arXiv subjects

William A. Callahan

Publications and source records attributed to William A. Callahan.

8 recordsLinked to original sources

arXiv2026

High-Temperature Hydrogen Sensors Based on Gallium Oxide Heterojunction Diodes

Long-term, high temperature operation of Ga2O3 devices is a crucial hurdle that must be overcome before widespread adoption of the technology can be achieved, but is largely absent from the overall body of work. Demonstrations up to this point show devices are either limited by material or dopant instability that leads to performance degradation with time. Herein, Ga2O3-based hydrogen sensors employing Pt Schottky and Cr2O3/Ga2O3 p-n diodes (Mg- and N-doped) were fabricated and evaluated for long-term stability at 600C for 800-1,800 hours, with cyclic exposure to N2 and low-concentration H2 (500-1,500 ppm). Transient current density (measured at -0.1 V) and periodic J-V characterization were used to track performance. Despite gradual declines in sensor signal and sensitivity, devices distinguished hydrogen concentrations throughout weeks of operation. Degradation was architecture-dependent: Cr2O3:Mg degraded gradually, consistent with known Mg migration; the Pt Schottky diode showed dramatic changes after 1,000 hours; and Cr2O3:N showed the lowest but most stable performance before failing at 800 hours. Thermionic emission and Lambert W-based modeling confirmed hydrogen exposure reduces interfacial barrier height via a proton-induced dipole mechanism common to both diode types. TEM of aged Pt Schottky diodes revealed Pt grain growth and microvoid formation as key degradation mechanisms. TOF-SIMS confirmed nitrogen dopants remain confined to the Cr2O3:N layer, supporting N-doping as a stable, lower-performance alternative to Mg-doping

cond-mat.mtrl-sci↗

arXiv2026

Autonomous Reliability Qualification of Ga$_2$O$_3$-based diode sensors via Safe Active Learning

Ultra-wide bandgap (UWBG) Ga$_2$O$_3$ is a promising semiconductor for high-power and high-temperature electronics. Reliable qualification of these devices under extreme operating conditions is essential, yet conventional reliability testing is inherently time-consuming. Autonomous experimentation offers a new paradigm by enabling measurement planning and model refinement to evolve in parallel in real time. We present a Safe Active Learning (SAL) framework for autonomous reliability characterization of Ga$_2$O$_3$-based diode sensors under coupled thermal and hydrogen stress. We first evaluate SAL in simulation, where it safely expands the explored region while learning the evolving rectification surface. Second, we demonstrate SAL experimentally on an automated high-temperature probe-station platform using a Pt/Cr$_2$O$_3$:Mg/$β$-Ga$_2$O$_3$ diode sensor of H$_2$ and temperature, spanning 0-800 ppm H$_2$ and 350-550 °C. Finally, we use the SAL-generated dataset for offline long-horizon forecasting of the diode current at a target voltage with a structured Gaussian-process model. Its condition-dependent Kohlrausch--Williams--Watts mean and residual covariance kernel were engineered with artificial-intelligence assistance using the SAL data and an auxiliary validation dataset spanning 1,000 hours at 400 °C across multiple H$_2$ concentrations. This dataset guided kernel design and validation, and the resulting model captures its long-time, saturating degradation trends. Although demonstrated here for a rectifying Ga$_2$O$_3$-based diode, SAL is applicable to other device classes whenever a suitable safety observable can be measured in situ.

physics.app-ph↗

arXiv2024

From Text to Test: AI-Generated Control Software for Materials Science Instruments

Large language models (LLMs) are transforming the landscape of chemistry and materials science. Recent examples of LLM-accelerated experimental research include virtual assistants for parsing synthesis recipes from the literature, or using the extracted knowledge to guide synthesis and characterization. Despite these advancements, their application is constrained to labs with automated instruments and control software, leaving much of materials science reliant on manual processes. Here, we demonstrate the rapid deployment of a Python-based control module for a Keithley 2400 electrical source measure unit using ChatGPT-4. Through iterative refinement, we achieved effective instrument management with minimal human intervention. Additionally, a user-friendly graphical user interface (GUI) was created, effectively linking all instrument controls to interactive screen elements. Finally, we integrated this AI-crafted instrument control software with a high-performance stochastic optimization algorithm to facilitate rapid and automated extraction of electronic device parameters related to semiconductor charge transport mechanisms from current-voltage (IV) measurement data. This integration resulted in a comprehensive open-source toolkit for semiconductor device characterization and analysis using IV curve measurements. We demonstrate the application of these tools by acquiring, analyzing, and parameterizing IV data from a Pt/Cr$_2$O$_3$:Mg/$β$-Ga$_2$O$_3$ heterojunction diode, a novel stack for high-power and high-temperature electronic devices. This approach underscores the powerful synergy between LLMs and the development of instruments for scientific inquiry, showcasing a path for further acceleration in materials science.

cond-mat.mtrl-sci↗

arXiv2024

Reliable operation of Cr$_2$O$_3$:Mg/ $β$-Ga$_2$O$_3$ p-n heterojunction diodes at 600$^\circ$C

$β$-Ga$_2$O$_3$-based semiconductor heterojunctions have recently demonstrated improved performance at high voltages and elevated temperatures and are thus promising for applications in power electronic devices and harsh-environment sensors. However, the long-term reliability of these ultra-wide band gap (UWBG) semiconductor devices remains barely addressed and may be strongly influenced by chemical reactions at the p-n heterojunction interface. Here, we experimentally demonstrate operation and evaluate the reliability of Cr$_2$O$_3$:Mg/ $β$-Ga$_2$O$_3$ p-n heterojunction diodes at during extended operation at 600$^\circ$C, as well as after 30 repeated cycles between 25-550$^\circ$C. The calculated pO2-temperature phase stability diagram of the Ga-Cr-O material system predicts that Ga$_2$O$_3$ and Cr$_2$O$_3$ should remain thermodynamically stable in contact with each other over a wide range of oxygen pressures and operating temperatures. The fabricated Cr$_2$O$_3$:Mg / $β$-Ga$_2$O$_3$ p-n heterojunction diodes show room-temperature on/off ratios >10$^4$ at $\pm$5V and a breakdown voltage (V$_{Br}$) of -390V. The leakage current increases with increasing temperature up to 600$^\circ$C, which is attributed to Poole-Frenkel emission with a trap barrier height of 0.19 eV. Over the course of a 140-hour thermal soak at 600$^\circ$C, both the device turn-on voltage and on-state resistance increase from 1.08V and 5.34 m$Ω$-cm$^2$ to 1.59V and 7.1 m$Ω$-cm$^2$ respectively. This increase is attributed to the accumulation of Mg and MgO at the Cr$_2$O$_3$/Ga$_2$O$_3$ interface as observed from TOF-SIMS analysis. These findings inform future design strategies of UWBG semiconductor devices for harsh environment operation and underscore the need for further reliability assessments for $β$-Ga$_2$O$_3$ based devices.

cond-mat.mtrl-sci↗

arXiv2024

NiGa$_{2}$O$_{4}$ interfacial layers in NiO/Ga$_{2}$O$_{3}$ heterojunction diodes at high temperature

NiO/Ga$_{2}$O$_{3}$ heterojunction diodes have attracted attention for high-power applications, but their high-temperature performance and reliability remain underexplored. Here we report on the time evolution of the static electrical properties in the widely studied p-NiO/n-Ga$_{2}$O$_{3}$heterojunction diodes and the formation of NiGa$_{2}$O$_{4}$ interfacial layers when operated at $550^{\circ}$C. Results of our thermal cycling experiment show an initial leakage current increase which stabilizes after sustained thermal load, due to reactions at the NiO-Ga$_{2}$O$_{3}$ interface. High-resolution TEM microstructure analysis of the devices after thermal cycling indicates that the NiO-Ga$_{2}$O$_{3}$ interface forms ternary compounds at high temperatures, and thermodynamic calculations suggest the formation of the spinel NiGa$_{2}$O$_{4}$ layer between NiO and Ga$_{2}$O$_{3}$. First-principles defect calculations find that NiGa$_{2}$O$_{4}$ shows low p-type intrinsic doping, and hence can also serve to limit electric field crowding at the interface. Vertical NiO/Ga$_{2}$O$_{3}$ diodes with intentionally grown 5 nm thin spinel-type NiGa$_{2}$O$_{4}$ interfacial layers show excellent device ON/OFF ratio of > 10$^{10}$($\pm$3 V), V$_{ON}$ of ~1.9 V, and breakdown voltage of ~ 1.2 kV for an initial unoptimized 300-micron diameter device. These p-n heterojunction diodes are promising for high-voltage, high-temperature applications.

cond-mat.mtrl-sci↗

arXiv2023

Ultrathin Stable Ohmic Contacts for High-Temperature Operation of $β$-Ga$_2$O$_3$ Devices

Beta gallium oxide ($β$-Ga$_2$O$_3$) shows significant promise in the high-temperature, high-power, and sensing electronics applications. However, long-term stable metallization layers for Ohmic contacts at high temperature present unique thermodynamic challenges. The current most common Ohmic contact design based on 20 nm of Ti has been repeatedly demonstrated to fail at even moderately elevated temperatures (300-400$^{\circ}$C) due to a combination of non-stoichiometric Ti/Ga$_2$O$_3$ interfacial reactions and kinetically favored Ti diffusion processes. Here we demonstrate stable Ohmic contacts for Ga$_2$O$_3$ devices operating up to 500-600$^{\circ}$C using ultrathin Ti layers with a self-limiting interfacial reaction. The ultrathin Ti layer in the 5nm Ti / 100nm Au contact stack is designed to fully oxidize while forming an Ohmic contact, thereby limiting both thermodynamic and kinetic instability. This novel contact design strategy results in an epitaxial conductive anatase titanium oxide interface layer that enables low-resistance Ohmic contacts that are stable both under long-term continuous operation (>500 hours) at 600$^{\circ}$C in vacuum ($\leq$ 10$^{-4}$ Torr), as well as after repeated thermal cycling (15 times) between room temperature and 550$^{\circ}$C in flowing N$_2$. This stable Ohmic contact design will accelerate the development of high-temperature devices by enabling research focus to shift towards rectifying contacts and other interfacial layers.

physics.app-ph↗

arXiv2021

Coupled Charge and Radiation Transport Processes in Thermophotovoltaic and Thermoradiative Cells

Accurate modeling of charge transport and both thermal and luminescent radiation is crucial to the understanding and design of radiative thermal energy converters. Charge carrier dynamics in semiconductors are well-described by the Poisson-drift-diffusion equations, and thermal radiation in emitter/absorber structures can be computed using multilayer fluctuational electrodynamics. These two types of energy flows interact through radiation absorption/luminescence and charge carrier generation/recombination. However, past research has typically only assumed limited interaction, with thermal radiation absorption as an input for charge carrier models to predict device performance. To examine this assumption, we develop a fully-coupled iterative model of charge and radiation transport in semiconductor devices, and we use our model to analyze near-field and far-field GaSb thermophotovoltaic and thermoradiative systems. By comparing our results to past methods that do not consider cross-influences between charge and radiation transport, we find that a fully-coupled approach is necessary to accurately model photon recycling and near-field enhancement of external luminescence. Because these effects can substantially alter device performance, our modeling approach can aid in the design of efficient thermophotovoltaic and thermoradiative systems.

cond-mat.mes-hall↗

arXiv2020

Solar Thermoradiative-Photovoltaic Energy Conversion

We propose a solar thermal energy conversion system consisting of a solar absorber, a thermoradiative cell or negative illumination photodiode, and a photovoltaic cell. Because it is a heat engine, this system can also be paired with thermal storage to provide reliable electricity generation. Heat from the solar absorber drives radiative recombination current in the thermoradiative cell, and its emitted light is absorbed by the photovoltaic cell to provide an additional photocurrent. Based on the principle of detailed balance, we calculate a limiting solar conversion efficiency of 85% for fully concentrated sunlight and 45% for one sun with an absorber and single-junction cells of equal areas. Ideal and nonideal solar thermoradiative-photovoltaic systems outperform solar thermophotovoltaic converters for low bandgaps and practical absorber temperatures. Their performance enhancement results from a high tolerance to nonradiative generation/recombination and an ability to minimize radiative heat losses. We show that a realistic device with all major losses could achieve increases in solar conversion efficiency by up to 7.9% (absolute) compared to a solar thermophotovoltaic device under low optical concentration. Our results indicate that these converters could serve as efficient heat engines for low cost single axis tracking systems.

physics.app-ph↗