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.

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.

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.

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.

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.

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.

Stabilization of the Nano-Sized 1T Phase through Rhenium Doping in the Metal-Organic CVD MoS2 Films.

Heterogeneous nanostructures composed of metastable tetragonal 1T-MoS2 and stable hexagonal 2H-MoS2 phases are highly promising for a wide range of applications, including catalysis and ion batteries, due to the high electrical conductivity and catalytic activity of the 1T phase. However, a controllable synthesis of stabilized 1T-MoS2 films over the wafer-scale area is challenging. In this work, a metal-organic chemical vapor deposition process allowing us to obtain ultrathin MoS2 films containing both 1T and 2H phases and control their ratio through rhenium doping was suggested. As a result, Mo1-xRexS2 films with a 1T-MoS2 fraction up to ≈30% were obtained, which were relatively stable under normal conditions for a long time. X-ray photoelectron spectroscopy and Raman spectroscopy also indicated that the 1T-MoS2 phase fraction increased with rhenium concentration increase saturating at Re concentrations above 5 at. %. Also, its concentration was found to significantly affect the film resistivity. Thus, the resistivity of the film containing approximately 30% of the 1T phase was about 130 times lower than that of the film without the 1T phase.

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.

Highly Sensitive Electrochemical Non-Enzymatic Uric Acid Sensor Based on Cobalt Oxide Puffy Balls-like Nanostructure.

Early-stage uric acid (UA) abnormality detection is crucial for a healthy human. With the evolution of nanoscience, metal oxide nanostructure-based sensors have become a potential candidate for health monitoring due to their low-cost, easy-to-handle, and portability. Herein, we demonstrate the synthesis of puffy balls-like cobalt oxide nanostructure using a hydrothermal method and utilize them to modify the working electrode for non-enzymatic electrochemical sensor fabrication. The non-enzymatic electrochemical sensor was utilized for UA determination using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The puffy balls-shaped cobalt oxide nanostructure-modified glassy carbon (GC) electrode exhibited excellent electro-catalytic activity during UA detection. Interestingly, when we compared the sensitivity of non-enzymatic electrochemical UA sensors, the DPV technique resulted in high sensitivity (2158 µA/mM.cm2) compared to the CV technique (sensitivity = 307 µA/mM.cm2). The developed non-enzymatic electrochemical UA sensor showed good selectivity, stability, reproducibility, and applicability in the human serum. Moreover, this study indicates that the puffy balls-shaped cobalt oxide nanostructure can be utilized as electrode material for designing (bio)sensors to detect a specific analyte.

A 3D Biocompatible Plasmonic Tweezer for Single Cell Manipulation.

Plasmonic tweezers are an emerging research topic because of their low input power and wide operating range from homogeneous particles to complex biological objects. But it is still challenging for plasmonic tweezers to trap or manipulate objects of tens of microns, especially in biological science. This study introduces a new 3D biocompatible plasmonic tweezer for single living cell manipulation in solution. The key design is a tapered tip whose three-layer surface structure consists of nanoprobe, gold nanofilm, and thermosensitive hydrogel, thiolated poly(N-isopropylacrylamide). Incident light excites the surface plasmon polaritons on gold film and generates heat to induce thermally driven phase transition of the thermosensitive hydrogel, which enables reversible binding between functionalized surface and cell membrane and avoids both thermal and mechanical stresses in the meanwhile. The 3D biocompatible plasmonic tweezer realizes selective capture, 3D pathway free transport, and position-controlled release of target cells, and it displays excellent biocompatibility, low energy consumption, and high operational flexibility.

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.

Hybrid Plasmonic Nanostructures and Their Applications.

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Transition metal dichalcogenide nanospheres for high-refractive-index nanophotonics and biomedical theranostics.

Recent developments in the area of resonant dielectric nanostructures have created attractive opportunities for concentrating and manipulating light at the nanoscale and the establishment of the new exciting field of all-dielectric nanophotonics. Transition metal dichalcogenides (TMDCs) with nanopatterned surfaces are especially promising for these tasks. Still, the fabrication of these structures requires sophisticated lithographic processes, drastically complicating application prospects. To bridge this gap and broaden the application scope of TMDC nanomaterials, we report here femtosecond laser-ablative fabrication of water-dispersed spherical TMDC (MoS2 and WS2) nanoparticles (NPs) of variable size (5 to 250 nm). Such NPs demonstrate exciting optical and electronic properties inherited from TMDC crystals, due to preserved crystalline structure, which offers a unique combination of pronounced excitonic response and high refractive index value, making possible a strong concentration of electromagnetic field in the NPs. Furthermore, such NPs offer additional tunability due to hybridization between the Mie and excitonic resonances. Such properties bring to life a number of nontrivial effects, including enhanced photoabsorption and photothermal conversion. As an illustration, we demonstrate that the NPs exhibit a very strong photothermal response, much exceeding that of conventional dielectric nanoresonators based on Si. Being in a mobile colloidal state and exhibiting superior optical properties compared to other dielectric resonant structures, the synthesized TMDC NPs offer opportunities for the development of next-generation nanophotonic and nanotheranostic platforms, including photothermal therapy and multimodal bioimaging.

Model of the SARS-CoV-2 Virus for Development of a DNA-Modified, Surface-Enhanced Raman Spectroscopy Sensor with a Novel Hybrid Plasmonic Platform in Sandwich Mode.

The recent severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection has posed a great challenge for the development of ultra-fast methods for virus identification based on sensor principles. We created a structure modeling surface and size of the SARS-CoV-2 virus and used it in comparison with the standard antigen SARS-CoV-2-the receptor-binding domain (RBD) of the S-protein of the envelope of the SARS-CoV-2 virus from the Wuhan strain-for the development of detection of coronaviruses using a DNA-modified, surface-enhanced Raman scattering (SERS)-based aptasensor in sandwich mode: a primary aptamer attached to the plasmonic surface-RBD-covered Ag nanoparticle-the Cy3-labeled secondary aptamer. Fabricated novel hybrid plasmonic structures based on "Ag mirror-SiO2-nanostructured Ag" demonstrate sensitivity for the detection of investigated analytes due to the combination of localized surface plasmons in nanostructured silver surface and the gap surface plasmons in a thin dielectric layer of SiO2 between silver layers. A specific SERS signal has been obtained from SERS-active compounds with RBD-specific DNA aptamers that selectively bind to the S protein of synthetic virion (dissociation constants of DNA-aptamer complexes with protein in the range of 10 nM). The purpose of the study is to systematically analyze the combination of components in an aptamer-based sandwich system. A developed virus size simulating silver particles adsorbed on an aptamer-coated sensor provided a signal different from free RBD. The data obtained are consistent with the theory of signal amplification depending on the distance of the active compound from the amplifying surface and the nature of such a compound. The ability to detect the target virus due to specific interaction with such DNA is quantitatively controlled by the degree of the quenching SERS signal from the labeled compound. Developed indicator sandwich-type systems demonstrate high stability. Such a platform does not require special permissions to work with viruses. Therefore, our approach creates the promising basis for fostering the practical application of ultra-fast, amplification-free methods for detecting coronaviruses based on SARS-CoV-2.

Detection of Hypertension-Induced Changes in Erythrocytes by SERS Nanosensors.

Surface-enhanced Raman spectroscopy (SERS) is a promising tool that can be used in the detection of molecular changes triggered by disease development. Cardiovascular diseases (CVDs) are caused by multiple pathologies originating at the cellular level. The identification of these deteriorations can provide a better understanding of CVD mechanisms, and the monitoring of the identified molecular changes can be employed in the development of novel biosensor tools for early diagnostics. We applied plasmonic SERS nanosensors to assess changes in the properties of erythrocytes under normotensive and hypertensive conditions in the animal model. We found that spontaneous hypertension in rats leads (i) to a decrease in the erythrocyte plasma membrane fluidity and (ii) to a decrease in the mobility of the heme of the membrane-bound hemoglobin. We identified SERS parameters that can be used to detect pathological changes in the plasma membrane and submembrane region of erythrocytes.

Thickness-Dependent Structural and Electrical Properties of WS2 Nanosheets Obtained via the ALD-Grown WO3 Sulfurization Technique as a Channel Material for Field-Effect Transistors.

Ultrathin WS2 films are promising functional materials for electronic and optoelectronic devices. Therefore, their synthesis over a large area, allowing control over their thickness and structure, is an essential task. In this work, we investigated the influence of atomic layer deposition (ALD)-grown WO3 seed-film thickness on the structural and electrical properties of WS2 nanosheets obtained via a sulfurization technique. Transmission electron microscopy indicated that the thinnest (1.9 nm) film contains rather big (up to 50 nm) WS2 grains in the amorphous matrix. The signs of incomplete sulfurization, namely, oxysulfide phase presence, were found by X-ray photoemission spectroscopy analysis. The increase in the seed-film thickness of up to 4.7 nm resulted in a visible grain size decrease down to 15-20 nm, which was accompanied by defect suppression. The observed structural evolution affected the film resistivity, which was found to decrease from ∼106 to 103 (µΩ·cm) within the investigated thickness range. These results show that the thickness of the ALD-grown seed layer may strongly affect the resultant WS2 structure and properties. Most valuably, it was shown that the growth of the thinnest WS2 film (3-4 monolayers) is most challenging due to the amorphous intergrain phase formation, and further investigations focused on preventing the intergrain phase formation should be conducted.

Hybrid Metal-Dielectric-Metal Sandwiches for SERS Applications.

The development of efficient plasmonic nanostructures with controlled and reproducible surface-enhanced Raman spectroscopy (SERS) signals is an important task for the evolution of ultrasensitive sensor-related methods. One of the methods to improving the characteristics of nanostructures is the development of hybrid structures that include several types of materials. Here, we experimentally investigate ultrathin gold films (3-9 nm) near the percolation threshold on Si/Au/SiO2 and Si/Au/SiO2/graphene multilayer structures. The occurring field enhanced (FE) effects were characterized by a recording of SERS signal from Crystal Violet dye. In this geometry, the overall FE principally benefits from the combination of two mechanisms. The first one is associated with plasmon excitation in Au clusters located closest to each other. The second is due to the gap plasmons' excitation in a thin dielectric layer between the mirror and corrugated gold layers. Experimentally obtained SERS signals from sandwiched structures fabricated with Au film of 100 nm as a reflector, dielectric SiO2 spacer of 50 nm and ultrathin gold atop could reach SERS enhancements of up to around seven times relative to gold films near the percolation threshold deposited on a standard glass substrate. The close contiguity of the analyte to graphene and nanostructured Au efficiently quenches the fluorescent background of the model compound. The obtained result shows that the strategy of combining ultrathin nano-island gold films near the percolation threshold with gap plasmon resonances is promising for the design of highly efficient SERS substrates for potential applications in ultrasensitive Raman detection.

Broadband Optical Properties of Atomically Thin PtS2 and PtSe2.

Noble transition metal dichalcogenides (TMDCs) such as PtS2 and PtSe2 show significant potential in a wide range of optoelectronic and photonic applications. Noble TMDCs, unlike standard TMDCs such as MoS2 and WS2, operate in the ultrawide spectral range from ultraviolet to mid-infrared wavelengths; however, their properties remain largely unexplored. Here, we measured the broadband (245-3300 nm) optical constants of ultrathin PtS2 and PtSe2 films to eliminate this gap and provide a foundation for optoelectronic device simulation. We discovered their broadband absorption and high refractive index both theoretically and experimentally. Based on first-principle calculations, we also predicted their giant out-of-plane optical anisotropy for monocrystals. As a practical illustration of the obtained optical properties, we demonstrated surface plasmon resonance biosensors with PtS2 or PtSe2 functional layers, which dramatically improves sensor sensitivity by 60 and 30%, respectively.

Optical Constants and Structural Properties of Epitaxial MoS2 Monolayers.

Two-dimensional layers of transition-metal dichalcogenides (TMDs) have been widely studied owing to their exciting potential for applications in advanced electronic and optoelectronic devices. Typically, monolayers of TMDs are produced either by mechanical exfoliation or chemical vapor deposition (CVD). While the former produces high-quality flakes with a size limited to a few micrometers, the latter gives large-area layers but with a nonuniform surface resulting from multiple defects and randomly oriented domains. The use of epitaxy growth can produce continuous, crystalline and uniform films with fewer defects. Here, we present a comprehensive study of the optical and structural properties of a single layer of MoS2 synthesized by molecular beam epitaxy (MBE) on a sapphire substrate. For optical characterization, we performed spectroscopic ellipsometry over a broad spectral range (from 250 to 1700 nm) under variable incident angles. The structural quality was assessed by optical microscopy, atomic force microscopy, scanning electron microscopy, and Raman spectroscopy through which we were able to confirm that our sample contains a single-atomic layer of MoS2 with a low number of defects. Raman and photoluminescence spectroscopies revealed that MBE-synthesized MoS2 layers exhibit a two-times higher quantum yield of photoluminescence along with lower photobleaching compared to CVD-grown MoS2, thus making it an attractive candidate for photonic applications.