skip to main content


Title: A simple simulation-derived descriptor for the deposition of polymer-wrapped carbon nanotubes on functionalized substrates
Controlling the deposition of polymer-wrapped single-walled carbon nanotubes (s-CNTs) onto functionalized substrates can enable the fabrication of s-CNT arrays for semiconductor devices. In this work, we utilize classical atomistic molecular dynamics (MD) simulations to show that a simple descriptor of solvent structure near silica substrates functionalized by a wide variety of self-assembled monolayers (SAMs) can predict trends in the deposition of s-CNTs from toluene. Free energy calculations and experiments indicate that those SAMs that lead to maximum disruption of solvent structure promote deposition to the greatest extent. These findings are consistent with deposition being driven by solvent-mediated interactions that arise from SAM-solvent interactions, rather than direct s-CNT-SAM interactions, and will permit the rapid computational exploration of potential substrate designs for controlling s-CNT deposition and alignment.  more » « less
Award ID(s):
1727523 2044997
NSF-PAR ID:
10358101
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Soft Matter
Volume:
18
Issue:
25
ISSN:
1744-683X
Page Range / eLocation ID:
4653 to 4659
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Manufacturing of printed electronics relies on the deposition of conductive liquid inks, typically onto polymeric or paper substrates. Among available conductive fillers for use in electronic inks, carbon nanotubes (CNTs) have high conductivity, low density, processability at low temperatures, and intrinsic mechanical flexibility. However, the electrical conductivity of printed CNT structures has been limited by CNT quality and concentration, and by the need for nonconductive modifiers to make the ink stable and extrudable. This study introduces a polymer‐free, printable aqueous CNT ink, and, via an ambient direct‐write printing process, presents the relationships between printing resolution, ink rheology, and ink‐substrate interactions. A model is constructed to predict printed feature sizes on impermeable substrates based on Wenzel wetting. Printed lines have conductivity up to 10 000 S m−1. The lines are flexible, with <5% change in DC resistance after 1000 bending cycles, and <3% change in DC resistance with a bending radius down to 1 mm. Demonstrations focus on i) conformality, via printing CNTs onto stickers that can be applied to curved surfaces, ii) interactivity using a CNT‐based button printed onto folded paper structure, and iii) capacitive sensing of liquid wicking into the substrate itself. Facile integration of surface mount components on printed circuits is enabled by the intrinsic adhesion of the wet ink.

     
    more » « less
  2. Modern-day chip manufacturing requires precision in placing chip materials on complex and patterned structures. Area-selective atomic layer deposition (AS-ALD) is a self-aligned manufacturing technique with high precision and control, which offers cost effectiveness compared to the traditional patterning techniques. Self-assembled monolayers (SAMs) have been explored as an avenue for realizing AS-ALD, wherein surface-active sites are modified in a specific pattern via SAMs that are inert to metal deposition, enabling ALD nucleation on the substrate selectively. However, key limitations have limited the potential of AS-ALD as a patterning method. The choice of molecules for ALD blocking SAMs is sparse; furthermore, deficiency in the proper understanding of the SAM chemistry and its changes upon metal layer deposition further adds to the challenges. In this work, we have addressed the above challenges by using nanoscale infrared spectroscopy to investigate the potential of stearic acid (SA) as an ALD inhibiting SAM. We show that SA monolayers on Co and Cu substrates can inhibit ZnO ALD growth on par with other commonly used SAMs, which demonstrates its viability towards AS-ALD. We complement these measurements with AFM-IR, which is a surface-sensitive spatially resolved technique, to obtain spectral insights into the ALD-treated SAMs. The significant insight obtained from AFM-IR is that SA SAMs do not desorb or degrade with ALD, but rather undergo a change in substrate coordination modes, which can affect ALD growth on substrates.

     
    more » « less
  3. Chemical self-assembly has garnered tremendous interest as a tool for generating nanometer-scale structures and devices. Organosilane self-assembled monolayers (SAMs) are of particular interest due to their ability to assemble on a wide range of substrates with varied chemical functionalities. Nanoshaving, an atomic force lithographic technique, has been demonstrated as a method to generate nanopatterns of organosilane SAMs. However, this method requires extremely high force setpoints, which rapidly dulls atomic force microscopy tips and degrades the resolution of the resulting nanopattern. In this work, we utilize Cu-ligated mercaptohexadecanoic acid (MHDA) multilayers to circumvent this limitation. Initially, a 10-undecenyltrichlorosilane (UTS) SAM is assembled onto a Si substrate, and the terminal olefin groups of the UTS SAM are oxidized to carboxyl groups. Subsequently, a Cu-ligated MHDA multilayer is assembled via the sequential deposition of Cu2+ ions and MHDA molecules. The interface between the oxidized UTS SAM and Cu-ligated MHDA multilayer serves as a natural low force breakpoint for nanoshaving. We demonstrate that the resulting nanopatterns can function as a chemical resist to fabricate metal nanostructures. 
    more » « less
  4. null (Ed.)
    Selective deposition of semiconducting carbon nanotubes (s-CNTs) into densely packed, aligned arrays of individualized s-CNTs is necessary to realize their potential in semiconductor electronics. We report the combination of chemical contrast patterns, topography, and pre-alignment of s-CNTs via shear to achieve selective-area deposition of aligned arrays of s-CNTs. Alternate stripes of surfaces favorable and unfavorable to s-CNT adsorption were patterned with widths varying from 2000 nm down to 100 nm. Addition of topography to the chemical contrast patterns combined with shear enabled the selective-area deposition of arrays of quasi-aligned s-CNTs (∼14°) even in patterns that are wider than the length of individual nanotubes (>500 nm). When the width of the chemical and topographical contrast patterns is less than the length of individual nanotubes (<500 nm), confinement effects become dominant enabling the selective-area deposition of much more tightly aligned s-CNTs (∼7°). At a trench width of 100 nm, we demonstrate the lowest standard deviation in alignment degree of 7.6 ± 0.3° at a deposition shear rate of 4600 s −1 , while maintaining an individualized s-CNT density greater than 30 CNTs μm −1 . Chemical contrast alone enables selective-area deposition, but chemical contrast in addition to topography enables more effective selective-area deposition and stronger confinement effects, with the advantage of removal of nanotubes deposited in spurious areas via selective lift-off of the topographical features. These findings provide a methodology that is inherently scalable, and a means to deposit spatially selective, aligned s-CNT arrays for next-generation semiconducting devices. 
    more » « less
  5. Abstract

    In recent years, area‐selective atomic layer deposition (AS‐ALD) has attracted increasing interest for its applications in back‐end interconnect processes, and selective deposition of Al2O3is of particular interest because Al2O3can serve as an etch hard mask. However, Al2O3is one of the most difficult ALD systems to block. In this work, a strategy is presented to enhance the blocking ability of dodecanethiol (DDT) self‐assembled monolayers (SAMs) against Al2O3ALD. It is shown that by conducting DDT deposition on a slightly oxidized Cu surface, which is mainly composed of Cu2O, rather than on a freshly acid‐etched Cu surface, which mainly consists of metallic Cu, the quality of the DDT SAM can be improved. It is further shown that the DDT SAMs formed on Cu2O‐covered Cu substrates are about 3–4 times more effective in blocking Al2O3than that on acid‐etched Cu surfaces when ALD is performed under subsaturation condition. However, as the Cu oxidation process continues, CuO is formed and the blocking ability of DDT degrades. Finally, selective Al2O3deposition on DDT‐treated Cu/low‐kpatterns using the combined strategy of Cu oxidation and subsaturation conditions achieves selectivity of 0.99 after 4 nm of Al2O3ALD.

     
    more » « less