Albert Alec Talin

Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices

Guests for Conductors Thin films of metal-organic framework (MOF) compounds are generally poor conductors because the linking organic groups are usually insulators with little π-orbital conjugation. Talin et al. (p. 66, published online 5 December) show that infiltrating films of the copper-based MOF HKUST-1 with the conjugated organic molecule 7,7,8,8-tetracyanoquinododimethane created an air-stable material with conductivities as high as 7 siemens per meter. Infiltrating a metal-organic framework with a conjugated organic molecule creates an air-stable conducting film. We report a strategy for realizing tunable electrical conductivity in metal-organic frameworks (MOFs) in which the nanopores are infiltrated with redox-active, conjugated guest molecules. This approach is demonstrated using thin-film devices of the MOF Cu3(BTC)2 (also known as HKUST-1; BTC, benzene-1,3,5-tricarboxylic acid) infiltrated with the molecule 7,7,8,8-tetracyanoquinododimethane (TCNQ). Tunable, air-stable electrical conductivity over six orders of magnitude is achieved, with values as high as 7 siemens per meter. Spectroscopic data and first-principles modeling suggest that the conductivity arises from TCNQ guest molecules bridging the binuclear copper paddlewheels in the framework, leading to strong electronic coupling between the dimeric Cu subunits. These ohmically conducting porous MOFs could have applications in conformal electronic devices, reconfigurable electronics, and sensors.

High-contrast and fast electrochromic switching enabled by plasmonics

With vibrant colours and simple, room-temperature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light—propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer—present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.

Li-Ion Synaptic Transistor for Low Power Analog Computing.

Nonvolatile redox transistors (NVRTs) based upon Li-ion battery materials are demonstrated as memory elements for neuromorphic computer architectures with multi-level analog states, write linearity, low-voltage switching, and low power dissipation. Simulations of backpropagation using the device properties reach ideal classification accuracy. Physics-based simulations predict energy costs per write operation of <10 aJ when scaled to 200 nm × 200 nm.

A MEMS Light Modulator Based on Diffractive Nanohole Gratings

We present the design, fabrication, and testing of a microelectromechanical systems (MEMS) light modulator based on pixels patterned with periodic nanohole arrays. Flexure-suspended silicon pixels are patterned with a two dimensional array of 150 nm diameter nanoholes using nanoimprint lithography. A top glass plate assembled above the pixel array is used to provide a counter electrode for electrostatic actuation. The nanohole pattern is designed so that normally-incident light is coupled into an in-plane grating resonance, resulting in an optical stop-band at a desired wavelength. When the pixel is switched into contact with the top plate, the pixel becomes highly reflective. A 3:1 contrast ratio at the resonant wavelength is demonstrated for gratings patterned on bulk Si substrates. The switching time is 0.08 ms and the switching voltage is less than 15V.

Mapping the Local Photoelectronic Properties of Polycrystalline Solar Cells Through High Resolution Laser-Beam-Induced Current Microscopy

To boost the efficiency of thin-film polycrystalline solar cells that are microscopically inhomogeneous, it is imperative to understand how the grain interiors (GIs) and grain boundaries (GBs) within these materials affect its overall electronic properties. By using an apertured near-field scanning optical microscope in an illumination mode, we determined the local photocurrent that is generated within the GIs and at the GBs with nanoscale resolution and correlate the results with surface morphology and composition.

Insights into capacity loss mechanisms of all-solid-state Li-ion batteries with Al anodes

The atomistic mechanism for lithiation/delithiation in all-solid-state batteries is still an open question, and the ‘holy grail’ to engineer devices with extended lifetime. Here, by combining real-time scanning electron microscopy in ultra-high vacuum with electrochemical cycling, we quantify the dynamic degradation of Al anodes in Li-ion all-solid-state batteries, a promising alternative for ultra lightweight devices. We find that AlLi alloy mounds are formed on the top surface of the Al anode and that degradation of battery capacity occurs because of Li trapped in them. Our approach establishes a new platform for probing the real-time degradation of electrodes, and can be expanded to other complex systems, allowing for high throughput characterization of batteries with nanoscale resolution.

Size dictated thermal conductivity of GaN

The thermal conductivity of n- and p-type doped gallium nitride (GaN) epilayers having thicknesses of 3–4u2009μm was investigated using time domain thermoreflectance. Despite possessing carrier concentrations ranging across 3 decades (1015–1018u2009cm–3), n-type layers exhibit a nearly constant thermal conductivity of 180u2009W/mK. The thermal conductivity of p-type epilayers, in contrast, reduces from 160 to 110u2009W/mK with increased doping. These trends—and their overall reduction relative to bulk—are explained leveraging established scattering models where it is shown that, while the decrease in p-type layers is partly due to the increased impurity levels evolving from its doping, size effects play a primary role in limiting the thermal conductivity of GaN layers tens of microns thick. Device layers, even of pristine quality, will therefore exhibit thermal conductivities less than the bulk value of 240u2009W/mK owing to their finite thickness.

Performance and Breakdown Characteristics of Irradiated Vertical Power GaN P-i-N Diodes

Electrical performance and defect characterization of vertical GaN P-i-N diodes before and after irradiation with 2.5 MeV protons and neutrons is investigated. Devices exhibit increase in specific on-resistance following irradiation with protons and neutrons, indicating displacement damage introduces defects into the p-GaN and n- drift regions of the device that impact on-state device performance. The breakdown voltage of these devices, initially above 1700 V, is observed to decrease only slightly for particle fluence <; 1013 cm-2. The unipolar figure of merit for power devices indicates that while the on-resistance and breakdown voltage degrade with irradiation, vertical GaN P-i-Ns remain superior to the performance of the best available, unirradiated silicon devices and on-par with unirradiated modern SiC-based power devices.

Imaging the Impact of Proton Irradiation on Edge Terminations in Vertical GaN PIN Diodes

Devices based on GaN have shown great promise for high power electronics, including their potential use as radiation tolerant components. An important step to realizing high power diodes is the design and implementation of an edge termination to mitigate field crowding, which can lead to premature breakdown. However, little is known about the effects of radiation on edge termination functionality. We experimentally examine the effects of proton irradiation on multiple field ring edge terminations in high power vertical GaN PIN diodes using in operando imaging with electron beam induced current (EBIC). We find that exposure to proton irradiation influences field spreading in the edge termination as well as carrier transport near the anode. By using depth-dependent EBIC measurements of hole diffusion length in homoepitaxial n-GaN we demonstrate that the carrier transport effect is due to a reduction in hole diffusion length following proton irradiation.

Crystalline Nanoporous Frameworks: a Nanolaboratory for Probing Excitonic Device Concepts.

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, andmorexa0» 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 %22Molecule%40MOF%22 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.«xa0less