Polystyrene microspheres with ultra-rough surfaces engineered using RIE technique and applied using SERS.

In this study, we successfully fabricated two ultra-rough surfaces based on polystyrene (PS) microspheres by employing the reactive ion etching (RIE) technique. Elemental analysis confirmed a stable AlF3 composition of the structures of these surfaces. We proposed the mechanism of the formation of these surfaces and performed SERS-related tests; the prepared substrates exhibited excellent SERS performance.

Bright luminescence from nontoxic all-inorganic low-dimensional cesium halide.

Due to the superiority of low cost, easy manufacture, and tunable light emission owing to the diversity of compositions and dimensionalities, the metal halides have appeared as a promising class of semiconductors. Nevertheless, the toxicity problem along with inherent instability of Pb-based metal halides greatly limits their large-scale applications. Based on this situation, it is necessary to develop eco-friendly materials, which could simultaneously maintain the excellent optoelectronic properties of lead materials. In this Letter, the one-dimensional Cu + -alloyed Cs2AgI3 has been successfully synthesized. An intense blue emission located at 469 nm with a large Stokes shift was observed. Density functional theory calculation indicated that the Cu+ ions could effectively modulate the density of state population, which was the key factor drastically boosting the photoluminescence quantum yield (PLQY). This kind of highly efficient metal halide may overcome the bottlenecks of toxicity and poor efficiency issues of blue emission and will have a promising prospect in the optoelectronic fields.

Inversion method for soil moisture content based on a distributed fiber optic acoustic sensing system.

The traditional measurement method can't achieve real-time monitoring of soil moisture content (SMC) within a two-dimensional area. To solve the above problems, we propose a rapid SMC monitoring method for two-dimensional area based on distributed acoustic sensing (DAS). DAS demodulates the backward Rayleigh scattering signal containing seismic wave sound velocity information from the active seismic source. The folding ruler approximation is employed to calculate the sound velocity of the soil, which is then inverted to determine the soil moisture content. The experiment measured the soil within a two-dimensional area formed by the seismic source and the acoustic sensing optical cable. The sensing optical cable and the active seismic source are organized into a two-dimensional area and the measurement range is 3 × 10 m with 33 points. The SMC ranges from 15% to 40%. The experiment shows that the absolute error between the measured values obtained by DAS and the water cut meter is 7%. This experiment verifies the feasibility of using the Rayleigh scattering properties to invert SMC and provides a new method for real-time monitoring of SMC in a large area.

Wafer-scale synthesis of a morphologically controllable silicon ordered array as a platform and its SERS performance.

In this study, we fabricated four different structures using single crystal silicon wafers for surface-enhanced Raman spectroscopy (SERS) applications. For single crystal silicon, different crystal orientations exhibit different physical and chemical properties. In chemical etching, the etching speed of different crystal planes also exhibits significant differences. We first used reactive ion etching (RIE) to process the surface of the substrate, and subsequently used KOH anisotropic wet etching technology to modify the surface of silicon wafers with different crystal orientations and produced four different results. In the RIE stage in an O2 atmosphere, the (110) silicon wafer formed a hexagonal hole structure, and the (100) silicon wafer formed an inverted pyramid hole structure; however, in the RIE-treated substrates in O2 and SF6 atmosphere, the (110) silicon wafer formed a pyramid with a diamond-shaped base, and the (100) silicon wafer showed a columnar structure with a "straw hat" at the top. The formation mechanisms of these four structures were elucidated. We also performed structure-related SERS characterizations of the four different structures and compared their performance differences.

Lab-on-Fiber Sensors with Ag/Au Nanocap Arrays Based on the Two Deposits of Polystyrene Nanospheres.

Surface-enhanced Raman spectroscopy (SERS) can boost the pristine Raman signal significantly which could be exploited for producing innovative sensing devices with advanced properties. However, the inherent complexity of SERS systems restricts their further applications in rapid detection, especially in situ detection in narrow areas. Here, we construct an efficient and flexible SERS-based Lab-on-Fiber (LOF) sensor by integrating Ag/Au nanocap arrays obtained by Ag/Au coating polystyrene nanospheres on the optical fiber face. We obtain rich "hot spots" at the nanogaps between neighboring nanocaps, and further achieve SERS performance with the assistance of laser-induced thermophoresis on the metal film that can achieve efficiency aggregation of detected molecules. We achieve a high Raman enhancement with a low detection limitation of 10-7 mol/L for the most efficient samples based on the above sensor. This sensor also exhibits good repeatability and stability under multiple detections, revealing the potential application for in situ detection based on the reflexivity of the optical fiber.

Well-Ordered Au Nanoarray for Sensitive and Reproducible Detection of Hepatocellular Carcinoma-Associated miRNA via CHA-Assisted SERS/Fluorescence Dual-Mode Sensing.

Ultra-sensitive detection of cancer-related biomarkers in serum is of great significance for early diagnosis, treatment, prognosis, and staging of cancer. In this work, we proposed a surface-enhanced Raman scattering and fluorescence (SERS/FL) dual-mode biosensor for hepatocellular carcinoma (HCC)-related miRNA (miR-224) detection using the composition of well-arranged Au nanoarrays (Au NAs) substrate coupled with the target-catalyzed hairpin assembly (CHA) strategy. The hot spots densely and uniformly distributed on the Au array offers considerably enhanced and reproducible SERS signals, along with their wide and open surface to facilitate miR-224 adsorption. By this sensing strategy, the target miR-224 can be detected in a wide linear range (1 fM to 1 nM) with a limit of detection of 0.34 fM in the SERS mode and 0.39 fM in the FL mode. Meanwhile, this biosensor with exceptional specificity and anti-interference ability can discriminate target miR-224 from other interference miRNAs. Practical analysis of human blood samples also demonstrated considerable reliability and repeatability of our developed strategy. Furthermore, this biosensor can distinguish HCC cancer subjects from normal ones and monitor HCC patients before and after hepatectomy as well as guide the distinct Barcelona clinic liver cancer (BCLC) stages. Overall, benefiting from a well-arranged Au nanoarray, CHA amplification strategy, and SERS/metal enhanced fluorescence effect, this established biosensor opens new avenues for the early prediction, warning, monitoring, and staging of HCC.

Shape controlled synthesis of concave octahedral Au@AuAg nanoparticles to improve their surface-enhanced Raman scattering performance.

In this work, a seed mediated strategy has been proposed to design and fabricate uniform octahedral shaped gold@gold-silver nanoparticles (Au@AuAg NPs) with unique concave structure and an AuAg alloy shell. The morphology and Au/Ag ratio of the Au@AuAg nanostructures can be delicately controlled by varying the concentration of reagents, namely the Au nanorod (NR) seeds, HAuCl4 and AgNO3 precursor. Besides, the investigation of the growth mechanism revealed that the morphology of the product also can be controlled by tuning the growth time. Furthermore, uniformly arranged assemblies of concave octahedral Au@AuAg NPs were prepared through a solvent evaporation self-assembly strategy and employed as surface-enhanced Raman scattering (SERS) substrates, effectively applied to the analysis of R6G for the examination of SERS performance. Satisfyingly, owing to the synergistic effect between the Au and Ag elements and concave structure, concave octahedral Au@AuAg NPs exhibit significantly higher SERS enhancement compared with traditional octahedral Au NPs, which have an enhancement factor of ∼1.3 × 107 and a detection limit as low as 10-10 M. Meanwhile, the SERS substrate reveals an excellent uniformity and reproducibility of the SERS performance. This work opens a new avenue toward bimetallic NPs with concave structure, which have broad application prospects in optics, SERS detection and other fields.

Fabrication of a three-dimensional (3D) SERS fiber probe and application of in situ detection.

Surface-enhanced Raman scattering (SERS) fiber probes are useful for remote and online detection of harmful molecules using the SERS effect. In this study, a 3-dimensional (3D) SERS optical fiber probe is proposed. The formation of the 3D optical fiber probe mainly included three steps: construction of monolayer polystyrene (PS) spheres as a mask on the end face of the fiber, reactive ion etching (RIE) for PS spheres and fibers, and metal sputtering deposition. Compared with flat surface fiber probes, these 3D SERS fiber probes are composed of ordered nanocolumn arrays, which have the advantages of a simple manufacturing process, low cost, high sensitivity, and good stability. The structures of the 3D SERS fiber probe can be well controlled by changing the size of the PS sphere and etching time. The formation of the nanocolumn was studied using time evolution experiments. The obtained fiber SERS probe has good stability and high sensitivity for the in situ detection of 4-aminothiophenol (4-ATP) in solution. Therefore, these 3D SERS fiber probes have potential applications in harmful molecules for real-time detection.

COVID-19 lockdowns, stimulus packages, travel bans, and stock returns.

This paper examines the effect of government responses of G7 countries to the coronavirus pandemic (COVID-19) on stock market returns. Using time-series data, we show that lockdowns, travel bans, and economic stimulus packages all had a positive effect on the G7 stock markets. However, lockdowns were most effective in cushioning the effects of COVID-19. Our results are robust to different measures of returns and controls for other factors of returns.

Fabrication of ZnO Nanocap-Ordered Arrays with Controllable Amount of Au Nanoparticles Decorated and Their Detection and Degradation Performance for Harmful Molecules.

This paper mainly presents a facile and cost-effective method to achieve large-scale ZnO nanocap (ZnO NC)-ordered arrays with a controllable amount of Au nanoparticles (Au NPs) decorated on their surface. The preparation process includes the construction of polystyrene nanosphere (PS) mask, metal deposition, and annealing process. The Au NPs/ZnO NCs have apparent hierarchical structure. Interestingly, the size and number of Au NPs can be controlled by changing the time of Au deposition and the diameter of PSs. Moreover, the Au NP/ZnO NC arrays can be used as a substrate to detect harmful dye molecules based on surface-enhanced Raman scattering (SERS) effect, and show ultrahigh sensitivity with a limit of detection (LoD) of 10-10 M for crystal violet (CV) molecules. In addition, the above substrate has achieved reusable detection due to their excellent photocatalytic degradation performance for harmful molecules. The finite difference time-domain (FDTD) simulation results have revealed that SERS "hot spots" are almost distributed at the junctions of Au NPs and ZnO NCs. The above results show that the composite substrates have a good prospect in practical applications in the future.

Ordered gold-coated glass nano-sting array with large density tips as highly SERS-active chips for detection of trace organophosphorous toxicant.

A simple and cost-effective route to fabricating gold-coated glass nano-stings' arrays is presented for highly efficient surface enhanced Raman spectroscopy (SERS) chips via reactive ion etching of the glass slide covered with polystyrene (PS) colloidal monolayer and sputtering deposition of gold on it. The as-fabricated SERS chips consist of the nearly-hemispherical particles with submicron-size, which are hexagonally arranged into the ordered arrays. There are many short and long Au-coated glass nano-stings standing vertically on the hemispherical particles, showing high density tips (up to 7.0 × 103 µm-2). The formation of such gold-coated glass hierarchically structured array is attributed to the geometry of PS colloidal monolayer and the nanoscale roughness of glass slide's surface. Further, it has been demonstrated that such gold-coated glass array chip is highly SERS-active and can be utilized to detect trace organophosphorous toxicant with the limit below ppt level and good reproducibility in measurements. The intensity of the Raman peak shows the linear relation, in logarithmic scale, with the organophosphorous concentration from ppt to ppm level, exhibiting the possibility of quantitative detection in a large concentration range. This work has demonstrated the cost-effective method to fabricate the high performance SERS chips for trace detection of toxic molecules.

Ultrathin Hexagonal PbO Nanosheets Induced by Laser Ablation in Water for Chemically Trapping Surface-Enhanced Raman Spectroscopy Chips and Detection of Trace Gaseous H2S.

Lead oxide (PbO) nanosheets are of significance in the design of functional devices. However, facile, green, and fast fabrication of ultrathin and homogenous PbO nanosheets with a chemically clean surface is still desirable. Herein, a simple and chemically clean route is developed for fabricating such nanosheets via laser ablation of a lead target in water for a short time and then ambient aging. The obtained PbO nanosheets are (002)-oriented with microsize in planar dimension and ∼15 nm in thickness. They are mostly hexagonal in shape. Experimental observations of the morphological evolution have revealed that the formation of such PbO nanosheets can be attributed to two processes: (i) laser ablation-induced formation of ultrafine Pb and PbO nanoparticles (NPs) and (ii) PbO NP aggregation and their oriented connection growth. Importantly, a composite surface-enhanced Raman spectroscopy (SERS) chip is designed and fabricated by covering a PbO nanosheet monolayer on a Au NP film. Such a composite SERS chip can be used for the fast and trace detection of gaseous H2S in which the PbO nanosheets can effectively chemically trap H2S molecules, demonstrating a new application of these PbO nanosheets. The response of this chip to H2S can be detected within 10 s, and the detection limit is below 1 ppb. Also, this PbO nanosheet-based chip is reusable by heating after use. This study not only deepens the understanding of the NP-based formation mechanism of nanosheets but also provides the renewable SERS chips for the highly efficient detection of trace gaseous H2S.

Dynamically Tunable Plasmonic Band for Reversible Colorimetric Sensors and Surface-Enhanced Raman Scattering Effect with Good Sensitivity and Stability.

A colorimetric sensor based on plasmonic nanoparticles (NPs) is a promising and convenient detection tool, but its reproducibility and adjustability remain a challenge because the NPs are mainly random and uncontrollable. Herein, a colorimetric sensor with good reversibility and reproducibility was prepared by embedding the two-dimensional (2D) Au NP arrays on the surface of the polyacrylamide hydrogel film to form 2D Au NP arrays attached a hydrogel composite. For this composite, with the change of the interspacing distance of Au NPs driven by the swelling-shrinking behavior of the hydrogel carrier, the diffraction peaks faded away and plasmonic coupling peaks appeared, accompanied by a series of obvious color changes (iridescence ↔ violet ↔ golden yellow ↔ red), which can be correlated to the applied water content. Importantly, the composite had good reproducibility as a result of a highly ordered array structure. Additionally, this colorimetric sensor with a dynamically tunable plasmonic band can be used as a high-quality surface-enhanced Raman scattering (SERS) substrate because the gap distance of the Au NPs can be uniformly controlled. We demonstrated that, as the active gap distance decreased, the SERS signals can be significantly intensified. When the water content reached 40%, this SERS substrate exhibited high sensitivity (10-10 M for 4-aminothiophenol and 10-9 M for thiram) and good reproducibility (relative standard deviation of <20%) using the excitation laser of 785 nm because of the small gap between two adjacent Au NPs and the highly ordered periodic structure. Such 2D Au NP arrays attached to a hydrogel composite could be a new strategy to obtain a high-quality colorimetric sensor and dynamic SERS substrate.

Engineering of flexible granular Au nanocap ordered array and its surface enhanced Raman spectroscopy effect.

Surface enhanced Raman spectroscopy (SERS) is a new and developing analytical technology in chemical and biological detection. However, traditional hard SERS substrates are struggling to meet the growing demand for flexible devices. In this work, we introduce a simple, cost-effective and large scale preparation route to form a flexible Au nanocap (AuNC) ordered array as SERS substrates via reactive ion etching (RIE) method and then Au deposition. We find RIE is an excellent method for nanoroughening the surface of polystyrene (PS) spheres. Such flexible SERS substrates exhibit high sensitivity and uniformity for detecting organic molecules. The finite-difference time-domain simulation results revealed that a strong electric field coupling effect existed not only in the gap site between the Au nanoparticles (AuNPs), but also in the connection position between the AuNCs and the single AuNP. This study not only offers a novel way for nanoroughening of PS spheres, but also acquires flexible and cheap SERS substrates for quick and sensitive detection of organic molecules.

Ultrathin and Isotropic Metal Sulfide Wrapping on Plasmonic Metal Nanoparticles for Surface Enhanced Ram Scattering-Based Detection of Trace Heavy-Metal Ions.

A facile and general strategy is presented for homogenous and ultrathin metal sulfide wrapping on plasmonic metal (PM) nanoparticles (NPs) based on a thiourea-induced isotropic shell growth. This strategy is typically implemented just via adding the thiourea into pre-formed PM colloidal solutions containing target metal ions. The validity of this strategy is demonstrated by taking the wrapped NPs with Au core and CuS shell or Au@CuS NPs as an example. They are successfully fabricated via adding the thiourea and Cu2+ solutions into pre-formed Au NP colloidal solution. The CuS shell layer is highly homogenous (<10% in relative standard deviation of shell thickness), regardless of the NPs' shape or curvature. The shell thickness can be controlled from tens down to 0.5 nm just by the addition of different amounts of shell precursors. The formation of the shell layer on the Au NPs can be attributed to the alternative deposition of Cu2+ and S2- ions on the thiourea-modified surface of Au NPs in the solution, which induces the isotropic shell growth. Further, this strategy is of good universality. Many other sulfide-wrapped PM NPs, such as Ag@CuS, Au@PtS2, Au@HgS, Ag@Ag2S NPs, and Ag@CuS nanorods, have been successfully obtained with homogeneous and ultrathin shells. Importantly, such ultrathin sulfide-wrapped PM NPs can be used for surface enhanced Raman scattering (SERS)-based detection of trace heavy-metal ions with strong anti-interference via the ion exchange process between the metal sulfide shell and heavy-metal ions. This study provides a simple and controllable route for wrapping the homogenous and ultrathin sulfide layers on the PM NPs, and such wrapped NPs have good practical applications in the SERS-based detection of trace heavy-metal ions.

Fabrication of Ag-nanosheets-built micro/nanostructured arrays via in situ conversion on Cu2O-coated Si nanocone platform and their highly structurally-enhanced SERS effect.

A controllable and flexible route is presented for the fabrication of Ag-nanosheets-built micro/nanostructural ordered arrays via in situ conversion on the Cu2O-coated silicon nanocone (SNC) platform in the AgNO3-contained solution. The platform is pre-prepared by the reactive ion etching of the organic colloidal monolayer-covered silicon wafer, Cu sputtering deposition and in situ oxidation. The obtained Ag micro/nanostructured array consists of nearly spherical and micro-sized particles, which are hexagonally arranged on the substrate. The spherical particles are built of the vertically standing and cross-linked nanosheets with about 30 nm in thickness. This Ag-nanosheets-built array shows high number density of the edges and nanogaps as well as the robust and homogeneous structure. Its formation is attributed to the in situ conversion reaction on the Cu2O-coated SNC platform and the preferentially-oriented connection of Ag nanoparticles. Such Ag array has shown significantly higher surface enhanced Raman scattering (SERS) activity than the Ag nanoparticles' film-covered SNC array, with the enhancement factor up to 107 and the detection limitation down to ∼1 ppt level to the test molecules 4-aminothiophenol, as well as the good reproducibility in measurements. This study not only presents a controllable and flexible fabrication route to the plasmonic micro/nanostructured arrays but also provides the highly efficient and the practical chips for the SERS-based devices.

Porous zeolite imidazole framework-wrapped urchin-like Au-Ag nanocrystals for SERS detection of trace hexachlorocyclohexane pesticides via efficient enrichment.

A core-shell configuration of the zeolite imidazole framework (ZIF-8) wrapped urchin-like Au-Ag alloyed nanocrystals (UAANs) were designed and fabricated via adding the pre-formed plasmonic nanoparticles into the ZIF-8 precursor solution with hexadecyltrimethyl ammonium bromide (CTAB). The UAANs are about 100 nm in size with high-density tips. The ZIF-8 shell layer is nanoporous and can be controlled in thickness from 10 nm to 40 nm by the CTAB concentration. Importantly, such ZIF-8 wrapped UAANs can be used as the highly efficient surface enhanced Raman scattering (SERS) substrates for detection of the trace hexachlorocyclohexane (HCH) molecules. The ZIF-8 shell layer with an appropriate thickness (-∼20 nm) can evidently increase the SERS performance of the UAANs to the trace γ-HCH and α-HCH. Such wrapping-enhanced SERS effect significantly increases, by a power function, with the decreasing HCH concentration, especially in the concentration below 10-6 M, which is attributed to the ever-increasing enrichment effect to the HCH molecules. The detection limit is down below 1.5 ppb. This work presents a highly efficient substrate for the SERS-based detection of the trace HCH, and also displays the potential application in the SERS detection of volatile small molecules.

Controllable corrosion-assisted fabrication of Au-Ag alloyed hollow nanocrystals for highly efficient and environmentally-stable SERS substrates.

Surface enhanced Raman scattering (SERS) substrates with both high activity and long term chemical-stability have been expected in the practical application of the SERS-based detection. In this paper, Au-Ag bimetal nanocrystals are fabricated based on the template-etching reaction in the Ag nanocubes-contained cetylpyridinium chloride (CPC) aqueous solution via adding the HAuCl4 solution. The obtained nanocrystals are Au-Ag alloyed and hollow in structure. Further, it has been found that with the increasing Au/Ag molar ratio, the shape of the alloyed nanocrystals evolve from the truncated nanocubes to the hollow boxes and then nanocages, showing the ever red-shifting surface plasmon resonance from the visible to the infrared region. The formation of the alloyed hollow nanocrystals is attributed to the preferential dissolution of the Ag nanocubes induced by CPC selective adsorption and the three to one galvanic replacement reaction between Ag and Au atoms. Importantly, such Au-Ag alloyed hollow nanocrystals, especially the ones with a low Au/Ag atomic ratio, show both high SERS activity and long term environmental stability compared with pure Ag or Au nanocrystals, and are the ideal candidate for the SERS substrate with practical application value. This work not only demonstrates the nanofabrication route to the alloyed hollow nanocrystals with controllable shapes and tunable optical properties in a large region, but also presents highly active and chemically-stable SERS substrates for the practical SERS-based detection.

Kinetically-Controlled Growth of Chestnut-Like Au Nanocrystals with High-Density Tips and Their High SERS Performances on Organochlorine Pesticides.

A modified seed growth route was developed to fabricate the Au nanocrystals with high-density tips based on kinetically-controlled growth via adjusting the adding rate of Au seeds into growth solution. The obtained Au nanostructures were chestnut-like in morphology and about 100 nm in size. They were built of the radial [111]-oriented nanoneedles and were 30⁻50 nm in length. There were about 120⁻150 tips in each nanocrystal. The formation of chestnut-like Au nanocrystals is ascribed to surfactant-induced preferential growth of seeds along direction [111]. Importantly, the chestnut-like Au configuration displayed powerful surface enhanced Raman scattering (SERS) performance (enhance factor > 107), owing to the high density of tips. Further, such film was used as a SERS substrate for the detection of lindane (γ-666) molecules (the typical organochlorine pesticide). The detection limit was about 10 ppb, and the relationship between SERS intensity I and concentration C of 666 accords with the double logarithm linear. This work presents a simple approach to Au nanocrystal with high-density tips, and provides a highly efficacious SERS-substrate for quantitative and trace recognition of toxic chlorinated pesticides.

Large Area α-Cu2S Particle-Stacked Nanorod Arrays by Laser Ablation in Liquid and Their Strong Structurally Enhanced and Stable Visible Photoelectric Performances.

A flexible route is developed for fabrication of large area α-Cu2S nanorod arrays (NRAs) on the basis of one-step laser ablation of a copper foil in CS2 liquid. It has been demonstrated that the obtained products are the high-temperature phase α-Cu2S and consist of the nanorods vertically standing on the Cu foil, exhibiting the array. The nanorods were about 1 µm in length and around 100 nm in thickness and built by stacking the nearly spherical and ⟨110⟩-oriented nanoparticles (NPs) up. Such array can be peeled off from the foil and remain freestanding. Further, it has been found that the ablation duration, the laser power, and the foil surface state are crucial to the formation of the Cu2S NRA. The formation of such oriented NP-stacked Cu2S NRAs is attributed to the laser-induced generation of α-Cu2S NPs and the NPs' deposition/oriented connection growth on the surface-vulcanized copper foil. Importantly, the visible photocurrent response of the α-Cu2S NRAs is 8 times higher than that of the Cu2S NPs' film with the equivalent thickness and also larger than that of previously reported Cu2S, showing significantly enhanced photoelectric performances. As an application, such NRAs have exhibited markedly enhanced visible photocatalytic activity and highly stable recycling performances, compared with the α-Cu2S NPs. Further studies have revealed that the enhanced performances are attributed to the structurally enhanced light trapping effect of the NRAs as well as short and smooth carrier diffusion path in the oriented NP-stacked nanorods. This work provides a new and simple method for fabrication of the large area Cu2S NRAs with high and stable photoelectric performances.