Cascade Bowl Multicavity Structure for In Situ Surface-Enhanced Raman Scattering Detection of Organic Gas Molecules.

With the increasing emphasis on atmospheric environmental protection, it is crucial to find an efficient, direct, and accurate method to identify pollutant species in the atmosphere. To solve this problem, we designed and prepared the cascade multicavity (CMC) structure composed with silver nanoparticles (Ag NPs) as a surface-enhanced Raman scattering (SERS) substrate with favorable light transmittance and flexibility. The multicavity structure distributed on the surface introducing the homogeneous connecting holes endows the structure to more fully utilize the incident light while slowing the gas movement rate. Theoretical and experimental results have demonstrated that the Ag NPs/cascade multicavity (Ag-CMC) SERS substrate is a highly sensitive SERS substrate that can be used for in situ detection of gases under non-perpendicularly incident laser irradiation or bending of the substrate. We believe that the SERS substrate can provide a more efficient and feasible way for in situ detection of gaseous pollutants.

Reversible Thermoelectric Regulation of Electromagnetic and Chemical Enhancement for Rapid SERS Detection.

Actively controlling surface-enhanced Raman scattering (SERS) performance plays a vital role in highly sensitive detection or in situ monitoring. Nevertheless, it is still challenging to achieve further modulation of electromagnetic enhancement and chemical enhancement simultaneously in SERS detection. In this study, a silver nanocavity structure with graphene as a spacer layer is coupled with thermoelectric semiconductor P-type gallium nitride (GaN) to form an electric-field-induced SERS (E-SERS) for dual enhancement. After applying the electric field, the intensity of SERS signals is further enhanced by over 10 times. The thermoelectric field enables fast and reproducible doping of graphene, thereby modulating its Fermi level over a wide range. The thermoelectric field also regulates the position of the plasmon resonance peak of the silver nanocavity structure, rendering synchronous dual electromagnetic and chemical regulation. Additionally, the method enables the trace detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). A detailed theoretical analysis is performed based on the experimental results and finite-element calculations, paving the way for the fabrication of high-efficient E-SERS substrates.

Thermoelectrically Driven Dual-Mechanism Regulation on SERS and Application Potential for Rapid Detection of SARS-CoV-2 Viruses and Microplastics.

Electric-induced surface-enhanced Raman scattering (E-SERS) has been widely studied for its flexible regulation of SERS after the substrate is prepared. However, the enhancement effect is not sufficiently high in the E-SERS technology reported thus far, and no suitable field of application exists. In this study, a highly sensitive thermoelectrically induced SERS substrate, Ag/graphene/ZnO (AGZ), was fabricated using ZnO nanoarrays (NRs), graphene, and Ag nanoparticles (NPs). Applying a temperature gradient to the ZnO NRs enhanced the SERS signals of the probe molecules by a factor of approximately 20. Theoretical and experimental results showed that the thermoelectric potential enables the simultaneous modulation of the Fermi energy level of graphene and the plasma resonance peak of Ag NPs, resulting in a double enhancement in terms of physical and chemical mechanisms. The AGZ substrate was then combined with a mask to create a wearable thermoelectrically enhanced SERS mask for collecting SARS-CoV-2 viruses and microplastics. Its SERS signal can be enhanced by the temperature gradient created between a body heat source (∼37 °C) and a cold environment. The suitability of this method for virus detection was also examined using a reverse transcription-polymerase chain reaction and SARS-CoV-2 virus antigen detection. This work offers new horizons for research of E-SERS, and its application potential for rapid detection of the SARS-CoV-2 virus and microplastics was also studied.

Asymmetric Schottky Barrier-Generated MoS2/WTe2 FET Biosensor Based on a Rectified Signal.

Field-effect transistor (FET) biosensors can be used to measure the charge information carried by biomolecules. However, insurmountable hysteresis in the long-term and large-range transfer characteristic curve exists and affects the measurements. Noise signal, caused by the interference coefficient of external factors, may destroy the quantitative analysis of trace targets in complex biological systems. In this report, a "rectified signal" in the output characteristic curve, instead of the "absolute value signal" in the transfer characteristic curve, is obtained and analyzed to solve these problems. The proposed asymmetric Schottky barrier-generated MoS2/WTe2 FET biosensor achieved a 105 rectified signal, sufficient reliability and stability (maintained for 60 days), ultra-sensitive detection (10 aM) of the Down syndrome-related DYRK1A gene, and excellent specificity in base recognition. This biosensor with a response range of 10 aM-100 pM has significant application potential in the screening and rapid diagnosis of Down syndrome.

Three-Dimensional MXene-AgNP Hollow Spheres for In Situ Surface-Enhanced Raman Scattering Detection of Catalysis Reactions.

MXenes are attractive candidates in the fields of surface-enhanced Raman scattering (SERS) and catalysis. However, most of the current studies on MXenes are based on blocks and nanosheets, limiting their SERS and catalytic properties. Herein, we have prepared 3D MXene hollow spheres wrapped with silver nanoparticles (Ti3C2-AgNP HSs) using a sacrificial template method, which exhibits excellent sensitivity with a low detection limit due to good light-trapping capability of the hollow sphere and strong localized surface plasmon resonance (LSPR) effect of AgNPs. Furthermore, it shows outstanding photocatalytic performance and realizes in situ SERS monitoring of the 4-nitrobenzenethiol (4-NTP) to 4-aminothiophenol (4-ATP) catalysis reaction. The finite-difference time-domain (FDTD) simulations confirm that 3D Ti3C2-AgNP hollow structures have stronger hot spots than 3D solid structures and higher SERS sensitivity for molecule detection. Therefore, it promises to be an excellent bifunctional material for highly sensitive SERS detection and the in situ monitoring of catalytic reactions.

Flexible Cascaded Wire-in-Cavity-in-Bowl Structure for High-Performance and Polydirectional Sensing of Contaminants in Microdroplets.

To improve the drawback of surface-enhanced Raman scattering (SERS) sensors that are sensitive to excitation angles and realize the monitoring of contaminants in complex environments, we have proposed and prepared a cascaded wire-in-cavity-in-bowl (WICIB) structure on flexible polydimethysiloxane, with feasibility for plasmonic coupling. We demonstrated that the WICIB structure can serve as a highly sensitive, homogeneous, and stable SERS substrate for conventional detection. The plasmonic coupling and distribution of the enhanced electromagnetic field were evidently proven by finite element simulations, and the strong electromagnetic field was regulated around the wire and inside the cavity, which is very beneficial for the polydirectional and in situ detection. By virtue of the triple synergistic enhancement effect and unique optical properties, we successfully achieved the in situ detection of the residual pollutant molecules, ziram and 2-naphthalenethiol, in microdroplets of apple juice and lake water. Accordingly, such a flexible SERS sensor exhibits great potential in on-site environmental monitoring.

Giant enhancement of the initial SERS activity for plasmonic nanostructures via pyroelectric PMN-PT.

Herein, a simply-prepared and highly sensitive electric field-induced surface-enhanced Raman spectroscopy (E-SERS) substrate is proposed by combining a pyroelectric material (PMN-PT) with the plasmonic silver nanoparticles (Ag NP). The intensity of SERS signals is further enhanced by more than 100 times after the application of positive or negative pyroelectric potentials. Theoretical calculations and experimental characterizations demonstrate that the chemical mechanism (CM) as induced by the charge transfer (CT) is mainly responsible for enhanced E-SERS. In addition, a novel nanocavity structure with PMN-PT/Ag/Al2O3/silver nanocubes (Ag NCs) was also introduced, which could effectively convert light energy into heat energy and realize a tremendous enhancement of SERS signals. These findings are expected to further accelerate the application of plasmonic metal nanoparticle-based pyroelectric materials in the fields of energy conversion, optical-sensors and photocatalysts.

Review on two-dimensional material-based field-effect transistor biosensors: accomplishments, mechanisms, and perspectives.

Field-effect transistor (FET) is regarded as the most promising candidate for the next-generation biosensor, benefiting from the advantages of label-free, easy operation, low cost, easy integration, and direct detection of biomarkers in liquid environments. With the burgeoning advances in nanotechnology and biotechnology, researchers are trying to improve the sensitivity of FET biosensors and broaden their application scenarios from multiple strategies. In order to enable researchers to understand and apply FET biosensors deeply, focusing on the multidisciplinary technical details, the iteration and evolution of FET biosensors are reviewed from exploring the sensing mechanism in detecting biomolecules (research direction 1), the response signal type (research direction 2), the sensing performance optimization (research direction 3), and the integration strategy (research direction 4). Aiming at each research direction, forward perspectives and dialectical evaluations are summarized to enlighten rewarding investigations.

Nanowire-in-bowl-shaped piezoelectric cavity structure for SERS directional detection of nanoplastics less than 50†nm.

The accurate detection of nanoplastics is crucial due to their harmful effects on the environment and human beings. However, there is a lack of detection methods for nanoplastics smaller than 50 nm. In this research, we successfully constructed an Ag/CuO nanowire (NW)/BaTiO3@Polyvinylidene fluoride (PVDF) Bowl-shaped substrate with a nanowire-in-Bowl-shaped piezoelectric cavity structure that can modulate surface-enhanced Raman scattering (SERS) by the piezoelectric effect by the virtue of the tip effect of the CuO NW and light focusing effect of the Bowl-shaped cavity. Due to its unique nanowire-in-Bowl-shaped structure and piezoelectrically modifiable ability, nanoplastics less than 50 nm were successfully detected and quantitatively analyzed. We believe that the Ag/CuO NW/BaTiO3@PVDF Bowl-shaped substrate can provide an efficient, accurate, and feasible way to achieve qualitative and quantitative detection of nanoplastics.

High-intensity vector signals for detecting SARS-CoV-2 RNA using CRISPR/Cas13a couple with stabilized graphene field-effect transistor.

False detection of SARS-CoV-2 is detrimental to epidemic prevention and control. The scalar nature of the detected signal and the imperfect target recognition property of developed methods are the root causes of generating false signals. Here, we reported a collaborative system of CRISPR-Cas13a coupling with the stabilized graphene field-effect transistor, providing high-intensity vector signals for detecting SARS-CoV-2. In this collaborative system, SARS-CoV-2 RNA generates a "big subtraction" signal with a right-shifted feature, whereas any untargets cause the left-shifted characteristic signal. Thus, the false detection of SARS-CoV-2 is eliminated. High sensitivity with 0.15 copies/µL was obtained. In addition, the wide concerned instability of the graphene field-effect transistor for biosensing in solution environment was solved by the hydrophobic treatment to its substrate, which should be a milestone in advancing it's engineering application. This collaborative system characterized by the high-intensity vector signal and amazing stability significantly advances the accurate SARS-CoV-2 detection from the aspect of signal nature.

SERS Sensing Using Graphene-Covered Silver Nanoparticles and Metamaterials for the Detection of Thiram in Soil.

Multilayer hyperbolic metamaterial (HMM)-based SERS substrates have received special consideration because they accommodate various propagation modes such as surface plasmonic polaritons (SPP). However, the SPP modes are difficult to generate in HMM due to their weak electric field enhancement. In this article, we designed novel SERS substrates consisting of graphene-covered AgNPs and HMM. The graphene-covered AgNPs work as an external coupling structure for hyperbolic metamaterials due to this structure exhibiting significant plasmonic effects as well as unique optical features. The localized surface plasmonic resonance (LSPR) of the graphene-covered AgNPs excited the SPP and thus formed a strong hot spot zone in the nanogap area of the graphene. The Raman experiment was performed using rhodamine 6G (R6G) and crystal violet (CV), which showed high stability and a maximum enhancement factor of 2.12 × 108. The COMSOL simulation further clarified that enhanced SERS performance was due to the presence of monolayer graphene and provided an atomically flat surface for organic molecules in a more controllable manner. Interestingly, the proposed SERS structure carries out quantitative detection of thiram in soil and can satisfy the basic environmental need for pesticide residue in the soil.

Plasmonic enhanced piezoelectric photoresponse with flexible PVDF@Ag-ZnO/Au composite nanofiber membranes.

The coordination of piezoelectric and plasmonic effects to regulate the separation and migration of photo-generated carriers is still a significant method to improve the performance of visible-light photoresponse. Herein, we propose the PVDF@Ag-ZnO/Au composite nanofiber membranes utilizing the piezoelectric and plasmonic effects to promote the photocatalytic degradation of organic dyes. Here, ZnO nanorods can generate a built-in electric field under vibration to separate electron-hole pairs. The Schottky junction formed by noble metal/semiconductor can not only inhibit the recombination of photo-generated carriers and accelerate the migration of carriers, but also enhance the utilization of visible light. In addition, the structure has excellent flexibility and easy recycling characteristics. We demonstrate that the plasmonic effect of noble metal can enhance the light response of membranes and broaden light absorption from ultraviolet to visible light region. With the help of the surface-enhanced Raman scattering (SERS), modulation effects of the piezoelectric effect on light response is proved. For catalytic processes, rhodamine B (98.8%) can be almost completely degraded using PVDF@Ag-ZnO/Au within 120 minutes in the piezoelectric photocatalysis process, which is 2.2 and 2.8 times higher than photocatalysis and piezoelectric catalysis, respectively. This work provides a promising strategy for harnessing solar and mechanical energy.

SERS enhancement induced by the Se vacancy defects in ultra-thin hybrid phase SnSex nanosheets.

Improving the photo-induced charge transfer (PICT) efficiency by adjusting the energy levels difference between adsorbed probe molecules and substrate materials is a key factor for boosting the surface enhanced Raman scattering (SERS) based on the chemical mechanism (CM). Herein, a new route to improve the SERS activity of two-dimensional (2D) selenium and tin compounds (SnSex, 1 ≤ x ≤ 2) by the hybrid phase materials is researched. The physical properties and the energy band structure of SnSex were analyzed. The enhanced SERS activity of 2D SnSex can be attribute to the coupling of the PICT resonance caused by the defect energy levels induced by Se vacancy and the molecular resonance Raman scattering (RRS). This established a relationship between the physical properties and SERS activity of 2D layered materials. The resonance probe molecule, rhodamine (R6G), which is used to detect the SERS performance of SnSex nanosheets. The enhancement factor (EF) of R6G on the optimized SnSe1.35 nanosheets can be as high as 2.6 × 106, with a detection limit of 10-10 M. The SERS result of the environmental pollution, thiram, shows that the SnSex nanosheets have a practical application in trace SERS detection, without the participation of metal particles. These results demonstrate that, through hybrid phase materials, the SERS sensitivity of 2D layered nanomaterials can be improved. It provides a kind of foreground non-metal SERS substrate in monitoring or detecting and provide a deep insight into the chemical SERS mechanism based on 2D layered materials.

The Origin of Mo2C Films for Surface-Enhanced Raman Scattering Analysis: Electromagnetic or Chemical Enhancement?

The relatively weak Raman enhanced factors of semiconductor-based substrate limit its further application in surface-enhanced Raman scattering (SERS). Here, a kind of two-dimensional (2D) semimetal material, molybdenum carbide (Mo2C) film, is prepared via a chemical vapor deposition (CVD) method, and the origin of SERS is investigated for the first time. The detection limits of the prepared Mo2C films for crystal violet (CV) and rhodamine 6G (R6G) molecules are low at 10-6 M and 10-8 M, respectively. Our detailed theoretical analysis, based on density functional theory and the finite element method, demonstrates that the enhancement of the 2D Mo2C film is indeed CM in nature rather than the EM effects. Besides, the basic doping strategies are proposed to further optimize the SERS sensitivity of Mo2C for Fermi level regulation. We believe this work will provide a helpful guide for developing a highly sensitive semimetal SERS substrate.

Qualitative and quantitative detection of microcystin-LR based on SERS-FET dual-mode biosensor.

Microcystin-LR (MC-LR), a kind of hepatoxin produced by cyanobacteria blooms, can promote liver cancer through long-term exposure even at low concentrations. In this study, a novel biosensor based on surface-enhanced Raman scattering (SERS) and field effect transistor (FET) dual sensing mode was developed by using gold nanoparticles (AuNPs)/graphene composite as sensing material. Based on the SERS sensing mode, the Raman fingerprint spectrum of MC-LR was obtained through the specific combination of MC-LR aptamer and MC-LR. The SERS enhanced effect of the AuNPs was also verified by theoretical simulation. By using FET sensing mode, the graphene field effect transistor (G-FET) biosensor respectively exhibited the detection limit as low as 0.62 aM and 0.91 aM in phosphate buffered saline (PBS) and human serum, and showed a good linear relationship in a wide range of 1 × 10-18 to 1 × 10-8 M in both solutions. Meanwhile, the sensor was utilized for the detection of MC-LR in actual water samples, and the complex components in the water did not interfere with MC-LR detection, indicating a significant high specificity of the sensor. The SERS-FET dual-mode biosensor can provide more detection options and improve the reliability of measurement results, which may has a great application prospect in the field of water environment detection.

Facilely Flexible Imprinted Hemispherical Cavity Array for Effective Plasmonic Coupling as SERS Substrate.

The focusing field effect excited by the cavity mode has a positive coupling effect with the metal localized surface plasmon resonance (LSPR) effect, which can stimulate a stronger local electromagnetic field. Therefore, we combined the self-organizing process for component and array manufacturing with imprinting technology to construct a cheap and reproducible flexible polyvinyl alcohol (PVA) nanocavity array decorating with the silver nanoparticles (Ag NPs). The distribution of the local electromagnetic field was simulated theoretically, and the surface-enhanced Raman scattering (SERS) performance of the substrate was evaluated experimentally. The substrate shows excellent mechanical stability in bending experiments. It was proved theoretically and experimentally that the substrate still provides a stable signal when the excited light is incident from different angles. This flexible substrate can achieve low-cost, highly sensitive, uniform and conducive SERS detection, especially in situ detection, which shows a promising application prospect in food safety and biomedicine.

MoS2-based multiple surface plasmonic coupling for enhanced surface-enhanced Raman scattering and photoelectrocatalytic performance utilizing the size effect.

MoS2-based heterostructures have received increasing attention for not only surface-enhanced Raman scattering (SERS) but also for enhanced photoelectrocatalytic (PEC) performance. This study presents a hydrothermal method for preparing vertical MoS2 nanosheets composed of in situ grown AuNPs with small size and chemically reduced AgNPs with large size to achieve the synergistic enhancement of SERS and PEC properties owing to the size effect of the plasmonic structure. Compared with pristine MoS2 nanosheets and unitary AuNPs or AgNPs composited with MoS2 nanosheets, the ternary heterostructure exhibited the strongest electromagnetic field and surface plasmon coupling, which was confirmed by finite-difference time-domain (FDTD) simulation and absorption spectra. In addition, the experimental results confirmed the outstanding SERS enhancement with an EF of 1.1×109, and the most efficient hydrogen evolution reaction (HER) activity with a sensitive photocurrent response, attributing to the multiple surface plasmonic coupling effects of the Au-Ag bimetal and efficient charge-transfer process between MoS2 and the bimetal. That is, it provides a robust method for developing multi-size bimetal-semiconductor complex nanocomposites for high-performance SERS sensors and PEC applications.

Preparation of a superhydrophobic AgNP/GF substrate and its SERS application in a complex detection environment.

Surface-enhanced Raman scattering (SERS) is widely considered to be a fingerprint spectrum that can realize molecular identification, and it continues to receive a lot of attention due to its high sensitivity and powerful qualitative analysis capabilities. In recent years, there has been a lot of work and reports on super-sensitive SERS substrates, but often the enhanced ability of the substrate is also effective for impurities and irrelevant molecules. Therefore, a problem that still remains to be solved is how to perform effective trace detection of specific substances in a complex detection environment. Herein, a superhydrophobic Ag nanoparticle/glass microfibre filter (AgNP/GF) substrate was designed to realize the Raman detection of complex multiphase solutions. The hydrophobic three-dimensional net-like structure provides efficient Raman enhancement, making the substrate have extremely high detection limits for dye molecules and even achieving specific detection of the hexane phase component (thiram molecule) in a multiphase solution.

Noble metal modified ReS2 nanocavity for surface-enhanced Raman spectroscopy (SERS) analysis.

The rhenium disulphide (ReS2) nanocavity-based surface enhanced Raman scattering (SERS) substrates ware fabricated on the gold-modified silicon pyramid (PSi) by thermal evaporation technology and hydrothermal method. In this work, the ReS2 nanocavity was firstly combined with metal nanostructures in order to improve the SERS properties of ReS2 materials, and the SERS response of the composite structure exhibits excellent performance in sensitivity, uniformity and repeatability. Numerical simulation reveals the synergistic effect of the ReS2 nanocavity and the plasmon resonance generated by the metal nanostructures. And the charge transfer between the metal, ReS2 and the analytes was also verified and plays an non-ignorable role. Besides, the plasmon-driven reaction for p-nitrothiophenol (PNTP) to p,p'-dimercaptobenzene (DMAB) conversion was successfully in-situ monitored. Most importantly, it is found for the first time that the SERS properties of ReS2 nanocavity-based substrates are strongly temperature dependent, and the SERS effect achieves the best performance at 45 °C. In addition, the low concentration detection of malachite green (MG) and crystal violet (CV) molecules in lake water shows its development potential in practical application.

Natural biomaterial sarcosine as an interfacial layer enables inverted organic solar cells to exhibit over 16.4% efficiency.

The natural biomaterial sarcosine as an electron transport layer (ETL) to modify ITO or ITO/ZnO was successfully introduced into inverted organic solar cells (OSCs) with PM6:BTP-BO-4Cl as the active layer. The introduction of sarcosine on the surface of ITO or ITO/ZnO resulted in lower work function (WF) and higher surface energy. The active layers processed on the surfaces of ITO or ITO/ZnO presented a more optimized morphology and a more ordered molecular arrangement after their modification with sarcosine. The introduction of sarcosine as an ETL promoted charge transport and collection in the OSCs. Therefore, the power conversion efficiency (PCE) of the OSCs increased to 13.53% from 3.86% by modifying ITO with sarcosine. The PCE of the OSCs with ZnO as ETLs improved to 16.45% from 14.85% by modifying ZnO with sarcosine. The improved PCEs benefited from the simultaneously improved short-circuit current density (JSC), fill factor (FF), and open-circuit voltage (VOC). Therefore, this work demonstrates that sarcosine has great potential as an ETL to improve the performance of OSCs.