RESUMEN
Electrical biosensors, including transistor-based devices (i.e., BioFETs), have the potential to offer versatile biomarker detection in a simple, low-cost, scalable, and point-of-care manner. Semiconducting carbon nanotubes (CNTs) are among the most explored nanomaterial candidates for BioFETs due to their high electrical sensitivity and compatibility with diverse fabrication approaches. However, when operating in solutions at biologically relevant ionic strengths, CNT-based BioFETs suffer from debilitating levels of signal drift and charge screening, which are often unaccounted for or sidestepped (but not addressed) by testing in diluted solutions. In this work, we present an ultrasensitive CNT-based BioFET called the D4-TFT, an immunoassay with an electrical readout, which overcomes charge screening and drift-related limitations of BioFETs. In high ionic strength solution (1X PBS), the D4-TFT repeatedly and stably detects subfemtomolar biomarker concentrations in a point-of-care form factor by increasing the sensing distance in solution (Debye length) and mitigating signal drift effects. Debye length screening and biofouling effects are overcome using a poly(ethylene glycol)-like polymer brush interface (POEGMA) above the device into which antibodies are printed. Simultaneous testing of a control device having no antibodies printed over the CNT channel confirms successful detection of the target biomarker via an on-current shift caused by antibody sandwich formation. Drift in the target signal is mitigated by a combination of: (1) maximizing sensitivity by appropriate passivation alongside the polymer brush coating; (2) using a stable electrical testing configuration; and (3) enforcing a rigorous testing methodology that relies on infrequent DC sweeps rather than static or AC measurements. These improvements are realized in a relatively simple device using printed CNTs and antibodies for a low-cost, versatile platform for the ongoing pursuit of point-of-care BioFETs.
RESUMEN
The addition of surface acoustic wave (SAW) technologies to microfluidics has greatly advanced lab-on-a-chip applications due to their unique and powerful attributes, including high-precision manipulation, versatility, integrability, biocompatibility, contactless nature, and rapid actuation. However, the development of SAW microfluidic devices is limited by complex and time-consuming micro/nanofabrication techniques and access to cleanroom facilities for multistep photolithography and vacuum-based processing. To simplify the fabrication of SAW microfluidic devices with customizable dimensions and functions, we utilized the additive manufacturing technique of aerosol jet printing. We successfully fabricated customized SAW microfluidic devices of varying materials, including silver nanowires, graphene, and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). To characterize and compare the acoustic actuation performance of these aerosol jet printed SAW microfluidic devices with their cleanroom-fabricated counterparts, the wave displacements and resonant frequencies of the different fabricated devices were directly measured through scanning laser Doppler vibrometry. Finally, to exhibit the capability of the aerosol jet printed devices for lab-on-a-chip applications, we successfully conducted acoustic streaming and particle concentration experiments. Overall, we demonstrated a novel solution-based, direct-write, single-step, cleanroom-free additive manufacturing technique to rapidly develop SAW microfluidic devices that shows viability for applications in the fields of biology, chemistry, engineering, and medicine.
RESUMEN
Three-dimensional (3D) graphene microstructures have the potential to boost performance in high-capacity batteries and ultrasensitive sensors. Numerous techniques have been developed to create such structures; however, the methods typically rely on structural supports, and/or lengthy post-print processing, increasing cost and complexity. Additive manufacturing techniques, such as printing, show promise in overcoming these challenges. This study employs aerosol jet printing for creating 3D graphene microstructures using water as the only solvent and without any post-print processing required. The graphene pillars exhibit conductivity immediately after printing, requiring no high-temperature annealing. Furthermore, these pillars are successfully printed in freestanding configurations at angles below 45° relative to the substrate, showcasing their adaptability for tailored applications. When graphene pillars are added to humidity sensors, the additional surface area does not yield a corresponding increase in sensor performance. However, graphene trusses, which add a parallel conduction path to the sensing surface, are found to improve sensitivity nearly 2×, highlighting the advantages of a topologically suspended circuit construction when adding 3D microstructures to sensing electrodes. Overall, incorporating 3D graphene microstructures to sensor electrodes can provide added sensitivity, and aerosol jet printing is a viable path to realizing these conductive microstructures without any post-print processing.
RESUMEN
Printed carbon nanotube thin-film transistors (CNT-TFTs) are candidates for flexible electronics with printability on a wide range of substrates. Among the layers comprising a CNT-TFT, the gate dielectric has proven most difficult to additively print owing to challenges in film uniformity, thickness, and post-processing requirements. Printed ionic dielectrics show promise for addressing these issues and yielding devices that operate at low voltages thanks to their high-capacitance electric double layers. However, the printing of ionic dielectrics in their various compositions is not well understood, nor is the impact of certain stresses on these materials. In this work, we studied three compositionally distinct ionic dielectrics in fully printed CNT-TFTs: the polar-fluorinated polymer elastomer PVDF-HFP; an ion gel consisting of triblock polymer PS-PMMA-PS and ionic liquid EMIM-TFSI; and crystalline nanocellulose (CNC) with a salt concentration of 0.05%. Although ion gel has been thoroughly studied, e-PVDF-HFP and CNC printing are relatively new and this study provides insights into their ink formulation, print processing, and performance as gate dielectrics. Using a consistent aerosol jet printing approach, each ionic dielectric was printed into similar CNT-TFTs, allowing for direct comparison through extensive characterization, including mechanical and electrical stress tests. The ionic dielectrics were found to have distinct operational dependencies based on their compositional and ionic attributes. Overall, the results reveal a number of trade-offs that must be managed when selecting a printable ionic dielectric, with CNC showing the strongest performance for low-voltage operation but the ion gel and elastomer exhibiting better stability under bias and mechanical stresses.
RESUMEN
Interest in point-of-care diagnostics has led to increasing demand for the development of nanomaterial-based electronic biosensors such as biosensor field-effect transistors (BioFETs) due to their inherent simplicity, sensitivity, and scalability. The utility of BioFETs, which use electrical transduction to detect biological signals, is directly dependent upon their electrical stability in detection-relevant environments. BioFET device structures vary substantially, especially in electrode passivation modalities. Improper passivation of electronic components in ionic solutions can lead to excessive leakage currents and signal drift, thus presenting a hinderance to signal detectability. Here, we harness the sensitivity of nanomaterials to study the effects of various passivation strategies on the performance and stability of a transistor-based biosensing platform based on aerosol-jet-printed carbon nanotube thin-film transistors. Specifically, non-passivated devices were compared to devices passivated with photoresist (SU-8), dielectric (HfO2), or photoresist + dielectric (SU-8 followed by HfO2) and were evaluated primarily by initial performance metrics, large-scale device yield, and stability throughout long-duration cycling in phosphate buffered saline. We find that all three passivation conditions result in improved device performance compared to non-passivated devices, with the photoresist + dielectric strategy providing the lowest average leakage current in solution (~2 nA). Notably, the photoresist + dielectric strategy also results in the greatest yield of BioFET devices meeting our selected performance criteria on a wafer scale (~90%), the highest long-term stability in solution (<0.01% change in on-current), and the best average on/off-current ratio (~104), hysteresis (~32 mV), and subthreshold swing (~192 mV/decade). This passivation schema has the potential to pave the path toward a truly high-yield, stable, and robust electrical biosensing platform.
RESUMEN
Ion gel-based dielectrics have long been considered for enabling low-voltage operation in printed thin-film transistors (TFTs), but their compatibility with in-place printing (a streamlined, direct-write printing approach where devices never leave the printer mid- or post-process) remains unexplored. Here, we demonstrate a simple and rapid 4-step in-place printing procedure for producing low-voltage electrolyte-gated carbon nanotube (CNT) thin-film transistors at low temperature (80 °C). This process consists of the use of polymer-wrapped CNT inks for printed channels, silver nanowire inks for printed electrodes, and imidazolium-based ion gel inks for printed gate dielectrics. We find that the efficacy of rinsing CNT films and printing an ion gel in-place is optimized using an elevated platen temperature (as opposed to external rinsing or post-process annealing), where resultant devices exhibited on/off-current ratios exceeding 103, mobilities exceeding 10 cm2V-1s-1, and gate hysteresis of only 0.1 V. Additionally, devices were tested under mechanical strain and long-term bias, showing exceptional flexibility and electrochemical stability over the course of 14-hour bias tests. The findings presented here widen the potential scope of print-in-place (PIP) devices and reveal new avenues of investigation for the improvement of bias stress stability in electrolyte-gated transistors.
RESUMEN
Two-dimensional (2D) materials offer exciting possibilities for numerous applications, including next-generation sensors and field-effect transistors (FETs). With their atomically thin form factor, it is evident that molecular activity at the interfaces of 2D materials can shape their electronic properties. Although much attention has focused on engineering the contact and dielectric interfaces in 2D material-based transistors to boost their drive current, less is understood about how to tune these interfaces to improve the long-term stability of devices. In this work, we evaluated molybdenum disulfide (MoS2) transistors under continuous electrical stress for periods lasting up to several days. During stress in ambient air, we observed temporary threshold voltage shifts that increased at higher gate voltages or longer stress durations, correlating to changes in interface trap states (ΔNit) of up to 1012 cm-2. By modifying the device to include either SU-8 or Al2O3 as an additional dielectric capping layer on top of the MoS2 channel, we were able to effectively reduce or even eliminate this unstable behavior. However, we found this encapsulating material must be selected carefully, as certain choices actually amplified instability or compromised device yield, as was the case for Al2O3, which reduced yield by 20% versus all other capping layers. Further refining these strategies to preserve stability in 2D devices will be crucial for their continued integration into future technologies.
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Sensors based on two-dimensional (2D) field-effect transistors (FETs) are extremely sensitive and can detect charged analytes with attomolar limits of detection (LOD). Despite some impressive LODs, the operating mechanisms and factors that determine the signal-to-noise ratio in 2D FET-based sensors remain poorly understood. These uncertainties, coupled with an expansive design space for sensor layout and analyte positioning, result in a field with many reported highlights but limited collective progress. Here, we provide insight into sensing mechanisms of 2D molybdenum disulfide (MoS2) FETs by realizing precise control over the position and charge of an analyte using a customized atomic force microscope (AFM), with the AFM tip acting as an analyte. The sensitivity of the MoS2 FET channel is revealed to be nonuniform, manifesting sensitive hotspots with locations that are stable over time. When the charge of the analyte is varied, an asymmetry is observed in the device drain-current response, with analytes acting to turn the device off leading to a 2.5× increase in the signal-to-noise ratio (SNR). We developed a numerical model, applicable to all FET-based charge-detection sensors, that confirms our experimental observation and suggests an underlying mechanism. Further, extensive characterization of a set of different MoS2 FETs under various analyte conditions, coupled with the numerical model, led to the identification of three distinct SNRs that peak with dependence on the layout and operating conditions used for a sensor. These findings reveal the important role of analyte position and coverage in determining the optimal operating bias conditions for maximal sensitivity in 2D FET-based sensors, which provides key insights for future sensor design and control.
RESUMEN
Thousands of reports have demonstrated the exceptional performance of sensors based on carbon nanotube (CNT) transistors, with promises of transformative impact. Yet, the effect of long-term bias stress on individual CNTs, critical for most sensing applications, has remained uncertain. Here, we report bias ranges under which CNT transistors can operate continuously for months or more without degradation. Using a custom characterization system, the impacts of defect formation and charge traps on the stability of CNT-based sensors under extended bias are determined. In addition to breakdown, which is well-known, we identify three additional operational modes: full stability, slow decay, and fast decay. We identify a current drift behavior that reduces dynamic range by over four orders of magnitude but is avoidable with appropriate sensing modalities. Identification of these stable operation modes and limits for nanotube-based sensors addresses concerns surrounding their development for a myriad of sensing applications.