Graphene, a 2D material with tunable optical properties, has recently attracted intense interest for reconfigurable metasurfaces. So far, the working wavelength of graphene‐based or hybrid graphene metasurfaces has been limited in the mid‐infrared and terahertz spectra. In this paper, by combining graphene with Au nanostructures, the authors demonstrate a near‐infrared tunable metasurface with decent modulation efficiency, weak dependence on graphene's carrier mobility, and small gate voltages, attributing to the unique interband transition of graphene. The experimental results agree well with numerical simulations. It is also shown that by properly designing the structural parameters of Au nanostructures, the hybrid graphene metasurface can be tunable in both near‐infrared and mid‐infrared regions.
Optical devices are highly attractive for biosensing as they can not only enable quantitative measurements of analytes but also provide information on molecular structures. Unfortunately, typical refractive index-based optical sensors do not have sufficient sensitivity to probe the binding of low-molecular-weight analytes. Non-optical devices such as field-effect transistors can be more sensitive but do not offer some of the significant features of optical devices, particularly molecular fingerprinting. We present optical conductivity-based mid-infrared (mid-IR) biosensors that allow for sensitive and quantitative measurements of low-molecular-weight analytes as well as the enhancement of spectral fingerprints. The sensors employ a hybrid metasurface consisting of monolayer graphene and metallic nano-antennas and combine individual advantages of plasmonic, electronic and spectroscopic approaches. First, the hybrid metasurface sensors can optically detect target molecule-induced carrier doping to graphene, allowing highly sensitive detection of low-molecular-weight analytes despite their small sizes. Second, the resonance shifts caused by changes in graphene optical conductivity is a well-defined function of graphene carrier density, thereby allowing for quantification of the binding of molecules. Third, the sensor performance is highly stable and consistent thanks to its insensitivity to graphene carrier mobility degradation. Finally, the sensors can also act as substrates for surface-enhanced infrared spectroscopy. We demonstrated the measurement of monolayers of sub-nanometer-sized molecules or particles and affinity binding-based quantitative detection of glucose down to 200 pM (36 pg/mL). We also demonstrated enhanced fingerprinting of minute quantities of glucose and polymer molecules.
more » « less- NSF-PAR ID:
- 10153584
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Light: Science & Applications
- Volume:
- 7
- Issue:
- 1
- ISSN:
- 2047-7538
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Graphene is an attractive material for all-optical modulation because of its ultrafast optical response and broad spectral coverage. However, all-optical graphene modulators reported so far require high pump fluence due to the ultrashort photo-carrier lifetime and limited absorption in graphene. We present modulator designs based on graphene-metal hybrid plasmonic metasurfaces with highly enhanced light-graphene interaction in the nanoscale hot spots at pump and probe (signal) wavelengths. Based on this design concept, we have demonstrated high-speed all-optical modulators at near and mid-infrared wavelengths (1.56 μm and above 6 μm) with significantly reduced pump fluence (1–2 orders of magnitude) and enhanced optical modulation. Ultrafast near-infrared pump-probe measurement results suggest that the modulators’ response times are ultimately determined by graphene’s ultrafast photocarrier relaxation times on the picosecond scale. The proposed designs hold the promise to address the challenges in the realization of ultrafast all-optical modulators for mid-and far-infrared wavelengths.
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The field of biosensing is in constant evolution, propelled by the need for sensitive, reliable platforms that provide consistent results, especially in the drug development industry, where small molecule characterization is of uttermost relevance. Kinetic characterization of small biochemicals is particularly challenging, and has required sensor developers to find solutions to compensate for the lack of sensitivity of their instruments. In this regard, surface chemistry plays a crucial role. The ligands need to be efficiently immobilized on the sensor surface, and probe distribution, maintenance of their native structure and efficient diffusion of the analyte to the surface need to be optimized. In order to enhance the signal generated by low molecular weight targets, surface plasmon resonance sensors utilize a high density of probes on the surface by employing a thick dextran matrix, resulting in a three-dimensional, multilayer distribution of molecules. Despite increasing the binding signal, this method can generate artifacts, due to the diffusion dependence of surface binding, affecting the accuracy of measured affinity constants. On the other hand, when working with planar surface chemistries, an incredibly high sensitivity is required for low molecular weight analytes, and furthermore the standard method for immobilizing single layers of molecules based on self-assembled monolayers (SAM) of epoxysilane has been demonstrated to promote protein denaturation, thus being far from ideal. Here, we will give a concise overview of the impact of tridimensional immobilization of ligands on label-free biosensors, mostly focusing on the effect of diffusion on binding affinity constants measurements. We will comment on how multilayering of probes is certainly useful in terms of increasing the sensitivity of the sensor, but can cause steric hindrance, mass transport and other diffusion effects. On the other hand, probe monolayers on epoxysilane chemistries do not undergo diffusion effect but rather other artifacts can occur due to probe distortion. Finally, a combination of tridimensional polymeric chemistry and probe monolayer is presented and reviewed, showing advantages and disadvantages over the other two approaches.more » « less
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Abstract Nanophotonic resonators can confine light to deep-subwavelength volumes with highly enhanced near-field intensity and therefore are widely used for surface-enhanced infrared absorption spectroscopy in various molecular sensing applications. The enhanced signal is mainly contributed by molecules in photonic hot spots, which are regions of a nanophotonic structure with high-field intensity. Therefore, delivery of the majority of, if not all, analyte molecules to hot spots is crucial for fully utilizing the sensing capability of an optical sensor. However, for most optical sensors, simple and straightforward methods of introducing an aqueous analyte to the device, such as applying droplets or spin-coating, cannot achieve targeted delivery of analyte molecules to hot spots. Instead, analyte molecules are usually distributed across the entire device surface, so the majority of the molecules do not experience enhanced field intensity. Here, we present a nanophotonic sensor design with passive molecule trapping functionality. When an analyte solution droplet is introduced to the sensor surface and gradually evaporates, the device structure can effectively trap most precipitated analyte molecules in its hot spots, significantly enhancing the sensor spectral response and sensitivity performance. Specifically, our sensors produce a reflection change of a few percentage points in response to trace amounts of the amino-acid proline or glucose precipitate with a picogram-level mass, which is significantly less than the mass of a molecular monolayer covering the same measurement area. The demonstrated strategy for designing optical sensor structures may also be applied to sensing nano-particles such as exosomes, viruses, and quantum dots.
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