Skip to content

Impact of gate electrode on free chlorine sensing performance in solution-gated graphene field-effect transistors

MetadataDetails
Publication Date2024-01-01
JournalRSC Advances
AuthorsMasato Sugawara, Takeshi Watanabe, Yasuaki Einaga, Shinji Koh
InstitutionsKeio University, Aoyama Gakuin University
Citations4
AnalysisFull AI Review Included
  • Core Innovation: The study optimizes solution-gated Graphene Field-Effect Transistors (GFETs) for highly sensitive free chlorine (FC) sensing by focusing on the electrochemical properties of the gate electrode.
  • Sensing Mechanism: FC acts as a p-dopant on the graphene channel, causing a shift in the Dirac Point Voltage (VDP). This shift is governed by the Nernst equation and the voltage distribution across the electric double layers (EDLs).
  • Performance Enhancement: Gate electrodes with low electric double-layer capacitance (CGE) and wide potential windows (Graphene and Boron-Doped Diamond, BDD) significantly amplify the VDP shift, improving sensitivity.
  • Material Comparison: Graphene (1.65 ”F cm-2) and BDD (2.68 ”F cm-2) gates demonstrated superior performance compared to the standard Au gate (27.3 ”F cm-2), especially at low concentrations.
  • Low Concentration Sensitivity: The absence of interfering surface redox species on carbon-based electrodes (Graphene/BDD) allows for accurate sensing in the low concentration range (0.1-0.2 ppm), suitable for tap water.
  • Durability Potential: BDD is highlighted as an ideal gate material due to its chemical stability and resistance to fouling, suggesting potential for durable, long-term continuous monitoring sensors.
ParameterValueUnitContext
Graphene Growth Temperature1000°CCVD process on Cu substrate
CH4 Flow Rate20sccmCVD reaction source gas
H2 Flow Rate2sccmCVD reaction source gas
Drain-Source Voltage (VDS)0.1VFixed voltage for transfer curve measurement
Au Gate EDL Capacitance (CGE)27.3”F cm-2Measured in 0.1 M PBS (pH 7)
Graphene Gate EDL Capacitance (CGE)1.65”F cm-2Measured in 0.1 M PBS (pH 7)
BDD Gate EDL Capacitance (CGE)2.68”F cm-2Measured in 0.1 M PBS (pH 7)
BDD Boron-to-Carbon (B/C) Ratio1%Used for BDD gate electrode deposition
Graphene 2D/G Intensity Ratio2.4N/ACharacteristic of single-layer graphene
Carrier Density Increase (10 ppm FC)34%Measured via Hall effect on graphene channel
FC Detection Limit (Graphene/BDD)0.1-0.2ppmSuitable for drinking water monitoring
FC Detection Limit (Au)0.5ppmLower sensitivity due to surface oxides
Standard Redox Potential (HClO)1.40VAgainst Standard Hydrogen Electrode (SHE)
  1. Graphene Channel Fabrication (CVD): Single-layer graphene was grown on a 35 ”m thick copper (Cu) substrate at 1000 °C using CVD with CH4 (20 sccm) and H2 (2 sccm).
  2. Transfer and Device Assembly: Graphene was transferred onto a quartz substrate using a PMMA-assisted wet etching process (0.5 M iron nitrate). Cr/Au (10 nm/40 nm) source and drain electrodes were evaporated to define the channel (7.5 mm length, 15 mm width).
  3. Gate Electrode Preparation:
    • Graphene Gate: Fabricated via the same CVD/transfer process, with an Au/Cr contact.
    • BDD Gate: Deposited on silicon wafers using Microwave Plasma-Assisted CVD (MPCVD) with methane and trimethyl boron (1% B/C ratio).
    • Au Gate: Fabricated by vacuum evaporation of Cr (10 nm)/Au (100 nm) on SiO2/Si substrates.
  4. Electrochemical Characterization: Cyclic Voltammetry (CV) was used to assess the potential window and stability of the gate electrodes. Electrochemical Impedance Spectroscopy (EIS) was used to quantify the electric double-layer capacitance (CGE).
  5. Sensing Protocol: Transfer curves (IDS vs. VGS) were measured in 0.1 M Phosphate Buffer Solution (PBS, pH 7). Free chlorine concentration was adjusted stepwise by adding standardized sodium hypochlorite (NaClO) solution.
  6. Signal Analysis: Free chlorine concentration was correlated with the shift in the Dirac Point Voltage (VDP) on the transfer curves, demonstrating the doping effect.
  • Drinking Water Safety: Continuous, highly sensitive monitoring of residual free chlorine (0.2-0.5 ppm range) at the point of delivery, crucial for public health and regulatory compliance.
  • Industrial Water Treatment: Real-time control and measurement of disinfection levels in food processing, beverage production, and industrial wastewater streams.
  • Durable Sensor Technology: Utilizing Boron-Doped Diamond (BDD) as the gate electrode material provides a platform for robust, long-lifetime sensors resistant to surface fouling and oxidation, reducing maintenance needs.
  • Advanced Sensor Integration: The GFET platform is suitable for integration with statistical methods like machine learning (ML) and multi-signal integration (e.g., dual-gate configurations) to enhance accuracy and robustness against interfering redox species.
  • Extended-Gate FET (EGFET) Design: The findings advocate for an EGFET structure using BDD, separating the sensitive graphene channel from direct liquid contact to improve long-term durability and practicality in liquid environments.
View Original Abstract

We investigated the role of gate electrodes in solution-gated graphene field-effect transistors for sensing free chlorine. Graphene and boron-doped diamond exhibit suitable electrochemical properties for gate electrodes.

  1. 2022 - Guidelines for Drinking-Water Quality