Michael S. Arnold

Sorting carbon nanotubes by electronic structure using density differentiation

The heterogeneity of as-synthesized single-walled carbon nanotubes (SWNTs) precludes their widespread application in electronics, optics and sensing. We report on the sorting of carbon nanotubes by diameter, bandgap and electronic type using structure-discriminating surfactants to engineer subtle differences in their buoyant densities. Using the scalable technique of density-gradient ultracentrifugation, we have isolated narrow distributions of SWNTs in which >97% are within a 0.02-nm-diameter range. Furthermore, using competing mixtures of surfactants, we have produced bulk quantities of SWNTs of predominantly a single electronic type. These materials were used to fabricate thin-film electrical devices of networked SWNTs characterized by either metallic or semiconducting behaviour.

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.

Efficiently Harvesting Excitons from Electronic Type-Controlled Semiconducting Carbon Nanotube Films

We have employed thin films of highly purified semiconducting carbon nanotubes as near-infrared optical absorbers in heterojunction photovoltaic and photodetector devices with the electron acceptor C(60). In comparison with previous implementations of more electrically heterogeneous carbon nanotube/C(60) devices, we have realized a 10× gain in zero-bias quantum efficiency (QE) and even more substantial gains in power conversion efficiency (η(p)). The semiconducting nanotube/C(60) heterojunctions are highly rectifying with a peak external QE, internal QE, and η(p) of 12.9 ± 1.3, 91 ± 22, and 0.6%, respectively, in the near-infrared. We show that the device efficiency is determined by the effective length scale for exciton migration in the nanotube films, confirm the high internal QE via photoluminescence quenching, and demonstrate that the driving force for exciton dissociation at the fullerene-fullerene heterointerface is optimized for diameters <1.0 nm. These results will guide the development of next-generation high-performance carbon nanotube-based solar cells and photosensitive devices.

Broad Spectral Response Using Carbon Nanotube/Organic Semiconductor/C60 Photodetectors

We demonstrate that photogenerated excitons in semiconducting carbon nanotubes (CNTs) can be efficiently dissociated by forming a planar heterojunction between CNTs wrapped in semiconducting polymers and the electron acceptor, C(60). Illumination of the CNTs at their near-infrared optical band gap results in the generation of a short-circuit photocurrent with peak external and internal quantum efficiencies of 2.3% and 44%, respectively. Using soft CNT-hybrid materials systems combining semiconducting small molecules and polymers, we have fabricated broad-band photodetectors with a specific detectivity >10(10) cm Hz(1/2) W(1-) from lambda = 400 to 1450 nm and a response time of tau = 7.2 +/- 0.2 ns.

Peptide amphiphile nanostructure–heparin interactions and their relationship to bioactivity

Heparin-protein interactions are important in many physiological processes including angiogenesis, the growth of new blood vessels from existing ones. We have previously developed a highly angiogenic self-assembling gel, wherein the self-assembly process is triggered by the interactions between heparin and peptide amphiphiles (PAs) with a consensus heparin binding sequence. In this report, this consensus sequence was scrambled and incorporated into a new peptide amphiphile in order to study its importance in heparin interaction and bioactivity. Heparin was able to trigger gel formation of the scrambled peptide amphiphile (SPA). Furthermore, the affinity of the scrambled molecule for heparin was unchanged as shown by isothermal titration calorimetry and high Förster resonance emission transfer efficiency. However, both the mobile fraction and the dissociation rate constant of heparin, using fluorescence recovery after photobleaching, were markedly higher in its interaction with the scrambled molecule implying a weaker association. Importantly, the scrambled peptide amphiphile-heparin gel had significantly less angiogenic bioactivity as shown by decreased tubule formation of sandwiched endothelial cells. Hence, we believe that the presence of the consensus sequence stabilizes the interaction with heparin and is important for the bioactivity of these new materials.

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.

Hydrodynamic Characterization of Surfactant Encapsulated Carbon Nanotubes Using an Analytical Ultracentrifuge

The hydrodynamic properties of surfactant encapsulated single-walled carbon nanotubes (SWNTs) have been characterized by optically measuring their spatial and temporal redistribution in situ in an analytical ultracentrifuge. The measured redistribution profiles are fit to the Lamm equation, thus determining the sedimentation, diffusion, and hydrodynamic frictional coefficients of the surfactant encapsulated SWNTs. For sodium cholate encapsulated SWNTs, we demonstrate that the technique of analytical ultracentrifugation can be utilized to determine the linear packing density of surfactant molecules along the length of the SWNTs, 3.6 +/- 0.8 nm(-1), and the anhydrous molar volume of the surfactant molecules on the SWNT surfaces, 270 +/- 20 cm(3) mol(-1). Additionally, analytical ultracentrifugation is used to measure and compare the sedimentation rates of bundled and isolated carbon nanotubes. This study should serve as a guide for designing centrifuge-based processing procedures for preparing samples of SWNTs for a wide variety of applications and studies. Additionally, the results obtained here should aid in understanding the hydrodynamic properties of SWNTs and the interactions between SWNTs and surfactants in aqueous solution.

Development of Lead Iodide Perovskite Solar Cells Using Three-Dimensional Titanium Dioxide Nanowire Architectures

Three-dimensional (3D) nanowire (NW) architectures are considered as superior electrode design for photovoltaic devices compared to NWs or nanoparticle systems in terms of improved large surface area and charge transport properties. In this paper, we report development of lead iodide perovskite solar cells based on a novel 3D TiO2 NW architectures. The 3D TiO2 nanostructure was synthesized via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) technique that also implemented the Kirkendall effect for complete ZnO NW template conversion. It was found that the film thickness of 3D TiO2 can significantly influence the photovoltaic performance. Short-circuit current increased with the TiO2 length, while open-circuit voltage and fill factor decreased with the length. The highest power conversion efficiency (PCE) of 9.0% was achieved with ∼ 600 nm long 3D TiO2 NW structures. Compared to other 1D nanostructure arrays (TiO2 nanotubes, TiO2-coated ZnO NWs and ZnO NWs), 3D TiO2 NW architecture was able to achieve larger amounts of perovskite loading, enhanced light harvesting efficiency, and increased electron-transport property. Therefore, its PCE is 1.5, 2.3, and 2.8 times higher than those of TiO2 nanotubes, TiO2-coated ZnO NWs, and ZnO NWs, respectively. The unique morphological advantages, together with the largely suppressed hysteresis effect, make 3D hierarchical TiO2 a promising electrode selection in designing high-performance perovskite solar cells.

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.

Polyfluorene-Sorted, Carbon Nanotube Array Field-Effect Transistors with Increased Current Density and High On/Off Ratio

Challenges in eliminating metallic from semiconducting single-walled carbon nanotubes (SWCNTs) and in controlling their alignment have limited the development of high-performance SWCNT-based field-effect transistors (FETs). We recently pioneered an approach for depositing aligned arrays of ultra-high-purity semiconducting SWCNTs, isolated using polyfluorene derivatives, called dose-controlled floating evaporative self-assembly. Here, we tailor FETs fabricated from these arrays to achieve on-conductance (G(on)) per width and an on-off ratio (G(on)/G(off)) of 261 μS/μm and 2 × 10(5), respectively, for a channel length (L(ch)) of 240 nm and 116 μS/μm and 1 × 10(6), respectively, for an L(ch) of 1 μm. We demonstrate 1400× greater G(on)/G(off) than SWCNT FETs fabricated by other methods, at comparable G(on) per width of ∼250 μS/μm and 30-100× greater G(on) per width at comparable G(on)/G(off) of 10(5)-10(7). The average G(on) per tube reaches 5.7 ± 1.4 μS at a packing density of 35 tubes/μm for L(ch) in the range 160-240 nm, limited by contact resistance. These gains highlight the promise of using ultra-high-purity semiconducting SWCNTs with controlled alignment for next-generation semiconductor electronics.