Band gap opening of metallic single-walled carbon nanotubes via noncovalent symmetry breaking.

Covalent bonding interactions determine the energy-momentum (E-k) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the E-k dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to-semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV.

Addressing Signal Drift and Screening for Detection of Biomarkers with Carbon Nanotube Transistors.

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.

Aerosol Jet Printing Conductive 3D Microstructures from Graphene Without Post-Processing.

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.

Aerosol-Jet-Printable Covalent Organic Framework Colloidal Inks and Temperature-Sensitive Nanocomposite Films.

With molecularly well-defined and tailorable 2D structures, covalent organic frameworks (COFs) have emerged as leading material candidates for chemical sensing, storage, separation, and catalysis. In these contexts, the ability to directly and deterministically print COFs into arbitrary geometries will enable rapid optimization and deployment. However, previous attempts to print COFs have been restricted by low spatial resolution and/or post-deposition polymerization that limits the range of compatible COFs. Here, these limitations are overcome with a pre-synthesized, solution-processable colloidal ink that enables aerosol jet printing of COFs with micron-scale resolution. The ink formulation utilizes the low-volatility solvent benzonitrile, which is critical to obtaining homogeneous printed COF film morphologies. This ink formulation is also compatible with other colloidal nanomaterials, thus facilitating the integration of COFs into printable nanocomposite films. As a proof-of-concept, boronate-ester COFs are integrated with carbon nanotubes (CNTs) to form printable COF-CNT nanocomposite films, in which the CNTs enhance charge transport and temperature sensing performance, ultimately resulting in high-sensitivity temperature sensors that show electrical conductivity variation by 4 orders of magnitude between room temperature and 300 °C. Overall, this work establishes a flexible platform for COF additive manufacturing that will accelerate the incorporation of COFs into technologically significant applications.

Centrifuge-Free Separation of Solution-Exfoliated 2D Nanosheets via Cross-Flow Filtration.

Solution-processed graphene is a promising material for numerous high-volume applications including structural composites, batteries, sensors, and printed electronics. However, the polydisperse nature of graphene dispersions following liquid-phase exfoliation poses major manufacturing challenges, as incompletely exfoliated graphite flakes must be removed to achieve optimal properties and downstream performance. Incumbent separation schemes rely on centrifugation, which is highly energy-intensive and limits scalable manufacturing. Here, cross-flow filtration (CFF) is introduced as a centrifuge-free processing method that improves the throughput of graphene separation by two orders of magnitude. By tuning membrane pore sizes between microfiltration and ultrafiltration length scales, CFF can also be used for efficient recovery of solvents and stabilizing polymers. In this manner, life cycle assessment and techno-economic analysis reveal that CFF reduces greenhouse gas emissions, fossil energy usage, water consumption, and specific production costs of graphene manufacturing by 57%, 56%, 63%, and 72%, respectively. To confirm that CFF produces electronic-grade graphene, CFF-processed graphene nanosheets are formulated into printable inks, leading to state-of-the-art thin-film conductivities exceeding 104 S m-1 . This CFF methodology can likely be generalized to other van der Waals layered solids, thus enabling sustainable manufacturing of the diverse set of applications currently being pursued for 2D materials.

Aerosol Jet Printing of SU-8 as a Passivation Layer Against Ionic Solutions.

To ensure stability for low-cost electronics used in direct contact with ionic solutions (such as electronic biosensors), electrodes are frequently passivated to protect against current leakage, which leads to corrosion. The epoxy-based polymer SU-8 yields favorable properties for passivation against ionic solutions. However, it is nearly universally patterned via cleanroom techniques, which increases device cost and fabrication complexity. Printing electronic components has been shown to be a viable approach for decreasing fabrication cost. Previous reports on SU-8 printing focus on the resultant printed structure, with little emphasis on its subsequent use as a passivation layer. Here, we demonstrate the printing of SU-8 with an aerosol jet printer using ultrasonic aerosolization. We show that SU-8 can be printed without reformulation, and that printed SU-8 is a viable passivation layer over conductive silver lines, when tested in ionic solutions. Extending the printed SU-8 film beyond the underlying conductive electrodes by 100 µm produced a six order of magnitude decrease in leakage current and resulted high stability over 20 voltage sweeps. Finally, we optimized post-printing cure time to 15 minutes at 160°C, which further minimized leakage current. While the development of low-cost, electronic biosensing devices has increasingly moved towards printing methods, the lack of a printed passivation strategy has hindered this transition. The advancements made in this study towards an aerosol jet printable SU-8 passivation layer provide useful progress towards a fully printed, stable electronic biosensing device.

Passivation Strategies for Enhancing Solution-Gated Carbon Nanotube Field-Effect Transistor Biosensing Performance and Stability in Ionic Solutions.

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.

In-Place Printing of Flexible Electrolyte-Gated Carbon Nanotube Transistors with Enhanced Stability.

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.

Printable and recyclable carbon electronics using crystalline nanocellulose dielectrics.

Electronic waste can lead to the accumulation of environmentally and biologically toxic materials and is a growing global concern. Developments in transient electronics-in which devices are designed to disintegrate after use-have focused on increasing the biocompatibility, whereas efforts to develop methods to recapture and reuse materials have focused on conducting materials, while neglecting other electronic materials. Here, we report all-carbon thin-film transistors made using crystalline nanocellulose as a dielectric, carbon nanotubes as a semiconductor, graphene as a conductor and paper as a substrate. A crystalline nanocellulose ink is developed that is compatible with nanotube and graphene inks and can be written onto a paper substrate using room-temperature aerosol jet printing. The addition of mobile sodium ions to the dielectric improves the thin-film transistor on-current (87 µA mm-1) and subthreshold swing (132 mV dec-1), and leads to a faster voltage sweep rate (by around 20 times) than without ions. The devices also exhibit stable performance over six months in ambient conditions and can be controllably decomposed, with the graphene and carbon nanotube inks recaptured for recycling (>95% recapture efficiency) and reprinting of new transistors. We demonstrate the utility of the thin-film transistors by creating a fully printed, paper-based biosensor for lactate sensing.

Fully printed prothrombin time sensor for point-of-care testing.

With an increasing number of patients relying on blood thinners to treat medical conditions, there is a rising need for rapid, low-cost, portable testing of blood coagulation time or prothrombin time (PT). Current methods for measuring PT require regular visits to outpatient clinics, which is cumbersome and time-consuming, decreasing patient quality of life. In this work, we developed a handheld point-of-care test (POCT) to measure PT using electrical transduction. Low-cost PT sensors were fully printed using an aerosol jet printer and conductive inks of Ag nanoparticles, Ag nanowires, and carbon nanotubes. Using benchtop control electronics to test this impedance-based biosensor, it was found that the capacitive nature of blood obscures the clotting response at frequencies below 10 kHz, leading to an optimized operating frequency of 15 kHz. When printed on polyimide, the PT sensor exhibited no variation in the measured clotting time, even when flexed to a 35 mm bend radius. In addition, consistent PT measurements for both chicken and human blood illustrate the versatility of these printed biosensors under disparate operating conditions, where chicken blood clots within 30 min and anticoagulated human blood clots within 20-100 s. Finally, a low-cost, handheld POCT was developed to measure PT for human blood, yielding 70% lower noise compared to measurement with a commercial potentiostat. This POCT with printed PT sensors has the potential to dramatically improve the quality of life for patients on blood thinners and, in the long term, could be incorporated into a fully flexible and wearable sensing platform.

Uniform and Stable Aerosol Jet Printing of Carbon Nanotube Thin-Film Transistors by Ink Temperature Control.

Semiconducting carbon nanotube (CNT) networks exhibit electrical, mechanical, and chemical properties attractive for thin-film applications, and printing allows for scalable and economically favorable fabrication of CNT thin-film transistors (TFTs). However, device-to-device variation of printed CNT-TFTs remains a concern, which largely stems from variations in printed CNT thin-film morphology and resulting properties. In this work, we overcome the challenges associated with printing uniformity and demonstrate an aerosol jet printing process that yields devices exhibiting a hole mobility of µh = 12.5 cm2/V·s with a relative standard deviation as small as 4% (from over 38 devices). The enabling factors of such high uniformity include control of the CNT ink bath temperature during printing, ink formulation with nonvolatile and viscosifying additives, and a thermal treatment for polymer removal. It is discovered that a low CNT ink temperature benefits aerosol jet printing uniformity and stability in both short-term (∼1 min) and long-term (∼1 h) printing settings. These findings shed light on the effect of a commonly overlooked dimension of CNT aerosol jet printing and provide a practical strategy for large-scale, high-consistency realization of CNT-TFTs.

Aerosol jet printing of biological inks by ultrasonic delivery.

Printing is a promising method to reduce the cost of fabricating biomedical devices. While there have been significant advancements in direct-write printing techniques, non-contact printing of biological reagents has been almost exclusively limited to inkjet printing. Motivated by this lacuna, this work investigated aerosol jet printing (AJP) of biological reagents onto a nonfouling polymer brush to fabricate in vitro diagnostic (IVD) assays. The ultrasonication ink delivery process, which had previously been reported to damage DNA molecules, caused no degradation of printed proteins, allowing printing of a streptavidin-biotin binding assay with sub-nanogram ml-1 analytical sensitivity. Furthermore, a carcinoembryogenic antigen IVD was printed and found to have sensitivities in the clinically relevant range (limit of detection of approximately 0.5 ng ml-1 and a dynamic range of approximately three orders of magnitude). Finally, the multi-material printing capabilities of the aerosol jet printer were demonstrated by printing silver nanowires and streptavidin as interconnected patterns in the same print job without removal of the substrate from the printer, which will facilitate the fabrication of mixed-material devices. As cost, versatility, and ink usage become more prominent factors in the development of IVDs, this work has shown that AJP should become a more widely considered technique for fabrication.

Flexible, Print-in-Place 1D-2D Thin-Film Transistors Using Aerosol Jet Printing.

Semiconducting carbon nanotubes (CNTs) printed into thin films offer high electrical performance, significant mechanical stability, and compatibility with low-temperature processing. Yet, the implementation of low-temperature printed devices, such as CNT thin-film transistors (CNT-TFTs), has been hindered by relatively high process temperature requirements imposed by other device layers-dielectrics and contacts. In this work, we overcome temperature constraints and demonstrate 1D-2D thin-film transistors (1D-2D TFTs) in a low-temperature (maximum exposure ≤80 °C) full print-in-place process (i.e., no substrate removal from printer throughout the entire process) using an aerosol jet printer. Semiconducting 1D CNT channels are used with a 2D hexagonal boron nitride (h-BN) gate dielectric and traces of silver nanowires as the conductive electrodes, all deposited using the same printer. The aerosol jet-printed 2D h-BN films were realized via proper ink formulation, such as utilizing the binder hydroxypropyl methylcellulose, which suppresses redispersion between adjacent printed layers. In addition to an ON/OFF current ratio up to 3.5 × 105, channel mobility up to 10.7 cm2·V-1·s-1, and low gate hysteresis, 1D-2D TFTs exhibit extraordinary mechanical stability under bending due to the nanoscale network structure of each layer, with minimal changes in performance after 1000 bending test cycles at 2.1% strain. It is also confirmed that none of the device layers require high-temperature treatment to realize optimal performance. These findings provide an attractive approach toward a cost-effective, direct-write realization of electronics.

Silver nanowire inks for direct-write electronic tattoo applications.

Room-temperature printing of conductive traces has the potential to facilitate the direct writing of electronic tattoos and other medical devices onto biological tissue, such as human skin. However, in order to achieve sufficient electrical performance, the vast majority of conductive inks require biologically harmful post-processing techniques. In addition, most printed conductive traces will degrade with bending stresses that occur from everyday movement. In this work, water-based inks consisting of high aspect ratio silver nanowires are shown to enable the printing of conductive traces at low temperatures and without harmful post-processing. Moreover, the traces produced from these inks retain high electrical performance, even while undergoing up to 50% bending strain and cyclic bending strain over a thousand bending cycles. This ink has a rapid dry time of less than 2 minutes, which is imperative for applications requiring the direct writing of electronics on sensitive surfaces. Demonstrations of conductive traces printed onto soft, nonplanar materials, including an apple and a human finger, highlight the utility of these new silver nanowire inks. These mechanically robust films are ideally suited for printing directly on biological substrates and may find potential applications in the direct-write printing of electronic tattoos and other biomedical devices.