Dominick J. Bindl

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.

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.

Semiconducting carbon nanotube aerogel bulk heterojunction solar cells.

Using a novel two-step fabrication scheme, we create highly semiconducting-enriched single-walled carbon nanotube (sSWNT) bulk heterojunctions (BHJs) by first creating highly porous interconnected sSWNT aerogels (sSWNT-AEROs), followed by back-filling the pores with [6,6]-phenyl-C(71)-butyric acid methyl ester (PC(71)BM). We demonstrate sSWNT-AERO structures with density as low as 2.5 mg cm(-3), porosity as high as 99.8%, and diameter of sSWNT fibers ≤ 10 nm. Upon spin coating with PC(71)BM, the resulting sSWNT-AERO-PC(71)BM nanocomposites exhibit highly quenched sSWNT photoluminescence, which is attributed to the large interfacial area between the sSWNT and PC(71)BM phases, and an appropriate sSWNT fiber diameter that matches the inter-sSWNT exciton migration length. Employing the sSWNT-AERO-PC(71)BM BHJ structure, we report optimized solar cells with a power conversion efficiency of 1.7%, which is exceptional among polymer-like solar cells in which sSWNTs are designed to replace either the polymer or fullerene component. A fairly balanced photocurrent is achieved with 36% peak external quantum efficiency (EQE) in the visible and 19% peak EQE in the near-infrared where sSWNTs serve as electron donors and photoabsorbers. Our results prove the effectiveness of this new method in controlling the sSWNT morphology in BHJ structures, suggesting a promising route towards highly efficient sSWNT photoabsorbing solar cells.

SEMICONDUCTING CARBON NANOTUBE PHOTOVOLTAIC PHOTODETECTORS

A photovoltaic photodetector harnessing near infrared band gap absorption by thin films of post-synthetically sorted semiconducting single walled carbon nanotubes (s-SWCNTs) is described. Peak specific detectivity of 6×1011 Jones at -0.1 V bias at 1210 nm is achieved using a heterojunction device architecture: indium tin oxide/ ca. 5 nm s-SWCNT / 120 nm C60 / 10 nm 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) / Ag. The photodiodes are characterized by a series resistance of 2.9 Ω cm2 and a rectification ratio of 104 at ±1V. These results are expected to guide the exploration of new classes of solution-processable, mechanically flexible, integrable, thin film photovoltaic photodetectors with tunable sensitivity in the visible and infrared spectra based on semiconducting carbon nanotubes.

Spectral resolution of states relevant to photoinduced charge transfer in modified pentacene/ZnO field-effect transistors

Pentacene field-effect transistors incorporating ZnO quantum dots can be used as a sensitive probe of the optical properties of a buried donor-acceptor interface. Photoinduced charge transfer between pentacene and ZnO in these devices varies with incident photon energy and reveals which energies will contribute most to charge transfer in other structures. A subsequent slow return to the dark state following the end of illumination arises from near-interface traps. Charge transfer has a sharp onset at 1.7 eV and peaks at 1.82 and 2.1 eV due to transitions associated with excitons, features absent in pentacene FETs without ZnO.