skip to main content

Title: Biochemical sensing in graphene-enhanced microfiber resonators with individual molecule sensitivity and selectivity

Photonic sensors that are able to detect and track biochemical molecules offer powerful tools for information acquisition in applications ranging from environmental analysis to medical diagnosis. The ultimate aim of biochemical sensing is to achieve both quantitative sensitivity and selectivity. As atomically thick films with remarkable optoelectronic tunability, graphene and its derived materials have shown unique potential as a chemically tunable platform for sensing, thus enabling significant performance enhancement, versatile functionalization and flexible device integration. Here, we demonstrate a partially reduced graphene oxide (prGO) inner-coated and fiber-calibrated Fabry-Perot dye resonator for biochemical detection. Versatile functionalization in the prGO film enables the intracavity fluorescent resonance energy transfer (FRET) to be chemically selective in the visible band. Moreover, by measuring the intermode interference via noise canceled beat notes and locked-in heterodyne detection with Hz-level precision, we achieved individual molecule sensitivity for dopamine, nicotine and single-strand DNA detection. This work combines atomic-layer nanoscience and high-resolution optoelectronics, providing a way toward high-performance biochemical sensors and systems.

; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Journal Name:
Light: Science & Applications
Nature Publishing Group
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Field-effect transistor (FET)-based biosensors allow label-free detection of biomolecules by measuring their intrinsic charges. The detection limit of these sensors is determined by the Debye screening of the charges from counter ions in solutions. Here, we use FETs with a deformed monolayer graphene channel for the detection of nucleic acids. These devices with even millimeter scale channels show an ultra-high sensitivity detection in buffer and human serum sample down to 600 zM and 20 aM, respectively, which are ∼18 and ∼600 nucleic acid molecules. Computational simulations reveal that the nanoscale deformations can form ‘electrical hot spots’ in the sensing channel which reduce the charge screening at the concave regions. Moreover, the deformed graphene could exhibit a band-gap, allowing an exponential change in the source-drain current from small numbers of charges. Collectively, these phenomena allow for ultrasensitive electronic biomolecular detection in millimeter scale structures.

  2. There has been an increasing need of technologies to manufacturing chemical and biological sensors for various applications ranging from environmental monitoring to human health monitoring. Currently, manufacturing of most chemical and biological sensors relies on a variety of standard microfabrication techniques, such as physical vapor deposition and photolithography, and materials such as metals and semiconductors. Though functional, they are hampered by high cost materials, rigid substrates, and limited surface area. Paper based sensors offer an intriguing alternative that is low cost, mechanically flexible, has the inherent ability to filter and separate analytes, and offers a high surface area, permeable framework advantageous to liquid and vapor sensing. However, a major drawback is that standard microfabrication techniques cannot be used in paper sensor fabrication. To fabricate sensors on paper, low temperature additive techniques must be used, which will require new manufacturing processes and advanced functional materials. In this work, we focus on using aerosol jet printing as a highresolution additive process for the deposition of ink materials to be used in paper-based sensors. This technique can use a wide variety of materials with different viscosities, including materials with high porosity and particles inherent to paper. One area of our efforts involves creatingmore »interdigitated microelectrodes on paper in a one-step process using commercially available silver nanoparticle and carbon black based conductive inks. Another area involves use of specialized filter papers as substrates, such as multi-layered fibrous membrane paper consisting of a poly(acrylonitrile) nanofibrous layer and a nonwoven poly(ethylene terephthalate) layer. The poly(acrylonitrile) nanofibrous layer are dense and smooth enough to allow for high resolution aerosol jet printing. With additively fabricated electrodes on the paper, molecularly-functionalized metal nanoparticles are deposited by molecularly-mediated assembling, drop casting, and printing (sensing and electrode materials), allowing full functionalization of the paper, and producing sensor devices with high surface area. These sensors, depending on the electrode configuration, are used for detection of chemical and biological species in vapor phase, such as water vapor and volatile organic compounds, making them applicable to human performance monitoring. These paper based sensors are shown to display an enhancement in sensitivity, as compared to control devices fabricated on non-porous polyimide substrates. These results have demonstrated the feasibility of paper-based printed devices towards manufacturing of a fully wearable, highly-sensitive, and wireless human performance monitor coupled to flexible electronics with the capability to communicate wirelessly to a smartphone or other electronics for data logging and analysis.« less
  3. Abstract

    Temperature is one of the most fundamental physical properties to characterize various physical, chemical, and biological processes. Even a slight change in temperature could have an impact on the status or dynamics of a system. Thus, there is a great need for high-precision and large-dynamic-range temperature measurements. Conventional temperature sensors encounter difficulties in high-precision thermal sensing on the submicron scale. Recently, optical whispering-gallery mode (WGM) sensors have shown promise for many sensing applications, such as thermal sensing, magnetic detection, and biosensing. However, despite their superior sensitivity, the conventional sensing method for WGM resonators relies on tracking the changes in a single mode, which limits the dynamic range constrained by the laser source that has to be fine-tuned in a timely manner to follow the selected mode during the measurement. Moreover, we cannot derive the actual temperature from the spectrum directly but rather derive a relative temperature change. Here, we demonstrate an optical WGM barcode technique involving simultaneous monitoring of the patterns of multiple modes that can provide a direct temperature readout from the spectrum. The measurement relies on the patterns of multiple modes in the WGM spectrum instead of the changes of a particular mode. It can provide usmore »with more information than the single-mode spectrum, such as the precise measurement of actual temperatures. Leveraging the high sensitivity of WGMs and eliminating the need to monitor particular modes, this work lays the foundation for developing a high-performance temperature sensor with not only superior sensitivity but also a broad dynamic range.

    « less
  4. Abstract

    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. Wemore »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.

    « less
  5. Abstract

    Fiber-based electronics enabling lightweight and mechanically flexible/stretchable functions are desirable for numerous e-textile/e-skin optoelectronic applications. These wearable devices require low-cost manufacturing, high reliability, multifunctionality and long-term stability. Here, we report the preparation of representative classes of 3D-inorganic nanofiber network (FN) films by a blow-spinning technique, including semiconducting indium-gallium-zinc oxide (IGZO) and copper oxide, as well as conducting indium-tin oxide and copper metal. Specifically, thin-film transistors based on IGZO FN exhibit negligible performance degradation after one thousand bending cycles and exceptional room-temperature gas sensing performance. Owing to their great stretchability, these metal oxide FNs can be laminated/embedded on/into elastomers, yielding multifunctional single-sensing resistors as well as fully monolithically integrated e-skin devices. These can detect and differentiate multiple stimuli including analytes, light, strain, pressure, temperature, humidity, body movement, and respiratory functions. All of these FN-based devices exhibit excellent sensitivity, response time, and detection limits, making them promising candidates for versatile wearable electronics.