Abstract Agricultural intensification has increased the use of chemical fertilizers, promoting plant growth and crop yield. Excessive use of nitrogen fertilizers leads to nutrient loss and low nitrogen use efficiency. Management of nitrogen fertilizer input requires close to real‐time information about the soil nitrate concentration. While there is extensive work developing nitrate ion sensing solutions for liquid media, few allow for in‐soil measurements. This study introduces inkjet‐printed potentiometric sensors, containing 2 electrodes, the reference electrode (RE) and the nitrate‐selective film‐encapsulated working electrode (WE). The interaction between the nitrate‐sensitive membrane and soil nitrate ions causes a change in potential across the RE and WE. Additionally, a hydrophilic Polyvinylidene Fluoride (PVDF) layer ensures the long‐term functionality of the sensor in wet soil environments by protecting it from charged soil particles while simultaneously allowing water to flow from the soil toward the sensor electrodes. The sensors are tested in sand and silt loam soil, demonstrating their versatility across soil types. The potential change can be related to the nitrate concentration in soil, with typical sensitivities of 45–55 mV decade−1. Overall, the use of the PVDF layer allows for direct sensing in moist soil environments, which is critical for developing soil nitrate sensors.
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Ultra-sensitive nitrate-ion detection via transconductance-enhanced graphene ion-sensitive field-effect transistors
Abstract Current potentiometric sensing methods are limited to detecting nitrate at parts-per-billion (sub-micromolar) concentrations, and there are no existing potentiometric chemical sensors with ultralow detection limits below the parts-per-trillion (picomolar) level. To address these challenges, we integrate interdigital graphene ion-sensitive field-effect transistors (ISFETs) with a nitrate ion-sensitive membrane (ISM). The work aims to maximize nitrate ion transport through the nitrate ISM, while achieving high device transconductance by evaluating graphene layer thickness, optimizing channel width-to-length ratio (RWL), and enlarging total sensing area. The captured nitrate ions by the nitrate ISM induce surface potential changes that are transduced into electrical signals by graphene, manifested as the Dirac point shifts. The device exhibits Nernst response behavior under ultralow concentrations, achieving a sensitivity of 28 mV/decade and establishing a record low limit of detection of 0.041 ppt (4.8 × 10−13M). Additionally, the sensor showed a wide linear detection range from 0.1 ppt (1.2 × 10−12M) to 100 ppm (1.2 × 10−3M). Furthermore, successful detection of nitrate in tap and snow water was demonstrated with high accuracy, indicating promising applications to drinking water safety and environmental water quality control.
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- Award ID(s):
- 2011401
- PAR ID:
- 10590042
- Publisher / Repository:
- Microsyst. Nanoeng.
- Date Published:
- Journal Name:
- Microsystems & Nanoengineering
- Volume:
- 10
- Issue:
- 1
- ISSN:
- 2055-7434
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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