Publications

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Semiconducting nanowires have been explored for a number of applications in optoelectronics such as photodetectors and solar cells. Currently, there is ample interest in identifying the mechanisms that lead to photoresponse in nanowires in order to improve and optimize performance. However, distinguishing among the different mechanisms, including photovoltaic, photothermoelectric, photoemission, bolometric, and photoconductive, is often difficult using purely optoelectronic measurements. In this work, we present an approach for performing combined and simultaneous thermoelectric and optoelectronic measurements on the same individual nanowire. We apply the approach to GaN/AlGaN core/shell and GaN/AlGaN/GaN core/shell/shell nanowires and demonstrate the photothermoelectric nature of the photocurrent observed at the electrical contacts at zero bias, for above- and below-bandgap illumination. Furthermore, the approach allows for the experimental determination of the temperature rise due to laser illumination, which is often obtained indirectly through modeling. We also show that under bias, both above- and below-bandgap illumination leads to a photoresponse in the channel with signatures of persistent photoconductivity due to photogating. Finally, we reveal the concomitant presence of photothermoelectric and photogating phenomena at the contacts in scanning photocurrent microscopy under bias by using their different temporal response. Furthermore, our approach is applicable to a broad range of nanomaterials to elucidate their fundamental optoelectronic and thermoelectric properties.

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Metal-organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained "emergent properties," such as electronic conductivity and energy transfer, by infiltrating MOF pores with "guest" molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. These examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.

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The goal of this Exploratory Express project was to expand the understanding of the physical properties of our recently discovered class of materials consisting of metal-organic frameworks with electroactive ‘guest’ molecules that together form an electrically conducting charge-transfer complex (molecule@MOF). Thin films of Cu₃(BTC)₂ were grown on fused silica using solution step-by-step growth and were infiltrated with the molecule tetracyanoquinodimethane (TCNQ). The infiltrated MOF films were extensively characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy, electrical conductivity, and thermoelectric properties. Thermopower measurements on TCNQ@Cu₃(BTC)₂ revealed a positive Seebeck coefficient of ~400 μV/k, indicating that holes are the primary carriers in this material. The high value of the Seebeck coefficient and the expected low thermal conductivity suggest that molecule@MOF materials may be attractive for thermoelectric power conversion applications requiring low cost, solution-processable, and non-toxic active materials.

Electro-optical organic materials hold great promise for the development of high-efficiency devices based on exciton formation and dissociation, such as organic photovoltaics (OPV) and organic light-emitting devices (OLEDs). However, the external quantum efficiency (EQE) of both OPV and OLEDs must be improved to make these technologies economical. Efficiency rolloff in OLEDs and inability to control morphology at key OPV interfaces both reduce EQE. Only by creating materials that allow manipulation and control of the intimate assembly and communication between various nanoscale excitonic components can we hope to first understand and then engineer the system to allow these materials to reach their potential. The aims of this proposal are to: 1) develop a paradigm-changing platform for probing excitonic processes composed of Crystalline Nanoporous Frameworks (CNFs) infiltrated with secondary materials (such as a complimentary semiconductor); 2) use them to probe fundamental aspects of excitonic processes; and 3) create prototype OPVs and OLEDs using infiltrated CNF as active device components. These functional platforms will allow detailed control of key interactions at the nanoscale, overcoming the disorder and limited synthetic control inherent in conventional organic materials. CNFs are revolutionary inorganic-organic hybrid materials boasting unmatched synthetic flexibility that allow tuning of chemical, geometric, electrical, and light absorption/generation properties. For example, bandgap engineering is feasible and polyaromatic linkers provide tunable photon antennae; rigid 1-5 nm pores provide an oriented, intimate host for triplet emitters (to improve light emission in OLEDs) or secondary semiconducting polymers (creating a charge-separation interface in OPV). These atomically engineered, ordered structures will enable critical fundamental questions to be answered concerning charge transport, nanoscale interfaces, and exciton behavior that are inaccessible in disordered systems. Implementing this concept also creates entirely new dimensions for device fabrication that could both improve performance, increase durability, and reduce costs with unprecedented control of over properties. This report summarizes the key results of this project and is divided into sections based on publications that resulted from the work. We begin in Section 2 with an investigation of light harvesting and energy transfer in a MOF infiltrated with donor and acceptor molecules of the type typically used in OPV devices (thiophenes and fullerenes, respectively). The results show that MOFs can provide multiple functions: as a light harvester, as a stabilizer and organizer or the infiltrated molecules, and as a facilitator of energy transfer. Section 3 describes computational design of MOF linker groups to accomplish light harvesting in the visible and facilitate charge separation and transport. The predictions were validated by UV-visible absorption spectroscopy, demonstrating that rational design of MOFs for light-harvesting purposes is feasible. Section 4 extends the infiltration concept discussed in Section to, which we now designate as "Molecule@MOF" to create an electrically conducting framework. The tailorability and high conductivity of this material are unprecedented, meriting publication in the journal Science and spawning several Technical Advances. Section 5 discusses processes we developed for depositing MOFs as thin films on substrates, a critical enabling technology for fabricating MOF-based electronic devices. Finally, in Section 6 we summarize results showing that a MOF thin film can be used as a sensitizer in a DSSC, demonstrating that MOFs can serve as active layers in excitonic devices. Overall, this project provides several crucial proofs-of- concept that the potential of MOFs for use in optoelectronic devices that we predicted several years ago [ 3 ] can be realized in practice.

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This report details the progress made in measuring the temperature dependence of the electronic and optoelectronic of devices made with individual carbon nanotubes.

We present many-body ab initio calculations of the electronic and optical properties of semiconducting zigzag carbon nanotubes under uniaxial strain. The GW approach is utilized to obtain the quasiparticle band gaps and is combined with the Bethe-Salpeter equation to obtain the optical absorption spectrum. We find that the dependence of the electronic band gaps on strain is more complex than previously predicted based on tight-binding models or density functional theory. In addition, we show that the exciton energy and exciton binding energy depend significantly on strain, with variations of tens of milli-electron-volts per percent strain, but despite these strong changes the absorbance is found to be nearly independent of strain. Our results provide new guidance for the understanding and design of optomechanical systems based on carbon nanotubes. © 2013 American Physical Society.

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Sandia National Laboratories (Sandia) and Lockheed Martin Corporation (LMC) collaborated to (1) evaluate the potential of carbon nanotubes as channels in infrared (IR) photodetectors; (2) assemble and characterize carbon nanotube electronic devices and measure the photocurrent generated when exposed to infrared light;(3) compare the performance of the carbon nanotube devices with that of traditional devices; and (4) develop and numerically implement models of electronic transport and opto-electronic behavior of carbon nanotube infrared detectors. This work established a new paradigm for photodetectors.

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