although Ti3C2 is a metal, its optical response becomes plasmonic (Re ε < 0) above 1415 nm, in contrast to the previous understanding. In addition to fundamental significance, this dual dielectric/plasmonic optical response opens a path for theranostic applications, as we demonstrated on the example of Ti3C2 nanospheres. Thus, our study revisits broadband (300-3300 nm) optical constants of Ti3C2 and broadens its application scope in photonics.

Lasing Effect in Symmetrical van der Waals Heterostructured Metasurfaces Due to Lattice-Induced Multipole Coupling.

New practical ways to reach the lasing effect in symmetrical metasurfaces have been developed and theoretically demonstrated. Our approach is based on excitation of the resonance of an octupole quasi-trapped mode (OQTM) in heterostructured symmetrical metasurfaces composed of monolithic disk-shaped van der Waals meta-atoms featured by thin photoluminescent layers and placed on a substrate. We revealed that the coincidence of the photoluminescence spectrum maximum of these layers with the wavelength of high-quality OQTM resonance leads to the lasing effect. Based on the solution of laser rate equations and direct full-wave simulation, it was shown that lasing is normally oriented to the metasurface plane and occurs from the entire area of metasurface consisting of MoS2/hBN/MoTe2 disks with line width of generated emission of only about 1.4 nm near the wavelength 1140 nm. This opens up new practical possibilities for creating surface emitting laser devices in subwavelength material systems.

Optical Nanoimaging of Surface Plasmon Polaritons Supported by Ultrathin Metal Films.

The physics of electrons, photons, and their plasmonic interactions change dramatically when one or more dimensions are reduced to atomic-level thicknesses. For example, graphene exhibits unique electrical, plasmonic, and optical properties. Likewise, atomic-thick metal films are expected to exhibit extraordinary quantum optical properties. Several methods of growing ultrathin metal films were demonstrated, but the quality of the obtained films was much worse compared to bulk films. In this work, we propose a new method of making ultrathin gold films that are close in their properties to bulk gold films. Excellent plasmonic properties are revealed by directly observing quasi-short- and quasi-long-range plasmons in such a film via scanning near-field optical microscopy. The results pave the way for the use of ultrathin gold films in flexible and transparent nanophotonics and optoelectronic applications.

Physisorption-Mediated Charge Transfer in TiS2 Nanodiscs: A Room Temperature Sensor for Highly Sensitive and Reversible Carbon Dioxide Detection.

Real-time and high-performance monitoring of trace carbon dioxide (CO2) has become a necessity due to its substantial impact on the global climate, human health, indoor occupancy, and crop productivity. Two-dimensional materials such as transition metal dichalcogenides (TMDs) have gained significant interest in gas sensing applications owing to their intrinsically high surface-to-volume ratio. However, the research has been limited to prominent TMDs such as WS2 and MoS2. Specifically, the chemiresistive sensing performance of titanium disulfide (TiS2) has rarely been investigated. We present an electric-field-assisted TiS2 nanodisc assembly for the fabrication of a low-cost, low-power CO2 gas sensor based on charge transfer between physisorbed CO2 analyte molecules and TiS2 nanodiscs operating at room temperature. The physiochemical properties of the synthesized TiS2 nanodiscs were investigated via scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Raman spectroscopy. The fabricated sensor demonstrated an ultra-high sensor response of 60%, a fast response time of 37 s toward 500 ppm CO2 gas, and the lowest detection limit of 5 ppm under ambient conditions. The low adsorption energies and vdW interaction between CO2 molecules and TiS2 resulted in easy desorption, allowing the sensor to self-recover without the need for external stimuli, which is hardly been witnessed in other 2D material analogues. Furthermore, the sensor has excellent reproducibility and stability for successive analyte exposures, as well as excellent selectivity for CO2 over other interfering gases. This reported sensor based on 2D TMDs is the first of its type to integrate such a broad range of sensor characteristics (such as high sensor response and sensitivity, rapid response and recovery times, a high signal-to-noise ratio, and excellent selectivity at room temperature) into a single, revolutionary device for CO2 detection.

van der Waals Materials for Overcoming Fundamental Limitations in Photonic Integrated Circuitry.

With the advance of on-chip nanophotonics, there is a high demand for high-refractive-index and low-loss materials. Currently, this technology is dominated by silicon, but van der Waals (vdW) materials with a high refractive index can offer a very advanced alternative. Still, up to now, it was not clear if the optical anisotropy perpendicular to the layers might be a hindering factor for the development of vdW nanophotonics. Here, we studied WS2-based waveguides in terms of their optical properties and, particularly, in terms of possible crosstalk distance. Surprisingly, we discovered that the low refractive index in the direction perpendicular to the atomic layers improves the characteristics of such devices, mainly due to expanding the range of parameters at which single-mode propagation can be achieved. Thus, using anisotropic materials offers new opportunities and novel control knobs when designing nanophotonic devices.

TiS3 Nanoribbons: A Novel Material for Ultra-Sensitive Photodetection across Extreme Temperature Ranges.

Photodetectors that can operate over a wide range of temperatures, from cryogenic to elevated temperatures, are crucial for a variety of modern scientific fields, including aerospace, high-energy science, and astro-particle science. In this study, we investigate the temperature-dependent photodetection properties of titanium trisulfide (TiS3)- in order to develop high-performance photodetectors that can operate across a wide range of temperatures (77 K-543 K). We fabricate a solid-state photodetector using the dielectrophoresis technique, which demonstrates a quick response (response/recovery time ~0.093 s) and high performance over a wide range of temperatures. Specifically, the photodetector exhibits a very high photocurrent (6.95 × 10-5 A), photoresponsivity (1.624 × 108 A/W), quantum efficiency (3.3 × 108 A/W·nm), and detectivity (4.328 × 1015 Jones) for a 617 nm wavelength of light with a very weak intensity (~1.0 × 10-5 W/cm2). The developed photodetector also shows a very high device ON/OFF ratio (~32). Prior to fabrication, the TiS3 nanoribbons were synthesized using the chemical vapor technique and characterized according to their morphology, structure, stability, and electronic and optoelectronic properties; this was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a UV-Visible-NIR spectrophotometer. We anticipate that this novel solid-state photodetector will have broad applications in modern optoelectronic devices.

Design of silicone interfaces with antibacterial properties.

Silicone implants are widely used for plastic or reconstruction medical applications. However, they can cause severe infections of inner tissues due to bacterial adhesion and biofilm growth on implant surfaces. The development of new antibacterial nanostructured surfaces can be considered as the most promising strategy to deal with this problem. In this article, we studied the influence of nanostructuring parameters on the antibacterial properties of silicone surfaces. Nanostructured silicone substrates with nanopillars of various dimensions were fabricated using a simple soft lithography technique. Upon testing of the obtained substrates, we identified the optimal parameters of silicone nanostructures to achieve the most pronounced antibacterial effect against the bacterial culture of Escherichia coli. It was demonstrated that up to 90% reduction in bacterial population compared to flat silicone substrates can be achieved. We also discussed possible underlying mechanisms behind the observed antibacterial effect, the understanding of which is essential for further progress in this field.

Elastic Gallium Phosphide Nanowire Optical Waveguides-Versatile Subwavelength Platform for Integrated Photonics.

Emerging technologies for integrated optical circuits demand novel approaches and materials. This includes a search for nanoscale waveguides that should satisfy criteria of high optical density, small cross-section, technological feasibility and structural perfection. All these criteria are met with self-assembled gallium phosphide (GaP) epitaxial nanowires. In this work, the effects of the nanowire geometry on their waveguiding properties are studied both experimentally and numerically. Cut-off wavelength dependence on the nanowire diameter is analyzed to demonstrate the pathways for fabrication of low-loss and subwavelength cross-section waveguides for visible and near-infrared (IR) ranges. Probing the waveguides with a supercontinuum laser unveils the filtering properties of the nanowires due to their resonant action. The nanowires exhibit perfect elasticity allowing fabrication of curved waveguides. It is demonstrated that for the nanowire diameters exceeding the cut-off value, the bending does not sufficiently reduce the field confinement promoting applicability of the approach for the development of nanoscale waveguides with a preassigned geometry. Optical X-coupler made of two GaP nanowires allowing for spectral separation of the signal is fabricated. The results of this work open new ways for the utilization of GaP nanowires as elements of advanced photonic logic circuits and nanoscale interferometers.

Broadband Optical Properties of Bi2Se3.

Materials with high optical constants are of paramount importance for efficient light manipulation in nanophotonics applications. Recent advances in materials science have revealed that van der Waals (vdW) materials have large optical responses owing to strong in-plane covalent bonding and weak out-of-plane vdW interactions. However, the optical constants of vdW materials depend on numerous factors, e.g., synthesis and transfer method. Here, we demonstrate that in a broad spectral range (290-3300 nm) the refractive index n and the extinction coefficient k of Bi2Se3 are almost independent of synthesis technology, with only a ~10% difference in n and k between synthesis approaches, unlike other vdW materials, such as MoS2, which has a ~60% difference between synthesis approaches. As a practical demonstration, we showed, using the examples of biosensors and therapeutic nanoparticles, that this slight difference in optical constants results in reproducible efficiency in Bi2Se3-based photonic devices.

Scanning Near-Field Optical Microscopy of Ultrathin Gold Films.

Ultrathin metal films are an essential platform for two-dimensional (2D) material compatible and flexible optoelectronics. Characterization of thin and ultrathin film-based devices requires a thorough consideration of the crystalline structure and local optical and electrical properties of the metal-2D material interface since they could be dramatically different from the bulk material. Recently, it was demonstrated that the growth of gold on the chemical vapor deposited monolayer MoS2 leads to a continuous metal film that preserves plasmonic optical response and conductivity even at thicknesses below 10 nm. Here, we examined the optical response and morphology of ultrathin gold films deposited on exfoliated MoS2 crystal flakes on the SiO2/Si substrate via scattering-type scanning near-field optical microscopy (s-SNOM). We demonstrate a direct relationship between the ability of thin film to support guided surface plasmon polaritons (SPP) and the s-SNOM signal intensity with a very high spatial resolution. Using this relationship, we observed the evolution of the structure of gold films grown on SiO2 and MoS2 with an increase in thickness. The continuous morphology and superior ability with respect to supporting SPPs of the ultrathin (≤10 nm) gold on MoS2 is further confirmed with scanning electron microscopy and direct observation of SPP fringes via s-SNOM. Our results establish s-SNOM as a tool for testing plasmonic films and motivate further theoretical research on the impact of the interplay between the guided modes and the local optical properties on the s-SNOM signal.

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.

Polyethyleneimine-Starch Functionalization of Single-Walled Carbon Nanotubes for Carbon Dioxide Sensing at Room Temperature.

There is an ever-growing interest in the detection of carbon dioxide (CO2) due to health risks associated with CO2 emissions. Hence, there is a need for low-power and low-cost CO2 sensors for efficient monitoring and sensing of CO2 analyte molecules in the environment. This study reports on the synthesis of single-walled carbon nanotubes (SWCNTs) that are functionalized using polyethyleneimine and starch (PEI-starch) in order to fabricate a PEI-starch functionalized SWCNT sensor for reversible CO2 detection under ambient room conditions (T = 25 °C; RH = 53%). Field-emission scanning electron microscopy, high-resolution transmission electron microscopy, Raman spectroscopy, and Fourier transform infrared spectroscopy are used to analyze the physiochemical properties of the as-synthesized gas sensor. Due to the large specific surface area of SWCNTs and the efficient CO2 capturing capabilities of the amine-rich PEI layer, the sensor possesses a high CO2 adsorption capacity. When exposed to varying CO2 concentrations between 50 and 500 ppm, the sensor response exhibits a linear relationship with an increase in analyte concentration, allowing it to operate reliably throughout a broad range of CO2 concentrations. The sensing mechanism of the PEI-starch-functionalized SWCNT sensor is based on the reversible acid-base equilibrium chemical reactions between amino groups of PEI and adsorbed CO2 molecules, which produce carbamates and bicarbonates. Due to the presence of hygroscopic starch that attracts more water molecules to the surface of SWCNTs, the adsorption capacity of CO2 gas molecules is enhanced. After multiple cycles of analyte exposure, the sensor recovers to its initial resistance level via a UV-assisted recovery approach. In addition, the sensor exhibits great stability and reliability in multiple analyte gas exposures as well as excellent selectivity to carbon dioxide over other interfering gases such as carbon monoxide, oxygen, and ammonia, thereby showing the potential to monitor CO2 levels in various infrastructure.

Self-assembled photonic structure: a Ga optical antenna on GaP nanowires.

Semiconductor nanowires are the perfect platform for nanophotonic applications owing to their resonant, waveguiding optical properties and technological capabilities providing control over their crystalline and chemical compositions. The vapor-liquid-solid growth mechanism allows the formation of hybrid metal-dielectric nanostructures promoting sub-wavelength light manipulation. In this work, we explore both experimentally and numerically the plasmonic effects promoted by a gallium (Ga) nanoparticle optical antenna decorating the facet of gallium phosphide (GaP) nanowires. Raman, photoluminescence and near-field mapping techniques are used to study the effects. We demonstrate several phenomena including field enhancement, antenna effect and increase in internal reflection. We show that the observed effects have to be considered when nanowires with a plasmonic particle are used in nanophotonic circuits and discuss the ways for utilization of these effects for efficient coupling of light into nanowire waveguide and field tailoring. The results open up promising pathways for the development of both passive and active nanophotonic elements, light harvesting and sensorics.

SERS uncovers the link between conformation of cytochrome c heme and mitochondrial membrane potential.

The balance between the mitochondrial respiratory chain activity and the cell's needs in ATP ensures optimal cellular function. Cytochrome c is an essential component of the electron transport chain (ETC), which regulates ETC activity, oxygen consumption, ATP synthesis and can initiate apoptosis. The impact of conformational changes in cytochrome c on its function is not understood for the lack of access to these changes in intact mitochondria. We have developed a novel sensor that uses unique properties of label-free surface-enhanced Raman spectroscopy (SERS) to identify conformational changes in heme of cytochrome c and to elucidate their role in functioning mitochondria. We have verified that molecule bond vibrations assessed by SERS are a reliable indicator of the heme conformation during changes in the inner mitochondrial membrane potential and ETC activity. We have demonstrated that cytochrome c heme reversibly switches between planar and ruffled conformations in response to the inner mitochondrial membrane potential (ΔΨ) and H+ concentration in the intermembrane space. This regulates the efficiency of the mitochondrial respiratory chain, thus, adjusting the mitochondrial respiration to the cell's consumption of ATP and the overall activity. We have found that under hypertensive conditions cytochrome c heme loses its sensitivity to ΔΨ that can affect the regulation of ETC activity. The ability of the proposed SERS-based sensor to track mitochondrial function opens broad perspectives in cell bioenergetics.

Non-Additive Optical Response in Transition Metal Dichalcogenides Heterostructures.

Van der Waals (vdW) heterostructures pave the way to achieve the desired material properties for a variety of applications. In this way, new scientific and industrial challenges and fundamental questions arise. One of them is whether vdW materials preserve their original optical response when assembled in a heterostructure. Here, we resolve this issue for four exemplary monolayer heterostructures: MoS2/Gr, MoS2/hBN, WS2/Gr, and WS2/hBN. Through joint Raman, ellipsometry, and reflectance spectroscopies, we discovered that heterostructures alter MoS2 and WS2 optical constants. Furthermore, despite the similarity of MoS2 and WS2 monolayers, their behavior in heterostructures is markedly different. While MoS2 has large changes, particularly above 3 eV, WS2 experiences modest changes in optical constants. We also detected a transformation from dark into bright exciton for MoS2/Gr heterostructure. In summary, our findings provide clear evidence that the optical response of heterostructures is not the sum of optical properties of its constituents.

Effective Method for the Determination of the Unit Cell Parameters of New MXenes.

MXenes are of great practical interest. While the physical properties of such a well-known MAX phase as Ti3AlC2 and the Ti3C2 MXene that is based on it have been widely studied, it is extremely important to study the properties of new four-component MAX-phases and the MXenes based on them. To do this, first, it is necessary to characterize the obtained materials. In this work, the Ti3-xNbxC2 MXene was characterized. Since the material is fairly new, there are no crystallographic data for such systems in the international databases. We proposed a method for the determination of the main unit cell parameters of the new Ti3-xNbxC2 MXene, which was based on a combination of the DFT method, TEM studies, and an X-ray diffraction analysis.

Tailoring of the Distribution of SERS-Active Silver Nanoparticles by Post-Deposition Low-Energy Ion Beam Irradiation.

The possibility of controlled scalable nanostructuring of surfaces by the formation of the plasmonic nanoparticles is very important for the development of sensors, solar cells, etc. In this work, the formation of the ensembles of silver nanoparticles on silicon and glass substrates by the magnetron deposition technique and the subsequent low-energy Ar+ ion irradiation was studied. The possibility of controlling the sizes, shapes and aerial density of the nanoparticles by the variation of the deposition and irradiation parameters was systematically investigated. Scanning electron microscopy studies of the samples deposited and irradiated in different conditions allowed for analysis of the morphological features of the nanoparticles and the distribution of their sizes and allowed for determination of the optimal parameters for the formation of the plasmonic-active structures. Additionally, the plasmonic properties of the resulting nanoparticles were characterized by means of linear spectroscopy and surface-enhanced Raman spectroscopy. Hereby, in this work, we demonstrate the possibility of the fabrication of silver nanoparticles with a widely varied range of average sizes and aerial density by means of a post-deposition ion irradiation technique to form nanostructured surfaces which can be applied in sensing technologies and surface-enhanced Raman spectroscopy (SERS).