Despite several decades of development, microfluidics lacks a sealing material that can be readily fabricated, leak-tight under high liquid water pressure, stable over a long time, and vacuum compatible. In this paper, we report the performances of a micro-scale processable sealing material for nanofluidic/microfluidics chip fabrication, which enables us to achieve all these requirements. We observed that micrometric walls made of SU-8 photoresist, whose thickness can be as low as 35 $μ$m, exhibit water pressure leak-tightness from 1.5 bar up to 5.5 bar, no water porosity even after 2 months of aging, and are able to sustain under $10^{-5}$ mbar vacuum. This sealing material is therefore reliable and versatile for building microchips, part of which must be isolated from liquid water under pressure or vacuum. Moreover, the fabrication process we propose does not require the use of aggressive chemicals or high-temperature or high-energy plasma treatment. It thus opens a new perspective to seal microchips where delicate surfaces such as nanomaterials are present.

Due to their atomically excellent structure and sp2-hybridization, carbon nanotubes (CNTs) have exceptional mechanical, thermal, and electrical properties. Single-walled CNTs (swCNTs) have recently gained interest as an intriguing host for the nanoscale confinement of fluids, with a variety of unexpected phenomena such as spontaneous filling, frictionless mass transport, unusual phase diagram etc[1]. The majority of these phenomena are still under debate and require experimental confirmation. However, it is challenging in this field to find experimental methods sensitive enough to carry out measurements at the level of individual nanotubes. The electronic properties of swCNTs are demonstrated to be sensitive to their diameter, defects, doping, adsorbates, and environment via swCNT field effect transistors (swCNT-FETs)[2], [3].In this contribution, we show that individual carbon nanotube field effect transistors (CNTFET) are the perfect tool for achieving this goal, enabling for the first time to accurate identification of water confined inside the nanotube. By investigating the electrical performances of several unopened and opened CNTFETs submitted to different atmosphere and temperature treatments, such as dry air, humidity, secondary vacuum, and current annealing, we demonstrate that it is possible to distinguish between water being outside and inside of the nanotube, just outside, or the nanotube free from water. Hence, we found that secondary vacuum and current annealing both shift the threshold gate voltage of opened swCNTs towards more negative values, however, the secondary vacuum had no effect on closed swCNTs compared to current annealing. In conclusion, the current annealing process is essential to distinguish water adsorbed outside from water confined inside swCNT. We demonstrate that this behavior is uniform across all devices’ metallicities, assuming that the nanotube’s surface has been pre-cleaned using current annealing. We will also discuss the mechanism behind the coupling of electronic transport and the presence of water.Our findings open up the possibility of using CNTFET to address long-standing issues in the nanofluidic community regarding the behavior of water confinement at the nanoscale, and also to use them for reliable, sensitive, and selective chemical and biological sensors.Reference:[1] T. A. Pascal, W. A. Goddard, and Y. Jung, “Entropy and the driving force for the filling of carbon nanotubes with water,” Proc. Natl. Acad. Sci., vol. 108, no. 29, pp. 11794–11798, 2011, doi: 10.1073/pnas.1108073108.[2] D. Cao et al., “Electronic sensitivity of carbon nanotubes to internal water wetting,” ACS Nano, vol. 5, no. 4, pp. 3113–3119, 2011, DOI: 10.1021/nn200251z.[3] I. Heller, A. M. Janssens, J. Männik, E. D. Minot, S. G. Lemay, and C. Dekker, “Identifying the mechanism of biosensing with carbon nanotube transistors,” Nano Lett., vol. 8, no. 2, pp. 591–595, 2008, DOI: 10.1021/nl072996i.

Carbon nanotubes (CNTs) possess extraordinary mechanical, thermal, and electrical properties due to their atomically perfect structure and sp2-hybridization. Recently, Single-wall CNTs (SWCNTs) have become an interesting host for the nanoscale confinement of fluids, with a wealth of surprising phenomena appearing: spontaneous filling, frictionless mass transport, unusual phase diagram, etc[1]. Most of these phenomena are still under debate and call for experimental confirmation. But the field is struggling with finding experimental approaches sensitive enough to carry out measurements at the level of individual nanotubes. SWCNT field effect transistors (SWCNT-FETs) showed that the electronic properties of SWCNTs are sensitive to their diameter, defects, doping, adsorbates, and environment [2], [3].In this contribution, we demonstrate that individual carbon nanotube field effect transistors (CNTFET) are excellent tools for this aim, for the first time allowing to precisely identify water confined inside the nanotube. By studying the electrical performances of several unopened and opened CNTFETs submitted to various atmosphere and temperature treatments, i.e. dry air, humidity, secondary vacuum, and current annealing, we show that it is possible to distinguish water being outside and inside the nanotube, just outside, or the nanotube free from water. We thus observed that for opened SWCNT both secondary vacuum and current annealing move threshold gate voltage towards more negative values, while for closed SWCNT secondary vacuum had no effect compared to current annealing. To sum up, the current annealing treatment is essential to distinguish water adsorbed outside from water confined inside. We show that this behavior is universal, as all devices' metallicities behave similarly, provided that the surface of the nanotube is pre-cleaned by current annealing. We will also discuss the mechanisms behind the coupling of electronic transport and the presence of water.Our results open up the possibility to use CNTFET for instance reliable, selective, and sensitive chemical and biological sensors, and also, to resolve the long-standing questions in the nanofluidic community about the behavior of water under nanoscale confinement.Reference:[1] T. A. Pascal, W. A. Goddard, and Y. Jung, “Entropy and the driving force for the filling of carbon nanotubes with water,” Proc. Natl. Acad. Sci., vol. 108, no. 29, pp. 11794–11798, 2011, doi: 10.1073/pnas.1108073108.[2] D. Cao et al., “Electronic sensitivity of carbon nanotubes to internal water wetting,” ACS Nano, vol. 5, no. 4, pp. 3113–3119, 2011, DOI: 10.1021/nn200251z.[3] I. Heller, A. M. Janssens, J. Männik, E. D. Minot, S. G. Lemay, and C. Dekker, “Identifying the mechanism of biosensing with carbon nanotube transistors,” Nano Lett., vol. 8, no. 2, pp. 591–595, 2008, DOI: 10.1021/nl072996i.