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Alloys between Ga2O3 and Al2O3 (AGO) present a rich material space exhibiting numerous structural phases with unique optoelectronic properties that make them attractive candidates as ultra-wide bandgap (UWBG) semiconductors for next-generation power devices. Here we review the properties of AGO, focusing on theoretical results on the thermodynamics of Al incorporation and its consequences on the electronic structure. We review predictions and progress in experimentally realizing these alloys, as well as how composition influences important optoelectronic variables such as the band gap, band offsets, transport properties, and n-type dopability. A number of these parameters, such as the breakdown field (related to the band gap) and electron mobility, are discussed in assessing AGO in terms of relevant power device figures of merit. Overall, the rapid progress and predicted properties highlight the promise of AGO as a model UWBG semiconductor platform with the potential to revolutionize power devices.

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. Here, we studied the role of imidazolium-based ionomers for electrocatalytic CO2 reduction to CO (CO2R) on Ag surfaces and found that they produce no effect on CO2R activity yet strongly promote the competing hydrogen evolution reaction (HER). By examining the dependence of HER and CO2R rates on concentrations of CO2 and HCO3-, we developed a kinetic model that attributes HER promotion to intrinsic promotion of HCO3- reduction by imidazolium ionomers. We also show that varying the ionomer structure by changing substituents on the imidazolium ring modulates the HER promotion. This ionomer-structure dependence was analyzed via Taft steric parameters and density functional theory calculations, which suggest that steric bulk from functionalities on the imidazolium ring reduces access of the ionomer to both HCO3- and the Ag surface, thus limiting the promotional effect. Our results help develop design rules for ionomer-catalyst interactions in CO2R and motivate further work into precisely uncovering the interplay between primary and secondary coordination in determining electrocatalytic behavior.

Advanced materials 34(37), 2204217 (2022). doi:10.1002/adma.202204217, Ga$_2$O$_3$ and its polymorphs are attracting increasing attention. The rich structural space of polymorphic oxide systems such as Ga$_2$O$_3$ offers potential for electronic structure engineering, which is of particular interest for a range of applications, such as power electronics. $γ$-Ga$_2$O$_3$ presents a particular challenge across synthesis, characterization, and theory due to its inherent disorder and resulting complex structure–electronic-structure relationship. Here, density functional theory is used in combination with a machine-learning approach to screen nearly one million potential structures, thereby developing a robust atomistic model of the $γ$-phase. Theoretical results are compared with surface and bulk sensitive soft and hard X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, spectroscopic ellipsometry, and photoluminescence excitation spectroscopy experiments representative of the occupied and unoccupied states of $γ$-Ga$_2$O$_3$. The first onset of strong absorption at room temperature is found at 5.1 eV from spectroscopic ellipsometry, which agrees well with the excitation maximum at 5.17 eV obtained by photoluminescence excitation spectroscopy, where the latter shifts to 5.33 eV at 5 K. This work presents a leap forward in the treatment of complex, disordered oxides and is a crucial step toward exploring how their electronic structure can be understood in terms of local coordination and overall structure., Published by Wiley-VCH, Weinheim

Ga

We construct a family of beryllium (Be) multiphase equation of state (EOS) models that consists of a baseline ("optimal") EOS and variations on the baseline to account for physics-based uncertainties. The Be baseline EOS is constructed to reproduce a set of self-consistent data and theory including known phase boundaries, the principal Hugoniot, isobars, and isotherms from diamond-anvil cell experiments. Three phases are considered, including the known hexagonal closed-packed (hcp) phase, the liquid, and the theoretically predicted high-pressure body-centered cubic (bcc) phase. Since both the high-temperature liquid and high-pressure bcc phases lack any experimental data, we carry out ab initio density functional theory (DFT) calculations to obtain new information about the EOS properties for these two regions. At extremely high temperature conditions (>87 eV), DFT-based quantum molecular dynamics simulations are performed for multiple liquid densities using the state-of-the-art Spectral Quadrature methodology in order to validate our selected models for the ion- and electron-thermal free energies of the liquid. We have also performed DFT simulations of hcp and bcc with different exchange-correlation functionals to examine their impact on bcc compressibility, which bound the hcp-bcc transition pressure to within 4 ± 0.5 Mbar. Our baseline EOS predicts the first density maximum along the Hugoniot to be 4.4-fold in compression, while the hcp-bcc-liquid triple-point pressure is predicted to be at 2.25 Mbar. In addition to the baseline EOS, we have generated eight variations to accommodate multiple sources of potential uncertainties such as (1) the choice of free-energy models, (2) differences in theoretical treatments, (3) experimental uncertainties, and (4) lack of information. These variations are designed to provide a reasonable representation of nonstatistical uncertainties for the Be EOS and may be used to assess its sensitivity to different inertial-confinement fusion capsule designs.

We report on the electrical properties of 2.0 eV bandgap (EG) CuInGaS2 (CIGS) solar absorbers integrated on SnO2:F (FTO) substrates and interfaced with CdS buffer layers for multijunction solar cells and photoelectrochemical water splitting devices. The averaged short-circuit photocurrent density measured on nine ITO/ZnO/CdS/CIGS/FTO cells was 10.0 mA cm−2, a value corresponding to 70% of the optical limit for a 2.0 eV-bandgap absorber. However, the averaged power conversion efficiency was low (avg.: 2.4%) and for the most part limited by modest open circuit voltage values (avg.: 587 mV). Solid-state analyses performed at low temperatures revealed poor energetic alignment at the CdS/CIGS top interface. An activation energy (1.1 eV) for the dominant recombination mechanism significantly lower than the CIGS bandgap was measured, implying that recombination takes place near the CdS/CIGS interface. This finding is supported by the large difference found between the quasi Fermi level splitting of the bare absorber (1.17 eV) and the open circuit voltage of the device. Complementary theoretical calculations identified Fermi level pinning as a possible cause for the poor interface energetics through Cd incorporation on both the Cu and the group-III sites, resulting in a large conduction band offset (∼0.9 eV) at the CdS/CIGS interface. This work underlines the need for new EG-tunable buffers coupled with optimized CIGS surface energetics (e.g. ordered vacancy compounds) for future chalcopyrite-based multijunction solar cells and photoelectrochemical water splitting devices.

Formate is an important value-added chemical that can be produced via electrochemical CO2 reduction reactions (CO2RR). Cu2O-based catalysts have previously demonstrated decent activity for formate ...

Engineering the electrolyte microenvironment represents an attractive route to tuning the selectivity of electrocatalytic reactions beyond catalyst composition and morphology. However, harnessing t...

Tuning the surface structure of the photoelectrode provides one of the most effective ways to address the critical challenges in artificial photosynthesis, such as efficiency, stability, and product selectivity, for which gallium nitride (GaN) nanowires have shown great promise. In the GaN wurtzite crystal structure, polar, semipolar, and nonpolar planes coexist and exhibit very different structural, electronic, and chemical properties. Here, through a comprehensive study of the photoelectrochemical performance of GaN photocathodes in the form of films and nanowires with controlled surface polarities we show that significant photoelectrochemical activity can be observed when the nonpolar surfaces are exposed in the electrolyte, whereas little or no activity is measured from the GaN polar

Superionic solid electrolytes have widespread use in energy devices, but the fundamental motivations for fast ion conduction are often elusive. In this Perspective, we draw upon atomistic simulations of a wide range of superionic conductors to illustrate some ways frustration can lower diffusion cation barriers in solids. Based on our studies of halides, oxides, sulfides and hydroborates and a survey of published reports, we classify three types of frustration that create competition between different local atomic preferences, thereby flattening the diffusive energy landscape. These include chemical frustration, which derives from competing factors in the anion–cation interaction; structural frustration, which arises from lattice arrangements that induce site distortion or prevent cation ordering; and dynamical frustration, which is associated with temporary fluctuations in the energy landscape due to anion reorientation or cation reconfiguration. For each class of frustration, we provide detailed simulation analyses of various materials to show how ion mobility is facilitated, resulting in stabilizing factors that are both entropic and enthalpic in origin. We propose the use of these categories as a general construct for classifying frustration in superionic conductors and discuss implications for future development of suitable descriptors and improvement strategies. This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO

Bridging polymer design with catalyst surface science is a promising direction for tuning and optimizing electrochemical reactors that could impact long-term goals in energy and sustainability. Particularly, the interaction between inorganic catalyst surfaces and organic-based ionomers provides an avenue to both steer reaction selectivity and promote activity. Here, we studied the role of imidazolium-based ionomers for electrocatalytic CO

Whole-chalcopyrite-based tandem devices for photoelectrochemical (PEC) water splitting have emerged as a promising route for obtaining ∼20% solar-to-hydrogen efficiencies. Here we pursue this appro...

We report ultra-high responsivity of epitaxial [Formula: see text] (TGO) Schottky UV-C photodetectors and experimentally identified the source of gain as deep-level defects, supported by first principles calculations. Epitaxial TGO films were grown by plasma-assisted molecular beam epitaxy on (−201) oriented n-type β-[Formula: see text] substrates. Fabricated vertical Schottky devices exhibited peak responsivities as high as 3.5 [Formula: see text] A/W at −5 V applied bias under 250 nm illumination with sharp cutoff shorter than 280 nm and fast rise/fall time in milliseconds order. Hyperspectral imaging cathodoluminescence (CL) spectra were examined to find the mid-bandgap defects, the source of this high gain. Irrespective of different tin mole fractions, the TGO epilayer exhibited extra CL peaks at the green band (∼2.20 eV) not seen in β-[Formula: see text] along with enhancement of the blue emission-band (∼2.64 eV) and suppression of the UV emission-band. Based on hybrid functional calculations of the optical emission expected for defects involving Sn in β-[Formula: see text], VGa–Sn complexes are proposed as potential defect origins of the observed green and blue emission-bands. Such complexes behave as acceptors that can efficiently trap photogenerated holes and are predicted to be predominantly responsible for the ultra-high photoconductive gain in the Sn-alloyed [Formula: see text] devices by means of thermionic emission and electron tunneling. Regenerating the VGa–Sn defect complexes by optimizing the growth techniques, we have demonstrated a planar Schottky UV-C photodetector of the highest peak responsivity.

The efficiency of state-of-the-art $\mathrm{Cd}\mathrm{Te}$ solar cells remains limited by the relatively low open-circuit voltage (${V}_{OC}$). Improving the front interface is key towards realizing a higher ${V}_{OC}$ after achieving the necessary bulk carrier density and lifetime. Recent efforts in identifying buffer layers beyond $\mathrm{Cd}\mathrm{S}$ have focused on ${\mathrm{Mg}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}\mathrm{O}$, which offers tunability of the band offsets, but often suffers from high interfacial defect densities. ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$-based buffer layers demonstrate tremendous improvements in interfacial defect passivation in crystalline silicon and dye-sensitized solar cells, leading to record high ${V}_{OC}$, yet remain largely unexplored in $\mathrm{Cd}\mathrm{Te}$-based devices. Here, we perform hybrid density-functional-theory calculations to investigate pure ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ and ${\mathrm{In}\mathrm{Ga}\mathrm{O}}_{3}$ alloys as a window layer in $\mathrm{Cd}\mathrm{Te}$ photovoltaics. We report calculated band offsets for several pairs of solid-solid interfaces comprising transparent conducting oxide (TCO) and $\mathrm{Cd}\mathrm{Te}$ heterojunctions. The results support a large conduction band offset spike of 0.67 eV for the $\mathrm{Cd}\mathrm{Te}/{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ (100) interface, while the offset is reduced to 0.18 eV for the ${\mathrm{In}\mathrm{Ga}\mathrm{O}}_{3}$ alloy and matches closely with the preferred optimum value of 0.2 eV. Device-level modeling tests of $\mathrm{Cd}\mathrm{Te}$ solar cells integrating our results indicate that the highest efficiency is achieved with ${\mathrm{In}\mathrm{Ga}\mathrm{O}}_{3}$ acting both as a buffer layer and TCO. Our results suggest that alloys of ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ and ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ may be attractive alternatives to ${\mathrm{Mg}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}\mathrm{O}$ for tailoring optimal conduction-band offsets of the buffer and TCO layers in high-efficiency $\mathrm{Cd}\mathrm{Te}$ thin-film solar cells.

Gallium oxide has emerged as a promising ultrawide-bandgap semiconductor for electronic applications. Part of the attraction of Ga2O3 is its ability to be alloyed with other materials (such as Al2O3) for band-gap engineering or doped with other elements (such as silicon) for modifying its electrical conductivity. But what is still unknown is how these alloying capabilities extend into the orthorhombic phases, or how well the ultrawide-bandgap AlGO alloys can be n-type doped. Here hybrid density functional theory calculations are used to determine the electronic structure of AlGO alloys. Conduction-band offsets of AlGO alloys in the orthorhombic phase are calculated, as are donor ionization energies as a function of Al content. In light of these results, we discuss band engineering and doping strategies in AlGO alloys for electronic device applications.

The combination of an ultrawide band gap and controllable $n$-type conductivity makes monoclinic gallium sesquioxide a promising material for high-power electronics. However, this technological development will require accurate knowledge about the identity and properties of prominent deep-level defects in the material. This work explores close-associate Ga-O divacancies. Owing to the low symmetry of the crystal structure, divacancies can potentially occur in a plethora of crystallographically inequivalent configurations. Hybrid functional calculations were performed to shed light on the relative stability of different divacancy configurations, the energy barriers for transformation between them, and trends in their electrical properties.

The electronic and optical properties of (InxGa1–x)2O3 alloys are highly tunable, giving rise to a myriad of applications including transparent conductors, transparent electronics, and solar-blind ...

We report a systematic first-principles study on positron annihilation parameters in the $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ lattice and Ga monovacancy defects complemented with orientation-dependent experiments of the Doppler broadening of the positron-electron annihilation. We find that both the $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ lattice and the considered defects exhibit unusually strong anisotropy in their Doppler broadening signals. This anisotropy is associated with low symmetry of the $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ crystal structure that leads to unusual kind of one-dimensional confinement of positrons even in the delocalized state in the lattice. In particular, the split Ga vacancies recently observed by scanning transmission electron microscopy produce unusually anisotropic positron annihilation signals. We show that in experiments, the positron annihilation signals in $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}$ samples seem to be often dominated by split Ga vacancies.

The search for new wide band gap materials is intensifying to satisfy the need for more advanced and energy efficient power electronic devices. Ga$_2$O$_3$ has emerged as an alternative to SiC and GaN, sparking a renewed interest in its fundamental properties beyond the main $\beta$-phase. Here, three polymorphs of Ga$_2$O$_3$, $\alpha$, $\beta$ and $\varepsilon$, are investigated using X-ray diffraction, X-ray photoelectron and absorption spectroscopy, and ab initio theoretical approaches to gain insights into their structure - electronic structure relationships. Valence and conduction electronic structure as well as semi-core and core states are probed, providing a complete picture of the influence of local coordination environments on the electronic structure. State-of-the-art electronic structure theory, including all-electron density functional theory and many-body perturbation theory, provide detailed understanding of the spectroscopic results. The calculated spectra provide very accurate descriptions of all experimental spectra and additionally illuminate the origin of observed spectral features. This work provides a strong basis for the exploration of the Ga$_2$O$_3$ polymorphs as materials at the heart of future electronic device generations., Comment: Updated manuscript version after peer review

Engineering the electrolyte microenvironment represents an attractive route to tuning the selectivity of electrocatalytic reactions beyond catalyst composition and morphology. However, harnessing the full potential of this approach requires understanding the interplay between voltage, electrolyte composition, and adsorbate binding within the electrical double layer, which is absent from the usual theoretical approaches. In this work, we apply a recently developed density functional theory (DFT)-continuum approach based on the effective screening medium method and reference interaction site model (ESM-RISM) to explore electrolyte effects with an enhanced description of the electrochemical interface. Applying this method to the binding of CO adsorbates in potassium-containing electrolytes on copper, a problem of direct relevance to CO

Boron phosphide has recently been identified as a potential high-hole-mobility transparent conducting material. This promise arises from its low hole effective masses. However, boron phosphide has a relatively small, 2 eV, indirect bandgap which will affect its transparency. In this work, we computationally study both optical absorption across the indirect gap and phonon-limited electronic transport to quantify the potential of boron phosphide as a $p$-type transparent conductor. We find that phonon-mediated indirect optical absorption is weak in the visible spectrum and that the phonon-limited hole mobility is very high (around 900 ${\mathrm{cm}}^{2}$/Vs) at room temperature. This exceptional mobility comes from the combination of a low hole effective mass and very weak scattering by polar phonon modes. We rationalize the weak scattering by the less ionic bonding in boron phosphide compared to oxides. We suggest that this could be a general advantage of nonoxides for $p$-type transparent conducting applications. Using our computed properties, we assess the transparent conductor figure of merit of boron phosphide and show that it exceeds by one order of magnitude that of established $p$-type transparent conductors, confirming the potential of this material.

Author(s): He, X; Ercius, P; Varley, J; Bailey, J; Zapalac, G; Nagle, T; Poplavskyy, D; Mackie, N; Bayman, A; Lordi, V; Rockett, A | Abstract: Elemental intermixing at the CdS/CuIn 1−x Ga x Se 2 (CIGS) heterojunction in thin-film photovoltaic devices plays a crucial role in carrier separation and thus device efficiency. Using scanning transmission electron microcopy in combination with energy dispersive X-ray mapping, we find that by controlling the oxygen in the sputtering gas during physical vapor deposition (PVD) of the CdS, we can tailor the degree of elemental intermixing. More oxygen suppresses Cu migration from the CIGS into the CdS, while facilitating Zn doping in the CdS from the ZnO transparent contact. Very high oxygen levels induce nanocrystallinity in the CdS, while moderate or no oxygen content can promote complete CdS epitaxy on the CIGS grains. Regions of cubic Cu 2 S phase were observed in the Cu-rich CdCuS when no oxygen is included in the CdS deposition process. In the process-of-record sample (moderate O 2 ) that exhibits the highest solar conversion efficiency, we observe a ~26-nm-thick Cu-deficient CIGS surface counter-doped with the highest Cd concentration among all of the samples. Cd movement into the CIGS was found to be less than 10nnm deep for samples with either high or zero O 2 . The results are consistent with the expectation that Cd doping of the CIGS surface and lack of Zn diffusion into the buffer both enhance device performance.

We report polarization dependent photoluminescence studies on unintentionally-, Mg-, and Ca-doped β-Ga2O3 bulk crystals grown by the Czochralski method. In particular, we observe a wavelength shift of the highest-energy UV emission which is dependent on the pump photon energy and polarization. For 240 nm (5.17 eV) excitation almost no shift of the UV emission is observed between E||b and E||c, while a shift of the UV emission centroid is clearly observed for 266 nm (4.66 eV), a photon energy lying between the band absorption onsets for the two polarizations. These results are consistent with UV emission originating from transitions between conduction band electrons and two differentially-populated self-trapped hole (STH) states. Calcuations based on hybrid and self-interaction-corrected density functional theories further validate that the polarization dependence is consistent with the relative stability of two STHs. This observation implies that the STHs form primarily at the oxygen atoms involved in the original photon absorption event, thus providing the connection between incident polarization and emission wavelength. The data imposes a lower bound on the energy separation between the self-trapped hole states of ~70–160 meV, which is supported by the calculations.

Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO2 (eCO2R); yet further improvements are required for their wide-scale deployment in carbon mitigation efforts. Here, we systematically investigate a family of dilute Cu-based alloys to explore their viability as active and selective catalysts for eCO2R through a combined theoretical–experimental approach. Using a quantum–classical modeling approach that accounts for dynamic solvation effects, we assess the stability and activity of model single-atom catalysts under eCO2R conditions. Our calculations identify that the presence of eCO2R intermediates, such as CO*, H*, and OH*, may dynamically influence the local catalyst surface composition. Additionally, we identify through binding energy descriptors of the CO*, CHO*, and OCCO* dimer intermediates that certain elements, such as group 13 elements (B, Al, and Ga), enhance the selectivity of C2+ species relative to pure Cu by facilitating CO dimerization. The theoretical work is corroborated by preliminary testing of eCO2R activity and selectivity of candidate dilute Cu-based alloy catalyst films prepared by electron beam evaporation in a zero-gap gas diffusion electrode-based reactor. Of all studied alloys, dilute CuAl was found to be the most active and selective toward C2+ products like ethylene, consistent with the theoretical predictions. We attribute the improved performance of dilute CuAl alloys to more favorable dimerization reaction energetics of bound CO species relative to that on pure Cu. In a broader context, the results presented here demonstrate the power of our simulation framework in terms of rational catalyst design.