Publications

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We investigate the sensitivity of silicon-oxide-nitride-silicon-oxide (SONOS) charge trapping memory technology to heavy-ion induced single-event effects. Threshold voltage ( V_T ) statistics were collected across multiple test chips that contained in total 18 Mb of 40-nm SONOS memory arrays. The arrays were irradiated with Kr and Ar ion beams, and the changes in their V_T distributions were analyzed as a function of linear energy transfer (LET), beam fluence, and operating temperature. We observe that heavy ion irradiation induces a tail of disturbed devices in the 'program' state distribution, which has also been seen in the response of floating-gate (FG) flash cells. However, the V_T distribution of SONOS cells lacks a distinct secondary peak, which is generally attributed to direct ion strikes to the gate-stack of FG cells. This property, combined with the observed change in the V_T distribution with LET, suggests that SONOS cells are not particularly sensitive to direct ion strikes but cells in the proximity of an ion's absorption can still experience a V_T shift. These results shed new light on the physical mechanisms underlying the V_T shift induced by a single heavy ion in scaled charge trap memory.

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The controlled fabrication of vertical, tapered, and high-aspect ratio GaN nanowires via a two-step top-down process consisting of an inductively coupled plasma reactive ion etch followed by a hot, 85% H3PO4 crystallographic wet etch is explored. The vertical nanowires are oriented in the [0001] direction and are bound by sidewalls comprising of 3362 ¯ } semipolar planes which are at a 12° angle from the [0001] axis. High temperature H3PO4 etching between 60 °C and 95 °C result in smooth semipolar faceting with no visible micro-faceting, whereas a 50 °C etch reveals a micro-faceted etch evolution. High-angle annular dark-field scanning transmission electron microscopy imaging confirms nanowire tip dimensions down to 8–12 nanometers. The activation energy associated with the etch process is 0.90 ± 0.09 eV, which is consistent with a reaction-rate limited dissolution process. The exposure of the 3362 ¯ } type planes is consistent with etching barrier index calculations. The field emission properties of the nanowires were investigated via a nanoprobe in a scanning electron microscope as well as by a vacuum field emission electron microscope. The measurements show a gap size dependent turn-on voltage, with a maximum current of 33 nA and turn-on field of 1.92 V nm−1 for a 50 nm gap, and uniform emission across the array.

The III-nitride semiconductors are attractive for on-chip, solid-state vacuum nanoelectronics, having high thermal and chemical stability, low electron affinity, and high breakdown fields. Here we report top-down fabricated, lateral gallium nitride (GaN)-based nanoscale vacuum electron diodes operable in air, with ultra-low turn-on voltages down to ~0.24 V, and stable high field emission currents, tested up to several microamps for single-emitter devices. We present gap-size and pressure dependent studies which provide insights into the design of future nanogap vacuum electron devices. The vacuum nanodiodes also show high resistance to damage from 2.5 MeV proton exposure. Preliminary results on the fabrication and characteristics of lateral GaN nano vacuum transistors will also be presented. The results show promise for a new class of robust, integrated, III-nitride based vacuum nanoelectronics.

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The performance of solid-state electrochemical systems is intimately tied to the potential and lithium distributions across electrolyte-electrode junctions that give rise to interface impedance. Here, we combine two operando methods, Kelvin probe force microscopy (KPFM) and neutron depth profiling (NDP), to identify the rate-limiting interface in operating Si-LiPON-LiCoO2 solid-state batteries by mapping the contact potential difference (CPD) and the corresponding Li distributions. The contributions from ions, electrons, and interfaces are deconvolved by correlating the CPD profiles with Li-concentration profiles and by comparisons with first-principles-informed modeling. We find that the largest potential drop and variation in the Li concentration occur at the anode-electrolyte interface, with a smaller drop at the cathode-electrolyte interface and a shallow gradient within the bulk electrolyte. Correlating these results with electrochemical impedance spectroscopy following battery cycling at low and high rates confirms a long-standing conjecture linking large potential drops with a rate-limiting interfacial process.

An intriguing new class of two-dimensional (2D) materials based on metal-organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a-Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion.

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The galvanostatic intermittent titration technique (GITT) is widely used to evaluate solid-state diffusion coefficients in electrochemical systems. However, the existing analysis methods for GITT data require numerous assumptions, and the derived diffusion coefficients typically are not independently validated. To investigate the validity of the assumptions and derived diffusion coefficients, we employ a direct-pulse fitting method for interpreting the GITT data that involves numerically fitting an electrochemical pulse and subsequent relaxation to a one-dimensional, single-particle, electrochemical model coupled with non-ideal transport to directly evaluate diffusion coefficients. Our non-ideal diffusion coefficients, which are extracted from GITT measurements of the intercalation regime of FeS2 and independently verified through discharge predictions, prove to be 2 orders of magnitude more accurate than ideal diffusion coefficients extracted using conventional methods. We further extend our model to a polydisperse set of particles to show the validity of a single-particle approach when the modeled radius is proportional to the total volume-to-surface-area ratio of the system.

The understanding and control of charge carrier interactions with defects at buried insulator/semiconductor interfaces is essential for achieving optimum performance in modern electronics. Here, we report on the use of scanning ultrafast electron microscopy (SUEM) to remotely probe the dynamics of excited carriers at a Si surface buried below a thick thermal oxide. Our measurements illustrate a previously unidentified SUEM contrast mechanism, whereby optical modulation of the space-charge field in the semiconductor modulates the electric field in the thick oxide, thus affecting its secondary electron yield. By analyzing the SUEM contrast as a function of time and laser fluence we demonstrate the diffusion mediated capture of excited carriers by interfacial traps.

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This project aimed to identify the performance-limiting mechanisms in mid- to far infrared (IR) sensors by probing photogenerated free carrier dynamics in model detector materials using scanning ultrafast electron microscopy (SUEM). SUEM is a recently developed method based on using ultrafast electron pulses in combination with optical excitations in a pump- probe configuration to examine charge dynamics with high spatial and temporal resolution and without the need for microfabrication. Five material systems were examined using SUEM in this project: polycrystalline lead zirconium titanate (a pyroelectric), polycrystalline vanadium dioxide (a bolometric material), GaAs (near IR), InAs (mid IR), and Si/SiO 2 system as a prototypical system for interface charge dynamics. The report provides detailed results for the Si/SiO 2 and the lead zirconium titanate systems.

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Automated vehicles (AV) hold great promise for improving safety, as well as reducing congestion and emissions. In order to make automated vehicles commercially viable, a reliable and highperformance vehicle-based computing platform that meets ever-increasing computational demands will be key. Given the state of existing digital computing technology, designers will face significant challenges in meeting the needs of highly automated vehicles without exceeding thermal constraints or consuming a large portion of the energy available on vehicles, thus reducing range between charges or refills. The accompanying increases in energy for AV use will place increased demand on energy production and distribution infrastructure, which also motivates increasing computational energy efficiency.

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Understanding the impact of high-energy electron radiation on device characteristics remains critical for the expanding use of semiconductor electronics in space-borne applications and other radiation harsh environments. Here, we report on in situ measurements of high-energy electron radiation effects on the hole diffusion length in low threading dislocation density homoepitaxial bulk n-GaN Schottky diodes using electron beam induced current (EBIC) in high-voltage scanning electron microscopy mode. Despite the large interaction volume in this system, quantitative EBIC imaging is possible due to the sustained collimation of the incident electron beam. This approach enables direct measurement of electron radiation effects without having to thin the specimen. Using a combination of experimental EBIC measurements and Monte Carlo simulations of electron trajectories, we determine a hole diffusion length of 264 ± 11 nm for n-GaN. Irradiation with 200 kV electron beam with an accumulated dose of 24 × 1016 electrons cm−2 led to an approximate 35% decrease in the minority carrier diffusion length.

Advanced GaN power devices are promising for many applications in high power electronics but performance limitations due to material quality in etched-and-regrown junctions prevent their widespread use. Carrier diffusion length is a critical parameter that not only determines device performance but is also a diagnostic of material quality. Here we present the use of electron-beam induced current to measure carrier diffusion lengths in continuously grown and etched-and-regrown GaN pin diodes as models for interfaces in more complex devices. Variations in the quality of the etched-and-regrown junctions are observed and shown to be due to the degradation of the n-type material. We observe an etched-and-regrown junction with properties comparable to a continuously grown junction.

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The rapidly increasing use of electronics in high-radiation environments and the continued evolution in transistor architectures and materials demand improved methods to characterize the potential damaging effects of radiation on device performance. Here, electron-beam-induced current is used to map hot-carrier transport in model metal-oxide semiconductor field-effect transistors irradiated with a 300 KeV focused He+ beam as a localized line spanning across the gate and bulk Si. By correlating the damage to the electronic properties and combining these results with simulations, the contribution of spatially localized radiation damage on the device characteristics is obtained. This identified damage, caused by the He+ beam, is attributed to localized interfacial Pb centers and delocalized positive fixed-charges, as surmised from simulations. Comprehension of the long-term interaction and mobility of radiation-induced damage are key for future design of rad-hard devices.

Liquid organic hydrogen carriers such as alcohols and polyols are a high-capacity means of transporting and reversibly storing hydrogen that demands effective catalysts to drive the (de)hydrogenation reactions under mild conditions. We employed a combined theory/experiment approach to develop MOF-74 catalysts for alcohol dehydrogenation and examine the performance of the open metal sites (OMS), which have properties analogous to the active sites in high-performance single-site catalysts and homogeneous catalysts. Methanol dehydrogenation was used as a model reaction system for assessing the performance of five monometallic M-MOF-74 variants (M = Co, Cu, Mg, Mn, Ni). Co-MOF-74 and Ni-MOF-74 give the highest H2 productivity. However, Ni-MOF-74 is unstable under reaction conditions and forms metallic nickel particles. To improve catalyst activity and stability, bimetallic (NixMg1-x)-MOF-74 catalysts were developed that stabilize the Ni OMS and promote the dehydrogenation reaction. An optimal composition exists at (Ni0.32Mg0.68)-MOF-74 that gives the greatest H2 productivity, up to 203 mL gcat-1 min-1 at 300 °C, and maintains 100% selectivity to CO and H2 between 225-275 °C. The optimized catalyst is also active for the dehydrogenation of other alcohols. DFT calculations reveal that synergistic interactions between the open metal site and the organic linker lead to lower reaction barriers in the MOF catalysts compared to the open metal site alone. This work expands the suite of hydrogen-related reactions catalyzed by MOF-74 which includes recent work on hydroformulation and our earlier reports of aryl-ether hydrogenolysis. Moreover, it highlights the use of bimetallic frameworks as an effective strategy for stabilizing a high density of catalytically active open metal sites. This journal is