Nathaniel S. Safron

Fabrication and Characterization of Large-Area, Semiconducting Nanoperforated Graphene Materials

We demonstrate the fabrication of nanoperforated graphene materials with sub-20-nm features using cylinder-forming diblock copolymer templates across >1 mm(2) areas. Hexagonal arrays of holes are etched into graphene membranes, and the remaining constrictions between holes interconnect forming a honeycomb structure. Quantum confinement, disorder, and localization effects modulate the electronic structure, opening an effective energy gap of 100 meV in the nanopatterned material. The field-effect conductivity can be modulated by 40x (200x) at room temperature (T = 105 K) as a result. A room temperature hole mobility of 1 cm(2) V(-1) s(-1) was measured in the fabricated nanoperforated graphene field effect transistors. This scalable strategy for modulating the electronic structure of graphene is expected to facilitate applications of graphene in electronics, optoelectronics, and sensing.

Dissociating excitons photogenerated in semiconducting carbon nanotubes at polymeric photovoltaic heterojunction interfaces.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have strong near-infrared and visible absorptivity and exceptional charge transport characteristics, rendering them highly attractive semiconductor absorbers for photovoltaic and photodetector technologies. However, these applications are limited by a poor understanding of how photogenerated charges, which are bound as excitons in s-SWCNTs, can be dissociated in large-area solid-state devices. Here, we measure the dissociation of excitons in s-SWCNT thin films that form planar heterojunction interfaces with polymeric photovoltaic materials using an exciton dissociation-sensitive photocapacitor measurement technique that is advantageously insensitive to optically induced thermal photoconductive effects. We find that fullerene and polythiophene derivatives induce exciton dissociation, resulting in electron and hole transfer, respectively, away from optically excited s-SWCNTs. Significantly weaker or no charge transfer is observed using wider gap polymers due to insufficient energy offsets. These results are expected to critically guide the development of thin film s-SWCNT-based photosensitive devices.

Highly Stretchable Carbon Nanotube Transistors with Ion Gel Gate Dielectrics

Field-effect transistors (FETs) that are stretchable up to 50% without appreciable degradation in performance are demonstrated. The FETs are based on buckled thin films of polyfluorene-wrapped semiconducting single-walled carbon nanotubes (CNTs) as the channel, a flexible ion gel as the dielectric, and buckled metal films as electrodes. The buckling of the CNT film enables the high degree of stretchability while the flexible nature of the ion gel allows it to maintain a high quality interface with the CNTs during stretching. An excellent on/off ratio of >10(4), a field-effect mobility of 10 cm(2) · V(-1) · s(-1), and a low operating voltage of <2 V are achieved over repeated mechanical cycling, with further strain accommodation possible. Deformable FETs are expected to facilitate new technologies like stretchable displays, conformal devices, and electronic skins.

Barrier-Guided Growth of Micro- and Nano-Structured Graphene

A novel approach for the rational synthesis of low-defect density, patterned graphene from the bottom up, called barrier-guided chemical vapor deposition, is introduced. A patterned barrier layer impedes the growth of graphene in selected areas of the copper substrate, guiding the growth of graphene into desired micro- and nano- structures with control over placement, orientation, and spatial and lateral extent.

Electronic transport and Raman scattering in size-controlled nanoperforated graphene.

We demonstrate the fabrication and study of the structure-property relationships of large-area (>1 cm(2)) semiconducting nanoperforated (NP) graphene with tunable constriction width (w = 7.5-14 nm), derived from CVD graphene using block copolymer lithography. Size-tunable constrictions were created while minimizing unintentional doping by using a dual buffer layer pattern-transfer method. An easily removable polymeric layer was sandwiched between an overlying silicon oxide layer and the underlying graphene. Perforation-size was controlled by overetching holes in the oxide prior to pattern transfer into graphene while the polymer protected the graphene from harsh conditions during oxide etching and lift off. The processing materials were removed using relatively mild solvents yielding the clean isolation of NP graphene and thereby facilitating Raman and electrical characterization. We correlate the D to G ratio as a function of w and show three regimes depending on w relative to the characteristic Raman relaxation length. Edge phonon peaks were also observed at 1450 and 1530 cm(-1) in the spectra, without the use of enhancement methods, due to high density of nanoconstricted graphene in the probe area. The resulting NP graphene exhibited semiconducting behavior with increasing ON/OFF conductance modulation with decreasing w at room temperature. The charge transport mobility decreases with increasing top-down reactive ion etching. From these comprehensive studies, we show that both electronic transport and Raman characteristics change in a concerted manner as w shrinks.

Semiconducting Two‐Dimensional Graphene Nanoconstriction Arrays

The fabrication and characterization of two-dimensional nanoconstriction arrays consisting of sub-20-nm graphene constrictions and interconnecting graphene islands are reported. The arrays are fabricated in a scalable top-down fashion using self-assembled close-packed polystyrene nanospheres as lithographic templates and characterized using electron microscopy, Raman spectroscopy, and charge transport measurements. At room temperature, the arrays behave as semiconductors with a field-effect conductance modulation of up to 450 and charge mobilities of ~1 cm(2) V(-1) s(-1) . The effective bandgap of the arrays scales inversely with the nanoconstriction width, indicating that its magnitude is determined by quantum confinement in the constrictions. At low temperatures, the arrays act as semiconductors, with increasing ON/OFF conductance modulation up to ∼1000, and simultaneously act as 2D arrays of coupled Coulomb islands affected by single-electron charging events. The high conductance modulation of these nanopatterned graphene materials, combined with the scalability of the patterning approach is expected to impact thin film, flexible, and transparent semiconductor electronics.

Orientation of a monolayer of dipolar molecules on graphene from X-ray absorption spectroscopy.

Recently, single-walled carbon nanotubes as well as graphene functionalized with azobenzene chromophores have drawn attention for applications in optoelectronics due to their ability to undergo cis-trans isomerization when exposed to light. The electronic properties of the nanocarbon materials at these unconventional interfaces can be tailored by gaining structural insight into the organic monolayers at the molecular level. In this work, we use polarization-dependent X-ray absorption spectroscopy to probe the orientation of three chromophores on graphene, all identical except for their terminal groups. All three terminal groups (methyl, nitro, and nitrile) are well-oriented, with a tilt angle of about 30° from the substrate for the shared azobenzene group. Density functional theory calculations are in good agreement with experimental results and give two similar, stable configurations for the orientation of these molecules on graphene.

Experimentally determined model of atmospheric pressure CVD of graphene on Cu

We investigate the critical methane concentration (CMC) during the atmospheric-pressure chemical vapor deposition (AP-CVD) of graphene on Cu from CH4. Above the CMC, graphene both nucleates and grows; below the CMC, it etches; while at the CMC, carbon intermediate species attach and detach from graphene at equal rates. By studying how the CMC varies with [H2] and temperature, we determine the reaction mechanism and the intermediates. We find that the CMC scales with [H2]3/2 and determine a single Arrhenius temperature dependence close to the expected equilibrium value. For [CH4] > CMC, the radial growth rate is proportional to the “building unit” supersaturation indicating that graphene growth occurs under capture-limited kinetics through an intermediate hydrocarbon that is first-order dependent on [CH4] and proportional to [H2]−3/2. We develop a CH4 decomposition and capture model which is consistent with all measurements indicating that the intermediate is CH. We find that uniform monolayer graphene can only be achieved in AP-CVD near the CMC, with a nucleation density that varies 5 orders of magnitude from 880 to 1075 °C. Thus, our work also provides a roadmap for growing uniform graphene at atmospheric pressure on Cu over a broad range of experimental conditions.

Transfer of pre-assembled block copolymer thin film to nanopattern unconventional substrates.

In this work, we demonstrate that a preassembled block copolymer (BCP) thin film can be floated, transferred, and utilized to effectively nanopattern unconventional substrates. As target substrates, we chose Cu foil and graphene/Cu foil since they cannot be nanopatterned via conventional processes due to the high surface roughness and susceptibility to harsh processing chemicals and etchants. Perpendicular hexagonal PMMA cylinder arrays in diblock copolymer poly(styrene-block-methyl methacrylate) [P(S-b-MMA)] thin films were preassembled on sacrificial SiO2/Si substrates. The BCP thin film was floated at the air/water interface off of a SiO2/Si substrate and then collected with the target substrate, leading to well-defined nanoporous PS templates on these uneven surfaces. We further show that the nanoporous template can be used for a subtractive process to fabricate nanoperforated graphene on Cu foil in sub-20 nm dimension, and for an additive process to create aluminum oxide nanodot arrays without any polymeric residues or use of harsh chemicals and etchants.

A facile route for fabricating graphene nanoribbon array transistors using graphoepitaxy of a symmetric block copolymer

We report a facile route to form densely packed graphene nanoribbon (GNR) arrays via graphoepitaxial assembly of symmetric P(S-b-MMA). Since guiding channels for graphoepitaxy are the source and drain electrodes in field effect transistor (FET) geometry, we avoid laborious nanopatterning and FET device fabrication processes. By grafting a random copolymer brush on the graphene FET device, perpendicular lamellar domains are aligned normal to the electrode direction, resulting in line arrays connecting the two electrodes. Through optimization of the reactive ion etching conditions, the vertically oriented lamellar domains were transferred to the underlying graphene, leading to GNR arrays that act as conducting channels. This is a simple and efficient fabrication process using the fundamental concepts developed for the graphoepitaxial assembly of symmetric BCPs to create densely packed sub- 20 nm GNR arrays, compared to conventional fabrication process.