Tunable mid-infrared photodetector based on graphene plasmons controlled by ferroelectric polarization for micro-spectrometer.

Surface plasmonic detectors have the potential to be key components of miniaturized chip-scale spectrometers. Graphene plasmons, which are highly confined and gate-tunable, are suitable forin situlight detection. However, the tuning of graphene plasmonic photodetectors typically relies on the complex and high operating voltage based on traditional dielectric gating technique, which hinders the goal of miniaturized and low-power consumption spectrometers. In this work, we report a tunable mid-infrared (MIR) photodetector by integrating of patterned graphene with non-volatile ferroelectric polarization. The polarized ferroelectric thin film provides an ultra-high surface electric field, allowing the Fermi energy of the graphene to be manipulated to the desired level, thereby exciting the surface plasmon polaritons effect, which is highly dependent on the free carrier density of the material. By exciting intrinsic graphene plasmons, the light transmittance of graphene is greatly enhanced, which improves the photoelectric conversion efficiency of the device. Additionally, the electric field on the surface of graphene enhanced by the graphene plasmons accelerates the carrier transfer efficiency. Therefore, the responsivity of the device is greatly improved. Our simulations show that the detectors have a tunable resonant spectral response of 9-14µm by reconstructing the ferroelectric domain and exhibit a high responsivity to 5.67 × 105A W-1at room temperature. Furthermore, we also demonstrate the conceptual design of photodetector could be used for MIR micro-spectrometer application.

An anti-scratch flexible SERS substrate for pesticide residue detection on the surface of fruits and vegetables.

We propose an anti-scratch flexible surface-enhanced Raman scattering substrate with arrayed nanocavity microstructures fabricated by colloidal lithography. The nanocavity microstructure of the substrate can well protect the inner gold nanoparticles during wipe sampling. The prepared flexible substrate was able to detect 4-aminothiophenol (4-ATP) with a concentration down to 1 fM. Furthermore, the substrate was used to detect 6-BA residues on the surface of apples and bean sprouts through wipe sampling, which shows great potential in the field of rapid on-site detection, especially in the detection of pesticide residues on the surface of fruits and vegetables.

Magnetic assembled 3D SERS substrate for sensitive detection of pesticide residue in soil.

Three-dimensional (3D) surface enhanced Raman scattering (SERS) substrates were produced by magnetic force assisting self-assembled nanoparticles in arrayed holes. Compared to '2D' plasmonic structures used in conventional SERS substrates, the 'hot spots' existed on whole depth of the 3D SERS substrates, which greatly enhanced the sensitivity. The prepared 3D SERS substrate was able to detect 4-aminothiophenol with a concentration down to 1 pM. Furthermore, the substrate was applied to detect hexachlorobenzene residue in soil, indicating its great potential for rapid and sensitive detection of extreme low concentrated molecules, especially pollutants residues in foods and environments.

Graphene-based polarization-sensitive longwave infrared photodetector.

We demonstrated a polarization-sensitive photodetector based on periodically crossed graphene ribbons theoretically. Localized surface plasmon is generated by patterned graphene structure with significantly enhanced incident light absorption. Broadband detection is observed from 10.5 to 16.5 µm. Moreover, the photoresponsivity reaches up to 1.717 A W-1 at the wavelength of 12.58 µm under 0° polarization, and the photoresponsivity is 0.212 A W-1 under 90° polarization. The tunability of photodetectors is achieved by changing the gate voltage to modulate the chemical potential of graphene. The finite difference time domain solutions are used to predict the performance of the photodetector with different polarization angles for longwave infrared (LWIR) light. The polarization-sensitive, tunable and broadband graphene photodetector provides a promising direction for high performance LWIR detection at room temperature.

Metal Carbonyls for the Biointerference-Free Ratiometric Surface-Enhanced Raman Spectroscopy-Based Assay for Cell-Free Circulating DNA of Epstein-Barr Virus in Blood.

By taking advantage of the spectral properties of metal carbonyls, we have designed a surface-enhanced Raman spectroscopy (SERS) ratiometric assay for measuring cell-free circulating DNA (cfDNA) from Epstein-Barr virus in blood for nasopharyngeal carcinoma (NPC). This assay consists of a rhenium carbonyl (Re-CO) to serve as a DNA probe, an osmium carbonyl (Os-CO) embedded within the SERS-active substrate as an internal reference, and a streptavidin layer on the surface of the substrate. Hybridization of cfDNA with biotinylated-capture sequence leads to immobilization of cfDNA on the substrate. The binding of Re-CO via daunorubicin (DNR) to cfDNA is accompanied by an appearance of a strong symmetry stretching vibrations peak at 2113 cm-1, which has spectral overlap with Os-CO (2025 cm-1). This results in an increase in the I2113/ I2025 ratio and quantitatively correlates with cfDNA. This SERS assay can be readily used to detect cfDNA in blood samples from patients due to the intensity ratio of I2113/ I2025 lying in a silent region (1780-2200 cm-1) in the SERS spectrum of the biomolecules.

A rapid and label-free SERS detection method for biomarkers in clinical biofluids.

A metal carbonyl-functionalized nanostructured substrate can be used in a rapid and simple assay for the detection of A1AT, a potential biomarker for bladder cancer, in clinical urine samples. The assay involves monitoring changes in the carbonyl stretching vibrations of the metal carbonyl via surface-enhanced Raman spectroscopy (SERS). These vibrations lie in the absorption spectral window of 1800-2200 cm(-1), which is free of any spectral interference from biomolecules.

Photoinduced whispering gallery mode microcavity resonator in a chalcogenide microfiber.

We demonstrate an approach to creating localized whispering gallery mode (WGM) microcavities by exploiting the photosensitivity of a chalcogenide (As2S3) microfiber. A highly prolate WGM microcavity with cavity quality factors (Q) exceeding 2×10(5) is fabricated and characterized. Without the need for geometrical shaping, our approach enables the cavity properties to be monitored during fabrication for the first time.

An Artificial Electrical-Chemical Mixed Synapse Based on Ion-Gated MoS2 Nanosheets for Real-Time Facilitation Index Tuning.

Tunability of facilitation in short-term memory (STM) provides great potential in bioinspired computing. Recently, several doping strategies were proposed to modify the intrinsic features of materials, resulting in the optimization of the facilitation index (FI). However, real-time scale tuning, which is implemented on the same synaptic device, has not yet been demonstrated. Inspired by the chemical-electrical mixed synapse structure in the brain, we propose a three-terminal artificial synapse based on an ion-gated MoS2 memristor. The gate terminal serves as a nonvolatile ionic pump via chemical intercalation, which effectively affects both the conductance baseline and the hysteresis degree of the STM effect of the memristor. We further modeled the postsynaptic current (PSC) behavior and used it for reservoir computing. Simulation results show that, due to the real-time tuning ability, the built reservoir can be programmed for specific handwritten recognition tasks with the pruning of neurons from 784 to 50. The developed artificial mixed synapse is promising for a downsampling module in neural network design.

Hybrid strategy of graphene/carbon nanotube hierarchical networks for highly sensitive, flexible wearable strain sensors.

One-dimensional and two-dimensional materials are widely used to compose the conductive network atop soft substrate to form flexible strain sensors for several wearable electronic applications. However, limited contact area and layer misplacement hinder the rapid development of flexible strain sensors based on 1D or 2D materials. To overcome these drawbacks above, we proposed a hybrid strategy by combining 1D carbon nanotubes (CNTs) and 2D graphene nanoplatelets (GNPs), and the developed strain sensor based on CNT-GNP hierarchical networks showed remarkable sensitivity and tenability. The strain sensor can be stretched in excess of 50% of its original length, showing high sensitivity (gauge factor 197 at 10% strain) and tenability (recoverable after 50% strain) due to the enhanced resistive behavior upon stretching. Moreover, the GNP-CNT hybrid thin film shows highly reproducible response for more than 1000 loading cycles, exhibiting long-term durability, which could be attributed to the GNPs conductive networks significantly strengthened by the hybridization with CNTs. Human activities such as finger bending and throat swallowing were monitored by the GNP-CNT thin film strain sensor, indicating that the stretchable sensor could lead to promising applications in wearable devices for human motion monitoring.

Tandem Quantification of Multiple Carbohydrates in Saliva Using Surface-Enhanced Raman Spectroscopy.

The detection of carbohydrates in human body fluids is critical for disease diagnosis and healthy monitoring. Despite recent advances in glucose sensing, multiplex detection of different carbohydrates within a single assay that is capable of efficiently providing richer health information remains challenging. Herein, we report a versatile surface-enhanced Raman spectroscopy-based platform for the quantitative detection of monosaccharides (glucose, fructose, and galactose) in one test using a displace-and-trap mechanism. Moreover, due to the use of multiple optical interference-free (1800-2200 cm-1) signal-independent Raman probes, the detection range of this platform (0.125-7 mg/dL) perfectly covers physiological concentrations, enabling the quantitative detection of glucose and galactose in clinical human saliva samples. This work provides a noninvasive and high-efficiency potential tool for the screening of clinical diabetes and other carbohydrate-related diseases.

Geometrically encoded SERS nanobarcodes for the logical detection of nasopharyngeal carcinoma-related progression biomarkers.

The limited availability of nasopharyngeal carcinoma-related progression biomarker array kits that offer physicians comprehensive information is disadvantageous for monitoring cancer progression. To develop a biomarker array kit, systematic identification and differentiation of a large number of distinct molecular surface-enhanced Raman scattering (SERS) reporters with high spectral temporal resolution is a major challenge. To address this unmet need, we use the chemistry of metal carbonyls to construct a series of unique SERS reporters with the potential to provide logical and highly multiplex information during testing. In this study, we report that geometric control over metal carbonyls on nanotags can produce 14 distinct barcodes that can be decoded unambiguously using commercial Raman spectroscopy. These metal carbonyl nanobarcodes are tested on human blood samples and show strong sensitivity (0.07 ng/mL limit of detection, average CV of 6.1% and >92% degree of recovery) and multiplexing capabilities for MMPs.

Optoplasmonic Hybrid Materials for Trace Detection of Methamphetamine in Biological Fluids through SERS.

Optoplasmonic materials comprising both photonic and plasmonic elements are of particular interest for the development of substrates for surface-enhanced Raman spectroscopy (SERS). In this work, a layer of analyte-carrying dielectric nano/microspheres is placed on top of a monolayer of gold nanoparticles to enhance the intensity of the electric (E-) field localization and to enrich the analyte close to the electromagnetic hot spots. Numerical simulations of the hybrid structure confirm an increased and spatially expanded E-field enhancement at the interface. Due to a decreasing filling fraction with increasing size of the dielectric spheres, simulations predict a saturated SERS enhancement for dielectric microspheres with a diameter larger than 4 µm, which is confirmed by experimental SERS measurements. The dielectric microsphere can be functionalized with surface ligands that facilitate the binding of target molecules in solution. The deposition of the analyte-loaded microspheres on the self-assembled gold nanoparticle ensures a high local concentration of analytes in the electromagnetic "hot" surface. The performance of the optoplasmonic SERS approach for detecting methamphetamine in saliva and urine is tested, and the detection of analytes at nanomolar (nM) concentrations is demonstrated.

Single-Layer Triboelectric Nanogenerators Based on Ion-Doped Natural Nanofibrils.

As emerging ambient energy harvesting technology, triboelectric nanogenerators (TENGs) have proven to be a robust power source and have demonstrated the unique ability to power micro-nano electronics autonomously to form self-powered devices. Although four working modes of TENGs have been developed to promote the feasibility of self-powered micro-nano systems, the relatively complicated structure composed of multilayer and movable components limits the practical applications of TENGs. Herein, we propose a single-layer triboelectric nanogenerator (SL-TENG) based on ion-doped natural nanofibrils. Compared with the simplest mode of currently existing TENGs, i.e., the single-electrode type, this novel single-electrode TENG further simplifies the configuration by the removal of the dielectric layer. The underlying mechanism of the proposed SL-TENG is comprehensively investigated through electrical measurements and the analysis of the effect of ion species at different concentrations. In contrast to conventional TENGs that require electrodes to realize charge transfer, it is revealed that the ions doped into natural nanofibrils effectively realize charge transfer due to the separation and migration of cations and anions. This new working principle based on the combination of electrons and ions enables TENGs to show greater potential for applications since the ultrasimple single-layer configuration enables them to be more easily integrated with other electronic components; additionally, the whole device of the proposed SL-TENG is biodegradable because the natural nanofibrils are completely extracted from carrots.

Label-free diagnosis for colorectal cancer through coffee ring-assisted surface-enhanced Raman spectroscopy on blood serum.

Surface-enhanced Raman spectroscopy (SERS) is garnering considerable attention for the swift diagnosis of pathogens and abnormal biological status, that is, cancers. In this work, a simple, fast and inexpensive optical sensing platform is developed by the design of SERS sampling and data analysis. The pretreatment of spectral measurement employed gold nanoparticle colloid mixing with the serum from patients with colorectal cancer (CRC). The droplet of particle-serum mixture formed coffee-ring-like region at the rim, providing strong and stable SERS profiles. The obtained spectra from cancer patients and healthy volunteers were analyzed by unsupervised principal component analysis (PCA) and supervised machine learning model, such as support-vector machine (SVM), respectively. The results demonstrate that the SVM model provides the superior performance in the classification of CRC diagnosis compared with PCA. In addition, the values of carcinoembryonic antigen from the blood samples were compiled with the corresponding SERS spectra for SVM calculation, yielding improved prediction results.

Simulation of tuning graphene plasmonic behaviors by ferroelectric domains for self-driven infrared photodetector applications.

We demonstrate a tunable longwave infrared photodetector with ultra-high sensitivity based on graphene surface plasmon polaritons controlled by ferroelectric domains. The simulated results show that the photodetector shows a tunable absorption peak, modulated by periodically polarized ferroelectric domains at the nanoscale, with an ultra-high responsivity up to 7.62 × 106 A W-1 and a detectivity of ∼6.24 × 1013 Jones (Jones = cm Hz1/2 W-1) in the wavelengths ranging from 5 to 20 µm at room temperature. The potential mechanism for the prominent performances of the proposed photodetector can be attributed to the highly confined graphene surface plasmons excited by the local electrical field across the interface of the graphene and ferroelectric layer resonant to the incident wavelength, which could be easily controlled by the features of the ferroelectric domains. Compared with the silicon-based graphene plasmonic photodetector using a complex process of micro-nano fabrication, the proposed photodetector provides the advantages of a more convenient and controllable technique without the need for patterning graphene, and lower energy consumption due to the non-volatile properties of the ferroelectrics without an additional contact electrode. The tunable spectral response and the ultra-high responsivity make the graphene plasmonic photodetector tuned by the ferroelectric domains promising in practical applications of micro-spectrometers and other light sensing devices.

A dual signal amplification nanosensor based on SERS technology for detection of tumor-related DNA.

A dual signal amplification method based on surface-enhanced Raman scattering (SERS) is developed by photo-triggered release of SERS probes from mesoporous silica-coated Au nanorods (SiO2@Au) and the use of a specially-designed SERS substrate with an internal reference. Two metal carbonyl (metal-CO) labels (Os-SCO and Re-SCO) are proposed here as novel interference-free labels. Results demonstrate that tumor-related DNA can be quantitatively detected by this reliable and ultra-sensitive SERS platform.

Ultra-Sensitive Strain Sensor Based on Flexible Poly(vinylidene fluoride) Piezoelectric Film.

A flexible 4 × 4 sensor array with 16 micro-scale capacitive units has been demonstrated based on flexible piezoelectric poly(vinylidene fluoride) (PVDF) film. The piezoelectricity and surface morphology of the PVDF were examined by optical imaging and piezoresponse force microscopy (PFM). The PFM shows phase contrast, indicating clear interface between the PVDF and electrode. The electro-mechanical properties show that the sensor exhibits excellent output response and an ultra-high signal-to-noise ratio. The output voltage and the applied pressure possess linear relationship with a slope of 12 mV/kPa. The hold-and-release output characteristics recover in less than 2.5 µs, demonstrating outstanding electro-mechanical response. Additionally, signal interference between the adjacent arrays has been investigated via theoretical simulation. The results show the interference reduces with decreasing pressure at a rate of 0.028 mV/kPa, highly scalable with electrode size and becoming insignificant for pressure level under 178 kPa.

Ultra-sensitive and plasmon-tunable graphene photodetectors for micro-spectrometry.

We demonstrate an ultra-sensitive photodetector based on a graphene/monolayer MoS2 vertical heterostructure working at room temperature. Highly confined plasmon waves are efficiently excited through a periodic array of monolayer graphene ribbons in which plasmon resonance has remarkably large oscillator strength, resulting in a sharp optical absorption peak in the normal-incidence transmission spectrum. A significant amount of electron-hole pairs are produced in graphene ribbons by optical absorption, separated by the built-in electric field across the graphene/MoS2 heterojunction. The responsivity reaches up to 1 × 107 A W-1 at room temperature due to very strong resonance in the heterostructure, yielding a highly sensitive graphene-based photodetector. Additionally, the absorption can be tuned over a wide spectral range (6-16 µm) by varying gate biasing. The ultra-sensitive, spectrally tunable photodetector could be potentially used as a promising candidate for mid-infrared micro-spectrometers.

Optical Interference-Free Surface-Enhanced Raman Scattering CO-Nanotags for Logical Multiplex Detection of Vascular Disease-Related Biomarkers.

Matrix metalloproteinases (MMPs), specifically MMP-2, MMP-7, and MMP-9, have been discovered to be linked to many forms of vascular diseases such as stroke, and their detection is crucial to facilitate clinical diagnosis. In this work, we prepared a class of optical interference-free SERS nanotags (CO-nanotags) that can be used for the purpose of multiplex sensing of different MMPs. Multiplex detection with the absence of cross-talk was achieved by using CO-nanotags with individual tunable intrinsic Raman shifts of CO in the 1800-2200 cm-1 region determined by the metal core and ligands of the metal carbonyl complex. Boolean logic was used as well to simultaneously probe for two proteolytic inputs. Such nanotags offer the advantages of convenient detection of target nanotags and high sensitivity as validated in the ischemia rat model.

Ultra-sensitive near-infrared graphene photodetectors with nanopillar antennas.

Graphene has been demonstrated as a candidate for optoelectronic devices due to its broad absorption spectrum and ultra-high carrier mobility. However, graphene is essentially transparent in visible and near-infrared regimes with an absorptivity of 2.3%, which largely limits its application in photodetection. Here, we show that metallic nanopillar antennas could improve light absorption in graphene detectors. The coupled antennas help to concentrate a free space electromagnetic wave around the nanopillars by localized surface plasmon resonance, strongly impacted by geometrical design. It is found that spectral selectivity can be realized by tuning key geometrical parameters such as period, radius, and height of the metallic nanopillar, leading to wavelength-tunable photodetectors within a broad range from 0.6 µm to 1.2 µm. With the optimized design, the detector exhibits an excellent photoresponsivity of 7 A W-1 at a wavelength of 0.82 µm.