Ag Nanoparticles@Au Nanograting Array as a 3D Flexible and Effective Surface-Enhanced Raman Scattering Substrate.

Surface-enhanced Raman scattering (SERS) is a powerful analytical technique for chemical identification, but it remains a great challenge to realize the large-scale and well-controlled fabrication of sensitive and repeatable SERS substrates. Here, we report a facile strategy to fabricate centimeter-sized periodic Au nanograting (Au-NG) decorated with well-arranged Ag nanoparticles (Ag-NPs) (denoted as Ag-NPs@Au-NG) as a three-dimensional (3D) flexible hybrid SERS substrate with high sensitivity and good reproducibility. The Au-NG patterns with periodic ridges and grooves are fabricated through nanoimprint lithography by employing a low-cost digital versatile disc (DVD) as a master mold, and the Ag-NPs are assembled by a well-controlled interface self-assembly method without any coupling agents. Multiple coupling electromagnetic field effects are created at the nanogaps between the Ag-NPs and Au-NG patterns, leading to high-density and uniform hot spots throughout the substrate. As a result, the Ag-NPs@Au-NG arrays demonstrate an ultrahigh SERS sensitivity as low as 10-13 M for rhodamine 6G with a high average enhancement factor (EF) of 1.85 × 108 and good signal reproducibility. For practical applications, toxic organic pollutants including crystal violet, thiram, and melamine have been successfully detected with high sensitivity at a low detection limit, showing a good perspective in the rapid detection of toxic organic pollutants.

Pt Single-Atoms on Structurally-Integrated 3D N-Doped Carbon Tubes Grid for Ampere-Level Current Density Hydrogen Evolution.

To date, the excellent mass-catalytic activities of Pt single-atoms catalysts (Pt-SACs) toward hydrogen evolution reaction (HER) are categorically confirmed; however, their high current density performance remains a challenge for practical applications. Here, a binder-free approach is exemplified to fabricate self-standing superhydrophilic-superaerphobic Pt-SACs cathodes by directly anchoring Pt-SAs via Pt-NxC4-x coordination bonds to the structurally-integrated 3D nitrogen-doped carbon tubes (N-CTs) array grid (denoted as Pt@N-CTs). The 3D Pt@N-CTs cathode with optimal Pt-SACs loading is capable of operating at a high current density of 1000 mA cm-2 with an ultralow overpotential of 157.9 mV with remarkable long-term stability over 11 days at 500 mA cm-2. The 3D super-wettable free-standing Pt@N-CTs possess interconnected vertical and lateral N-CTs with hierarchical-sized open channels, which facilitates the mass transfer. The binder-free immobilization adding to the large surface area and 3D-interconnected open channels endow Pt@N-CTs cathodes with high accessible active sites, electrical conductivity, and structural stability that maximize the utilization efficiency of Pt-SAs to achieve ampere-level current density HER at low overpotentials.

Phase-Tunable Molybdenum Boride Ceramics as an Emerging Sensitive and Reliable SERS Platform in Harsh Environments.

Traditional surface-enhanced Raman scattering (SERS) sensors rely heavily on the use of plasmonic noble metals, which have limitations due to their high cost and lack of physical and chemical stability. Hence, it is imperative to explore new materials as SERS platforms that can withstand high temperatures and harsh conditions. In this study, the SERS effect of molybdenum boride ceramic powders is presented with an enhancement factor of 5 orders, which is comparable to conventional noble metal substrates. The molybdenum boride powders synthesized through liquid-phase precursor and carbothermal reduction have ß-MoB, MoB2, and Mo2B5 phases. Among these phases, ß-MoB demonstrates the most significant SERS activity, with a detection limit for rhodamine 6G (R6G) molecules of 10-9 m. The impressive SERS enhancement can be attributed to strong molecule interactions and prominent charge interactions between R6G and the various phases of molybdenum boride, as supported by theoretical calculations. Additionally, Raman measurements show that the SERS activity remains intact after exposure to high temperature, strong acids, and alkalis. This research introduces a novel molybdenum boride all-ceramic SERS platform capable of functioning in harsh conditions, thereby showing the promising of boride ultrahigh-temperature ceramics for detection applications in extreme environments.

Template-assisted fabrication of Ag-nanoparticles@ZnO-nanorods array as recyclable 3D surface enhanced Raman scattering substrate for rapid detection of trace pesticides.

We present a template-assisted fabrication method for a large-scale ordered arrays of ZnO nanorods (ZnO-NRs) modified with Ag nanoparticles (Ag-NPs), which possess high-density three-dimensional (3D) hot spots uniformly dispersed all over the substrate, being beneficial to ultrahigh sensitivity of surface enhanced Raman scattering (SERS) detection. These achieved Ag-NPs@ZnO-NRs arrays show high sensitivity, good spectral uniformity and reproducibility as substrates for SERS detection. Using the arrays, both dye molecules (rhodamine 6G, R6G) and organic pollutants like toxic pesticides (thiram and methyl parathion) are detected, with the detection limits of thiram and methyl parathion being 0.79 × 10-9 M and 1.51 × 10-8 M, respectively. In addition, the Ag-NPs@ZnO-NRs arrays have a self-cleaning function because the analyte molecules can be photocatalytic degraded using ultraviolet irradiation, showing that the 3D recyclable arrays have promising opportunities to be applied in rapid SERS-based detection of toxic organic pesticides.

Silver nanoparticle-assembled micro-bowl arrays for sensitive SERS detection of pesticide residue.

It is of great significance to develop a simple and effective method for constructing large-scale high-quality surface-enhanced Raman scattering (SERS) substrate. Here, an Ag nanoparticle-assembled micro-bowl array was prepared by a close-packed polystyrene (PS) sphere monolayer templated electrodeposition approach. The fabricated Ag nanoparticle-assembled micro-bowl array shows high SERS sensitivity to rhodamine 6G (R6G) under an ultra-low concentration of 1 fM, and exhibits excellent SERS spectral uniformity with a small relative standard deviation (RSD) of 7.6% and good reproducibility (a RSD ∼8.2% for the average peak intensities from different batches of SERS substrates). The fabricated micro-bowl array SERS substrate was employed to detect pesticide residue (thiram and methyl parathion) on vegetables. The limit of detections (LODs) for the two pesticides are lower than the maximum residue limits (MRLs) set by the European Union respectively, showing promising application in rapid inspection of food safety.

Plasmonic hot electrons for sensing, photodetection, and solar energy applications: A perspective.

In plasmonic metals, surface plasmon resonance decays and generates hot electrons and hot holes through non-radiative Landau damping. These hot carriers are highly energetic, which can be modulated by the plasmonic material, size, shape, and surrounding dielectric medium. A plasmonic metal nanostructure, which can absorb incident light in an extended spectral range and transfer the absorbed light energy to adjacent molecules or semiconductors, functions as a "plasmonic photosensitizer." This article deals with the generation, emission, transfer, and energetics of plasmonic hot carriers. It also describes the mechanisms of hot electron transfer from the plasmonic metal to the surface adsorbates or to the adjacent semiconductors. In addition, this article highlights the applications of plasmonic hot electrons in photodetectors, photocatalysts, photoelectrochemical cells, photovoltaics, biosensors, and chemical sensors. It discusses the applications and the design principles of plasmonic materials and devices.

Long-range surface plasmon resonance and surface-enhanced Raman scattering on X-shaped gold plasmonic nanohole arrays.

A multilayered architecture including a thin Au film supporting an X-shaped nanohole array and a thick continuous Au film separated by a Cytop dielectric layer is reported in this work. Long-range surface plasmon resonance (LR-SPR) was generated at the top Au/water interface, which also resulted in a long-range surface-enhanced Raman scattering (LR-SERS) effect. LR-SPR originates from the coupling of surface plasmons (SPs) propagating along the opposite sides of the thin Au film embedded in a symmetric refractive index environment with Cytop (n = 1.34) and water (n = 1.33). The finite-difference time-domain (FDTD) simulation method was used to investigate the optimal dimensions of the substrate by studying the reflectance spectra and electric field profiles. The calculated optimal structure was then fabricated via electron beam lithography, and its LR-SERS performance was demonstrated by detecting rhodamine 6G and 4-mercaptobenzoic acid in the refractive index-matched environment. We believe that this structure as a LR-SPR or LR-SERS substrate can have broad applications in biosensing.

A flexible transparent Ag-NC@PE film as a cut-and-paste SERS substrate for rapid in situ detection of organic pollutants.

This report presents a simple and inexpensive fabrication approach to a flexible transparent composite film as a "cut-and-paste" surface-enhanced Raman scattering (SERS) substrate for in situ detection of organic pollutants. First, a self-assembled monolayer of Ag-nanocubes (Ag-NCs) is obtained at the air/water interface. Then, the Ag-NC monolayer is retrieved onto a flexible transparent polyethylene (PE) film to achieve an Ag-NC@PE composite film as a flexible SERS substrate. As the Ag-NCs in the monolayer are closely and uniformly packed on the PE film, the Ag-NC@PE composite film shows high SERS-activity with good signal homogeneity and reproducibility. Furthermore, the flexible transparent Ag-NC@PE composite film is "cut into" small pieces and directly "pasted" onto contaminated fruits for in situ SERS detection, as a result 10 nM thiram, 1 µM 4-polychlorinated biphenyl and 10 nM methyl parathion contaminants on oranges are detected, respectively. Therefore the Ag-NC@PE composite film is an inexpensive and effective SERS substrate for rapid in situ detection of organic pollutants in aqueous solutions, on fruits and other solid objects.

Fabrication of hexagonally patterned flower-like silver particle arrays as surface-enhanced Raman scattering substrates.

Hierarchical assembly of plasmonic nanostructures can induce high surface-enhanced Raman scattering (SERS) activity. However, it is a challenge to uniformly disperse the hierarchical nanostructures onto a planar substrate to achieve SERS signal reproducibility. This report presents a facile route to fabricate a hexagonally patterned flower-like silver particle array as the SERS substrate. First, hexagonally ordered silver hemisphere arrays with smooth surface are molded in the pores of an anodic aluminum oxide template. Ag-nanosheets are then electrodeposited onto the surface of individual silver hemispheres. The numerous nano-edges and nano-gaps between adjacent nanosheets render a large number of hot spots, leading to high SERS activity over a larger area of chip. The silver flower-like array is employed as the SERS substrate, which is able to detect 0.1 nM rhodamine 6 G and 1 µM 3,3',4,4'-tetrachlorobiphenyl (PCB-77, a persistent organic pollutant).

An ordered array of hierarchical spheres for surface-enhanced Raman scattering detection of traces of pesticide.

An ordered array of hierarchically-structured core-nanosphere@space-layer@shell-nanoparticles has been fabricated for surface-enhanced Raman scattering (SERS) detection. To fabricate this hierarchically-structured chip, a long-range ordered array of Au/Ag-nanospheres is first patterned in the nano-bowls on the planar surface of ordered nanoporous anodic titanium oxide template. A ultra-thin alumina middle space-layer is then conformally coated on the Au/Ag-nanospheres, and Ag-nanoparticles are finally deposited on the surface of the alumina space-layer to form an ordered array of Au/Ag-nanosphere@Al2O3-layer@Ag-nanoparticles. Finite-difference time-domain simulation shows that SERS hot spots are created between the neighboring Ag-nanoparticles. The ordered array of hierarchical nanostructures is used as the SERS-substrate for a trial detection of methyl parathion (a pesticide) in water and a limit of detection of 1 nM is reached, indicating its promising potential in rapid monitoring of organic pollutants in aquatic environment.

Ag Nanoparticle-Grafted PAN-Nanohump Array Films with 3D High-Density Hot Spots as Flexible and Reliable SERS Substrates.

A facile fabrication approach of large-scale flexible films is reported, with one surface side consisting of Ag-nanoparticle (Ag-NP) decorated polyacrylonitrile (PAN) nanohump (denoted as Ag-NPs@PAN-nanohump) arrays. This is achieved via molding PAN films with ordered nanohump arrays on one side and then sputtering much smaller Ag-NPs onto each of the PAN-nanohumps. Surface-enhanced Raman scattering (SERS) activity of the Ag-NPs@PAN-nanohump array films can be improved by curving the flexible PAN film with ordered nanohump arrays during the Ag-sputtering process to increase the density of the Ag-NPs on the sidewalls of the PAN-nanohumps. More 3D hot spots are thus achieved on a large-scale. The Ag-NPs@PAN-nanohump array films show high SERS activity with good Raman signal reproducibility for Rhodamine 6G probe molecules. To trial their practical application, the Ag-NPs@PAN-nanohump array films are employed as SERS substrates for trace detection of trinitrotoluene and a congener of polychlorinated biphenyls. A lower detection limit of 10(-12) m and 10(-5) m can be achieved, respectively. Furthermore, the flexible Ag-NPs@PAN-nanohump array films can also be utilized as swabs to probe traces of methyl parathion on the surface of fruits such as apples. The as-fabricated SERS substrates therefore have promising potential for applications in rapid safety inspection and environmental protection.

Ag-nanoparticle-decorated Ge nanocap arrays protruding from porous anodic aluminum oxide as sensitive and reproducible surface-enhanced Raman scattering substrates.

We report on the fabrication of Ag nanoparticle (Ag NP) decorated germanium (Ge) nanocap (Ag-NPs@Ge-nanocap) arrays protruding from highly ordered porous anodic aluminum oxide (AAO) template as highly sensitive and uniform surface-enhanced Raman scattering (SERS) substrates. The hybrid SERS substrates are fabricated via a combinatorial process of AAO template-assisted growth of Ge nanotubes with each tube having a hemispherical nanocap on the AAO pore bottom, wet chemical etching of the remaining aluminum and the AAO barrier layer to expose the Ge nanocaps, and sputtering Ag NPs on the Ge nanocap arrays. Because sufficient SERS "hot spots" are created from the electromagnetic coupling among the Ag NPs on the Ge nanocap and the highly ordered Ge nanocap arrays also have semiconducting chemical supporting enhancement, the hybrid SERS substrates have high SERS sensitivity and good signal reproducibility. Using the hybrid SERS substrates, Rhodamine 6G with a concentration down to 10(-11) M is identified, and one congener of highly toxic polychlorinated biphenyls with a concentration as low as 10(-6) M is also recognized, showing great potential for SERS-based rapid detection of organic pollutants in the environment.

Label-free selective SERS detection of PCB-77 based on DNA aptamer modified SiO2@Au core/shell nanoparticles.

A label-free approach to selective detection of 3,3',4,4'-tetrachlorobiphenyl (PCB77) using aptamer modified silica-Au/core-shell nanoparticles (denoted as SiO2@Au core/shell NPs) through surface enhanced Raman scattering (SERS) spectroscopy was proposed. The devised system consisted of SiO2@Au core/shell NPs fixed on the amino-silane functionalized glass slides with the PCB77-binding aptamers attached covalently to the gold surfaces through a thiol linker. The aptamers made of single-stranded DNA (ssDNA) oligomers with one end standing on the Au surface changed the conformation upon conjugation with PCB77, which correspondingly caused the spectral response of the ssDNA oligomers. The intensity ratio I(660 cm(-1))/I(736 cm(-1)) decreased with the amount of PCB77 added, which thus allowed us to measure trace amounts of PCB77 in a selective and quantitative way. This work therefore demonstrates that the design of aptamer-modified SiO2@Au core/shell NPs can be utilized for label-free SERS detection of persistent organic pollutants (POPs) in the environment.

Ordered arrays of Au-nanobowls loaded with Ag-nanoparticles as effective SERS substrates for rapid detection of PCBs.

Large-scale hexagonally close-packed arrays of Au-nanobowls (Au-NBs) with tens of Ag-nanoparticles (Ag-NPs) dispersed in each bowl (denoted as Ag-NPs@Au-NB arrays) are achieved and utilized as effective surface-enhanced Raman scattering (SERS) substrates. The field enhancement benefiting from the special particle-in-cavity geometrical structure as well as the high density of SERS hot spots located in the sub-10 nm gaps between adjacent Ag-NPs and at the particle-cavity junctions all together contribute to the high SERS activity of the Ag-NPs@Au-NB arrays; meanwhile the ordered morphological features of the Ag-NPs@Au-NB arrays guarantee uniformity and reproducibility of the SERS signals. By modifying the Ag-NPs@Au-NB arrays with mono-6-thio-ß-cyclodextrin, the SERS detection sensitivity to 3,3('),4,4(')-tetrachlorobiphenyl (PCB-77, one congener of polychlorinated biphenyls (PCBs, kinds of persistent organic pollutants which represent a global environmental hazard)) can be further improved and a low concentration down to 5 × 10(-7) M can still be examined, showing promising potential for application in rapid detection of trace-level PCBs in the environment.

Ag-nanoparticles-decorated NiO-nanoflakes grafted Ni-nanorod arrays stuck out of porous AAO as effective SERS substrates.

NiO-nanoflakes (NiO-NFs) grafted Ni-nanorod (Ni-NR) arrays stuck out of the porous anodic aluminum oxide (AAO) template are achieved by a combinatorial process of AAO-confined electrodeposition of Ni-NRs, selectively etching part of the AAO template to expose the Ni-NRs, wet-etching the exposed Ni-NRs in ammonia to obtain Ni(OH)2-NFs grafted onto the cone-shaped Ni-NRs, and annealing to transform Ni(OH)2-NFs in situ into NiO-NFs. By top-view sputtering, Ag-nanoparticles (Ag-NPs) are decorated on each NiO-NFs grafted Ni-NR (denoted as NiO-NFs@Ni-NR). The resultant Ag-NPs-decorated NiO-NFs@Ni-NR (denoted as Ag-NPs@NiO-NFs@Ni-NR) arrays exhibit not only strong surface-enhanced Raman scattering (SERS) activity but also reproducible SERS-signals over the whole array. It is demonstrated that the strong SERS-activity is mainly ascribed to the high density of sub-10 nm gaps (hot spots) between the neighboring Ag-NPs, the semiconducting NiO-NFs induced chemical enhancement effect, and the lightning rod effect of the cone-shaped Ni-NRs. The three-level hierarchical nanostructure arrays stuck out of the AAO template can be utilized to probe polychlorinated biphenyls (PCBs, a kind of global environmental hazard) with a concentration as low as 5 × 10(-6) M, showing promising potential in SERS-based rapid detection of organic environmental pollutants.

High Density 3D Carbon Tube Nanoarray Electrode Boosting the Capacitance of Filter Capacitor.

Electric double-layer capacitors (EDLCs) with fast frequency response are regarded as small-scale alternatives to the commercial bulky aluminum electrolytic capacitors. Creating carbon-based nanoarray electrodes with precise alignment and smooth ion channels is crucial for enhancing EDLCs' performance. However, controlling the density of macropore-dominated nanoarray electrodes poses challenges in boosting the capacitance of line-filtering EDLCs. Herein, a simple technique to finely adjust the vertical-pore diameter and inter-spacing in three-dimensional nanoporous anodic aluminum oxide (3D-AAO) template is achieved, and 3D compactly arranged carbon tube (3D-CACT) nanoarrays are created as electrodes for symmetrical EDLCs using nanoporous 3D-AAO template-assisted chemical vapor deposition of carbon. The 3D-CACT electrodes demonstrate a high surface area of 253.0 m2 g-1, a D/G band intensity ratio of 0.94, and a C/O atomic ratio of 8. As a result, the high-density 3D-CT nanoarray-based sandwich-type EDLCs demonstrate a record high specific areal capacitance of 3.23 mF cm-2 at 120 Hz and exceptional fast frequency response due to the vertically aligned and highly ordered nanoarray of closely packed CT units. The 3D-CT nanoarray electrode-based EDLCs could serve as line filters in integrated circuits, aiding power system miniaturization.

Ostwald-ripening-induced growth of parallel face-exposed Ag nanoplates on micro-hemispheres for high SERS activity.

Ag nanoplates, as two-dimensional plasmonic nanostructures, have attracted intensive attention due to their strong shape-dependent optical properties and related applications. Here parallel face-exposed Ag nanoplates vertically grown on micro-hemisphere surfaces have been achieved by firstly electrodepositing the micro-hemispheres assembled by Ag nanoplates, whose planar surfaces are stuck together, on indium tin oxide substrates, and then Ostwald ripening the as-electrodeposited micro-hemispheres in water. The sizes of the nanoplates and the gaps between the neighboring nanoplates have been tailored by tuning the Ostwald-ripening duration, so that the SERS activity of the micro-hemispheres has been remarkably improved. The improved SERS activity can be well explained by our systematic finite-element simulation. Therefore, Ostwald ripening offers a route to the synthesis of Ag nanoplates, and the optimization of plasmon coupling and SERS activity of nanostructure-assembled systems.

Manipulating Coupled Field Enhancement in Slot-under-Groove Nanoarrays for Universal Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) is an ultrasensitive spectroscopic technique that can identify materials and chemicals based on their inelastic light-scattering properties. In general, SERS relies on sub-10 nm nanogaps to amplify the Raman signals and achieve ultralow-concentration identification of analytes. However, large-sized analytes, such as proteins and viruses, usually cannot enter these tiny nanogaps, limiting the practical applications of SERS. Herein, we demonstrate a universal SERS platform for the reliable and sensitive identification of a wide range of analytes. The key to this success is the prepared "slot-under-groove" nanoarchitecture arrays, which could realize a strongly coupled field enhancement with a large spatial mode distribution via the hybridization of gap-surface plasmons in the upper V-groove and localized surface plasmon resonance in the lower slot. Therefore, our slot-under-groove platform can simultaneously deliver high sensitivity for small-sized analytes and the identification of large-sized analytes with a large Raman gain.

Well-defined nanoclusters as fluorescent nanosensors: a case study on Au(25) (SG)(18).

The fluorescence of nanoparticles has attracted much attention in recent research, but in many cases the underlying mechanisms are difficult to evaluate due to the polydispersity of nanoparticles and their unknown structures, in particular the surface structures. Recent breakthroughs in the syntheses and structure determinations of well-defined gold nanoclusters provide opportunities to conduct in-depth investigations. Devising well-defined nanocluster sensors based on fluorescence change is of particular interest not only for scientific studies but also for practical applications. Herein, the potential of the glutathionate (SG)-capped Au(25) nanocluster as a silver ion sensor is evaluated. The Ag(+) detection limit of approximately 200 nM, based on the fluorescence enhancement and good linear fluorescence response in the silver ion concentration range from 20 nM to 11 µM, in combination with the good selectivity among 20 types of metal cations, makes Au(25) (SG)(18) a good candidate for fluorescent sensors for silver ions. Further experiments reveal three important factors responsible for the unique fluorescence enhancement caused by silver ions: 1) the oxidation state change of Au(25) (SG)(18) ; 2) the interaction of neutral silver species (Ag(0) , reduced by Au(25) (SG)(18) (-) ) with Au(25) (SG)(18) ; and 3) the interaction of Ag(+) with Au(25) (SG)(18.) Experiments demonstrate the very different chemistry of hydrophobic Au(25) (SC(2) H(4) Ph)(18) and hydrophilic Au(25) (SG)(18) in the reaction with silver ions. This work indicates another potential application of gold nanoclusters, offers new strategies for nanocluster-based chemical sensing, and reveals a new way to influence nanocluster chemistry for potential applications.

Galvanic-cell-induced growth of Ag nanosheet-assembled structures as sensitive and reproducible SERS substrates.

SERS up: Ag nanosheet-assembled structures with controlled morphologies were achieved on indium tin oxide substrates by galvanic-cell-induced growth (see figure). These structures exhibit a highly active and homogeneous surface-enhanced Raman scattering (SERS) effect, and show promising potential as reliable SERS substrates for detection of trace polychlorinated biphenyls.