Rishabh M. Jain

Polymer‐Free Near‐Infrared Photovoltaics with Single Chirality (6,5) Semiconducting Carbon Nanotube Active Layers

We demonstrate a polymer-free carbon-based photovoltaic device that relies on exciton dissociation at the SWNT/C(60) interface, as shown in the figure. Through the construction of a carbon-based photovoltaic completely free of polymeric active or transport layers, we show both the feasibility of this novel device as well as inform the mechanisms for inefficiencies in SWNTs and carbon based solar cells.

Boronic acid library for selective, reversible near-infrared fluorescence quenching of surfactant suspended single-walled carbon nanotubes in response to glucose

We describe the high-throughput screening of a library of 30 boronic acid derivatives to form complexes with sodium cholate suspended single-walled carbon nanotubes (SWNTs) to screen for their ability to reversibly report glucose binding via a change in SWNT fluorescence. The screening identifies 4-cyanophenylboronic acid which uniquely causes a reversible wavelength red shift in SWNT emission. The results also identify 4-chlorophenylboronic acid which demonstrates a turn-on fluorescence response when complexed with SWNTs upon glucose binding in the physiological range of glucose concentration. The mechanism of fluorescence modulation in both of these cases is revealed to be a photoinduced excited-state electron transfer that can be disrupted by boronate ion formation upon glucose binding. The results allow for the elucidation of design rules for such sensors, as we find that glucose recognition and transduction is enabled by para-substituted, electron-withdrawing phenyl boronic acids that are sufficiently hydrophobic to adsorb to the nanotube surface.

A Kinetic Model for the Deterministic Prediction of Gel-Based Single-Chirality Single-Walled Carbon Nanotube Separation

We propose a kinetic model that describes the separation of single-chirality semiconducting carbon nanotubes based on the chirality-selective adsorption to specific hydrogels. Experimental elution profiles of the (7,3), (6,4), (6,5), (8,3), (8,6), (7,5), and (7,6) species are well described by an irreversible, first-order site association kinetic model with a single rate constant describing the adsorption of each SWNT to the immobile gel phase. Specifically, we find first-order binding rate constants for seven experimentally separated nanotubes normalized by the binding site molarity (M(θ)): k₇,₃ = 3.5 × 10⁻⁵ M(θ)⁻¹ s⁻¹, k₆,₄ = 7.7 × 10⁻⁸ M(θ)⁻¹ s⁻¹, k₈,₃ = 2.3 × 10⁻⁹ M(θ)⁻¹ s⁻¹, k₆,₅ = 3.8 × 10⁻⁹ M(θ)⁻¹ s⁻¹, k₇,₅ = 1.9 × 10⁻¹¹ M(θ)⁻¹ s⁻¹, k₈,₆ = 7.7 × 10⁻¹² M(θ)⁻¹ s⁻¹, and k₇,₆ = 3.8 × 10⁻¹² M(θ)⁻¹ s⁻¹. These results, as well as additional control experiments, unambiguously identify the separation process as a selective adsorption. Unlike certain chromatographic processes with retention time dependence, this separation procedure can be scaled to arbitrarily large volumes, as we demonstrate. This study provides a foundation for both the mechanistic understanding of gel-based SWNT separation as well as the potential industrial-scale realization of single-chirality production of carbon nanotubes.

A Ratiometric Sensor Using Single Chirality Near-Infrared Fluorescent Carbon Nanotubes: Application to In Vivo Monitoring

Advances in the separation and functionalization of single walled carbon nanotubes (SWCNT) by their electronic type have enabled the development of ratiometric fluorescent SWCNT sensors for the first time. Herein, single chirality SWCNT are independently functionalized to recognize either nitric oxide (NO), hydrogen peroxide (H(2)O(2)), or no analyte (remaining invariant) to create optical sensor responses from the ratio of distinct emission peaks. This ratiometric approach provides a measure of analyte concentration, invariant to the absolute intensity emitted from the sensors and hence, more stable to external noise and detection geometry. Two distinct ratiometric sensors are demonstrated: one version for H(2)O(2), the other for NO, each using 7,6 emission, and each containing an invariant 6,5 emission wavelength. To functionalize these sensors from SWCNT isolated from the gel separation technique, a method for rapid and efficient coating exchange of single chirality sodium dodecyl sulfate-SWCNT is introduced. As a proof of concept, spatial and temporal patterns of the ratio sensor response to H(2)O(2) and, separately, NO, are monitored in leaves of living plants in real time. This ratiometric optical sensing platform can enable the detection of trace analytes in complex environments such as strongly scattering media and biological tissues.

Quantitative Theory of Adsorptive Separation for the Electronic Sorting of Single-Walled Carbon Nanotubes

Recently, several important advances in techniques for the separation of single-walled carbon nanotubes (SWNTs) by chiral index have been developed. These new methods allow for the separation of SWNTs through selective adsorption and desorption of different (n,m) chiral indices to and from a specific hydrogel. Our group has previously developed a kinetic model for the chiral elution order of separation; however, the underlying mechanism that allows for this separation remains unknown. In this work, we develop a quantitative theory that provides the first mechanistic insights for the separation order and binding kinetics of each SWNT chirality (n,m) based on the surfactant-induced, linear charge density, which we find ranges from 0.41 e(-)/nm for (7,3) SWNTs in 17 mM sodium dodecyl sulfate (SDS) to 3.32 e(-)/nm for (6,5) SWNTs in 105 mM SDS. Adsorption onto the hydrogel support is balanced by short-distance hard-surface and long-distance electrostatic repulsive SWNT/substrate forces, the latter of which we postulate is strongly dependent on surfactant concentration and ultimately leads to gel-based single-chirality semiconducting SWNT separation. These molecular-scale properties are derived using bulk-phase, forward adsorption rate constants for each SWNT chirality in accordance with our previously published model. The theory developed here quantitatively describes the experimental elution profiles of 15 unique SWNT chiralities as a function of anionic surfactant concentration between 17 and 105 mM, as well as phenomenological observations of the impact of varying preparatory conditions such as extent of ultrasonication and ultracentrifugation. We find that SWNT elution order and separation efficiency are primarily driven by the morphological change of SDS surfactant wrapping on the surface of the nanotube, mediated by SWNT chirality and the ionic strength of the surrounding medium. This work provides a foundational understanding for high-purity, preparative-scale separation of as-produced SWNT mixtures into isolated, single-chirality fractions.

Deterministic modelling of carbon nanotube near-infrared solar cells

Photovoltaics (PVs) using single-walled carbon nanotubes (SWNTs) as near-infrared photo-absorbers have progressed rapidly, offering promise for long-wavelength light harvesting devices. Despite this interest the fundamental design questions remain, such as optimal device thickness, nanotube orientation, density, and the impact of impurities. To address this challenge, we develop a deterministic model of SWNT PVs derived directly from SWNT photophysics using photon, exciton, and charge carrier population balances. The model accounts for arbitrary distributions of nanotube chiralities, lengths, orientations, defect types and concentrations, bundle fraction and size, and density. We show that feasible devices can achieve external quantum efficiencies above 60%. We reveal a sharply optimal device thickness that is a function of nanotube density, orientation, and quenching site concentration. This thickness stems from a tradeoff between exciton generation and diffusion to the electrodes, and is at a minimum at the limit of close-packed nanotube density. We show that this minimum characterizes a given device design and scales with mean nanotube length to exponent 0.4. The normalized difference between optimal thickness and this close-packed limit scales inversely with density to the 0.24 power. Practically, in-plane aligned nanotube configurations yield optimal thicknesses less than 10 nm, increasing to a range of 50 to 200 nm for vertical alignment. Due to weak inter-SWNT exciton transport relative to exceptional intra-SWNT diffusion, vertically-aligned films are unambiguously favored at densities above 3% of the close-packed limit; at lower densities however an optimum emerges at an intermediate angle to compensate for weaker light absorption of vertical nanotubes. Comparison to published experimental devices displays the models utility for device design.